WO2025217387A1 - Silk coating of musical instruments and musical instrument components and accessories - Google Patents

Silk coating of musical instruments and musical instrument components and accessories

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Publication number
WO2025217387A1
WO2025217387A1 PCT/US2025/024042 US2025024042W WO2025217387A1 WO 2025217387 A1 WO2025217387 A1 WO 2025217387A1 US 2025024042 W US2025024042 W US 2025024042W WO 2025217387 A1 WO2025217387 A1 WO 2025217387A1
Authority
WO
WIPO (PCT)
Prior art keywords
bow
silk
silk fibroin
coated
hair
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/US2025/024042
Other languages
French (fr)
Inventor
Fiorenzo G. Omenetto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tufts University
Original Assignee
Tufts University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tufts University filed Critical Tufts University
Publication of WO2025217387A1 publication Critical patent/WO2025217387A1/en
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D189/00Coating compositions based on proteins; Coating compositions based on derivatives thereof
    • GPHYSICS
    • G10MUSICAL INSTRUMENTS; ACOUSTICS
    • G10DSTRINGED MUSICAL INSTRUMENTS; WIND MUSICAL INSTRUMENTS; ACCORDIONS OR CONCERTINAS; PERCUSSION MUSICAL INSTRUMENTS; AEOLIAN HARPS; SINGING-FLAME MUSICAL INSTRUMENTS; MUSICAL INSTRUMENTS NOT OTHERWISE PROVIDED FOR
    • G10D1/00General design of stringed musical instruments
    • G10D1/04Plucked or strummed string instruments, e.g. harps or lyres
    • G10D1/05Plucked or strummed string instruments, e.g. harps or lyres with fret boards or fingerboards
    • G10D1/08Guitars
    • GPHYSICS
    • G10MUSICAL INSTRUMENTS; ACOUSTICS
    • G10DSTRINGED MUSICAL INSTRUMENTS; WIND MUSICAL INSTRUMENTS; ACCORDIONS OR CONCERTINAS; PERCUSSION MUSICAL INSTRUMENTS; AEOLIAN HARPS; SINGING-FLAME MUSICAL INSTRUMENTS; MUSICAL INSTRUMENTS NOT OTHERWISE PROVIDED FOR
    • G10D3/00Details of, or accessories for, stringed musical instruments, e.g. slide-bars
    • G10D3/22Material for manufacturing stringed musical instruments; Treatment of the material

Definitions

  • the disclosure herein relates to a stringed instrument having at least one of a nut, peg, bridge, saddle, string post, tuner, machine head, tuning key, fret, fretboard, fingerboard, guitar slide, or capstan located on at least one of a neck or a headstock for engaging a string to adjust pitch, the at least one of a nut, peg, bridge, saddle, string post, tuner, machine head, tuning key, fret, fretboard, fingerboard, guitar slide, or capstan including a silk fibroin coating of at least a portion of the at least one of a nut, peg, bridge, saddle, string post, tuner, machine head, tuning key, guitar slide, or capstan.
  • the disclosure herein relates to a string picking implement (e.g., a guitar pick/plectrum) for a stringed musical instrument (e.g., a guitar), the string picking implement including: a pick body having a tip adapted for audibly engaging strings of the stringed musical instrument, and the strings configured to vibrate in response to the audibly engaging; and a silk fibroin coating of at least a portion of the pick body.
  • a string picking implement e.g., a guitar pick/plectrum
  • a stringed musical instrument e.g., a guitar
  • the string picking implement including: a pick body having a tip adapted for audibly engaging strings of the stringed musical instrument, and the strings configured to vibrate in response to the audibly engaging; and a silk fibroin coating of at least a portion of the pick body.
  • the disclosure herein relates to a bow for a stringed musical instrument (e.g., a violin, a viola, a cello, a contrabass, etc.), the bow including: a stick; a frog; bow hair adapted for audibly engaging strings of the musical instrument and configured to vibrate in response to the audibly engaging; and a silk fibroin coating of at least a portion of the bow hair.
  • a stringed musical instrument e.g., a violin, a viola, a cello, a contrabass, etc.
  • the bow including: a stick; a frog; bow hair adapted for audibly engaging strings of the musical instrument and configured to vibrate in response to the audibly engaging; and a silk fibroin coating of at least a portion of the bow hair.
  • the disclosure herein relates to a silk-coated bow for a stringed musical instrument, the silk-coated bow including: a stick; a frog; natural animal bow hair adapted for audibly engaging strings of the musical instrument and configured to vibrate in response to the audibly engaging; and a silk fibroin coating of the natural animal bow hair to form a silk-coated bow hair, wherein the natural animal bow hair possesses at least one bow hair characteristic that is inferior to a corresponding bow hair characteristic of the silk-coated bow hair.
  • the disclosure herein relates to a bow for stringed musical instruments, the bow including: a stick; a frog; and bow hair adapted for audibly engaging strings of the musical instrument and configured to vibrate in response to the audibly engaging; wherein at least a portion of the bow hair is impregnated with a silk fibroin.
  • the disclosure herein relates to a method, including: applying a regenerated silk fibroin solution to bow hair for a bow for a string musical instrument on at least a portion of the bow hair; and drying the regenerated silk fibroin solution on the bow hair to form a silk fibroin coating.
  • the disclosure herein relates to a method, including: contacting at least a portion of bow hair for a bow for a stringed musical instrument with a regenerated silk fibroin solution, wherein contacting delivers the regenerated silk fibroin solution into the portion of bow hair; and drying the regenerated silk fibroin solution to impregnate the portion of bow hair with an impregnated silk fibroin.
  • the disclosure herein relates to a method of augmenting a musical instrument having a resonating portion with at least one natural frequency, the method including: applying uncured silk fibroin to the resonating portion; and while maintaining application of an acoustic frequency to the resonating portion, curing the uncured silk fibroin to form a silk fibroin modified portion.
  • the term “a” may be understood to mean “at least one”; (ii) the term “or” may be understood to mean “and/or”; (iii) the terms “comprising” and “including” may be understood to encompass itemized components or steps whether presented by themselves or together with one or more additional components or steps; and (iv) the terms “about” and “approximately” are used as equivalents and may be understood to permit standard variation as would be understood by those of ordinary skill in the art; and (v) where ranges are provided, endpoints are included.
  • composition as used herein, may be used to refer to a discrete physical entity that comprises one or more specified components.
  • a composition may be of any form - e.g., gas, gel, liquid, solid, etc.
  • composition may refer to a combination of two or more entities for use in a single embodiment or as part of the same article.
  • the combination of entities result in physical admixture, that is, combination as separate co-entities of each of the components of the composition is possible; however many practitioners in the field may find it advantageous to prepare a composition that is an admixture of two or more of the ingredients in a pharmaceutically acceptable carrier, diluent, or excipient, making it possible to administer the component ingredients of the combination at the same time.
  • the term “substantially” refers to the qualitative condition of exhibiting total or near-total extent or degree of a characteristic or property of interest.
  • One of ordinary skill in the biological arts will understand that biological and chemical phenomena rarely, if ever, go to completion and/or proceed to completeness or achieve or avoid an absolute result.
  • the term “substantially” is therefore used herein to capture the potential lack of completeness inherent in many biological and chemical phenomena.
  • silk fibroin refers to silk fibroin protein whether produced by silkworm, spider, or other insect, or otherwise generated (Lucas et al., Adv. Protein Chem., 13: 107-242 (1958)). Any type of silk fibroin can be used in different embodiments described herein.
  • Silk fibroin produced by silkworms such as Bombyx inori, is the most common and represents an earth-friendly, renewable resource.
  • silk fibroin used in a silk film may be attained by extracting sericin from the cocoons of B. mori. Organic silkworm cocoons are also commercially available.
  • silks there are many different silks, however, including spider silk (e.g., obtained from Nephila clavipes), transgenic silks, genetically engineered silks, such as silks from bacteria, yeast, mammalian cells, transgenic animals, or transgenic plants, and variants thereof, that can be used. See, e.g., WO 97/08315 and U.S. Pat. No. 5,245,012, each of which is incorporated herein by reference in their entireties.
  • spider silk e.g., obtained from Nephila clavipes
  • transgenic silks e.g., obtained from Nephila clavipes
  • genetically engineered silks such as silks from bacteria, yeast, mammalian cells, transgenic animals, or transgenic plants, and variants thereof, that can be used. See, e.g., WO 97/08315 and U.S. Pat. No. 5,245,012, each of which is incorporated herein by reference in their entireties.
  • Coating and impregnating bow hair or other portions of musical instruments with a silk fibroin solution is a sustainable route to increase the durability /strength of the portions (e.g., by slowing degradation of natural products, such as natural bow hair), provide improved durability and playability, improve or alter the sound quality or vibrational behavior, or generate specific acoustic capabilities in the instruments.
  • Regenerated silk fibroin solution is disclosed throughout this specification in various embodiments and methods, and may be used for either coating, application, or impregnation of bow hair, resonating portions, or other portions of musical instruments.
  • the regenerated silk fibroin solution may be as described in International Patent Application Pubs. No. WO 2014/145002 and WO 2014/011644, both of which are incorporated by reference herein in their entirety.
  • the regenerated silk fibroin solution may include a silk fibroin concentration by weight within a range of 0.1% to 50%, or within a range of 1% to 5%.
  • the regenerated silk fibroin solution may include silk fibroin having an average molecular weight in a range between 3.5 kDa and 200 kDa.
  • the regenerated silk fibroin solution may further include at least one of a flavorant, a colorant, or a functionalizing agent.
  • the regenerated silk fibroin solution may be prepared by a process that includes boiling for a period of time within a range of 1 minute to and 120 minutes. In some embodiments, boiling may be at an atmospheric boiling pressure. In some embodiments, boiling may be at a temperature within a range of 30° C and 120° C.
  • a stringed instrument e.g., a guitar, a bass, a violin, a viola, a cello, a contrabass, etc.
  • a stringed instrument includes many different components, such as a nut, peg, bridge, saddle, string post, tuner, machine head, tuning key, fret, fretboard, fingerboard, a guitar slide, or capstan, which are located on at least one of a neck or a headstock of the stringed instrument.
  • the components engage a string to adjust pitch and any of the components can include a silk fibroin coating of at least a portion of the component.
  • any of the components of embodiments of the stringed instrument, string picking implement, bow, or silk-coated bow may include or be formed from a cane material, a natural porous material, a cane material, a natural material, a wood material, padouk, rosewood, a spruce material, a coconut material, a beech material, an oak material, a flax material, a sisal material, a Miscanthus material, a hemp material, a cellulose material, Brazilwood, sandalwood, pernambuco, or ipe.
  • the stringed instruments may be as described in U.S. Pat. No. 8,110,729, which is incorporated herein by reference in entirety for all purposes.
  • a string picking implement such as a guitar pick or plectrum, for a stringed musical instrument (e.g., a guitar) includes a pick body having a tip adapted for audibly engaging strings of the stringed musical instrument.
  • the strings are configured to vibrate in response to the audibly engaging.
  • a bow for a stringed musical instrument (e.g., a violin, a viola, a cello, a contrabass, etc.) includes a stick, a frog, bow hair adapted for audibly engaging strings of the musical instrument and configured to vibrate in response to the audibly engaging, and a silk fibroin coating of at least a portion of the bow hair.
  • the silk fibroin fills a plurality of pores of the bow hair.
  • a silk-coated bow for a stringed musical instrument includes a stick, a frog, natural animal bow hair adapted for audibly engaging strings of the musical instrument and configured to vibrate in response to the audibly engaging, and a silk fibroin coating of the natural animal bow hair to form a silk-coated bow hair.
  • the natural animal bow hair possesses at least one bow hair characteristic that is inferior to a corresponding bow hair characteristic of the silk-coated bow hair.
  • the at least one bow hair characteristic is a timbre characteristic, a resonant frequency characteristic, a dynamics characteristic, an articulation characteristic, an envelope characteristic, a springiness characteristic, a durability characteristic, a flexibility characteristic, a vibratory characteristic, a tonal characteristic, or a spectral characteristic.
  • the silk-coated bow hair has a resonant frequency that is within 10%, within 5%, within 1%, or within 0. 1% of a comparison resonant frequency of a comparison natural animal bow hair that lacks the silk fibroin coating.
  • a spectral centroid of a tone played on the silk-coated bow hair is at least 1%, at least 2%, at least 5%, or at least 10% higher than a comparison spectral centroid of the tone played on a comparison natural animal bow hair that lacks the silk fibroin coating.
  • the silk-coated bow hair has a timbre that is within 10%, within 5%, within 1%, or within 0. 1 % of a comparison timbre of a comparison natural animal bow hair that lacks the silk fibroin coating.
  • the silk-coated bow hair has a springiness that is within 10%, within 5%, within 1%, or within 0.1% of a comparison springiness of a comparison natural animal bow hair that lacks the silk fibroin coating.
  • the silk-coated bow hair is playable for at least three times, at least twice, at least 1.75 times, at least 1.5 times, or at least 1.25 times as many hours as a comparison natural animal bow hair that lacks the silk fibroin coating.
  • the silk-coated bow hair exhibits playability at a defined timbre for at least three times, at least twice, at least 1.75 times, at least 1.5 times, or at least 1.25 times as many hours as a comparison natural animal bow hair that lacks the silk fibroin coating.
  • the silk- coated bow hair comprises at least one of increased durability, resistance to changes with humidity /moisture, increased lifespan, reduced degradation, improved sound quality, improved responsiveness, or improved playing characteristics.
  • the silk fibroin fills a plurality of pores of the bow hair.
  • a bow for stringed musical instruments includes a stick, a frog, and bow hair adapted for audibly engaging strings of the musical instrument and configured to vibrate in response to the audibly engaging, wherein at least a portion of the bow hair is impregnated with a silk fibroin.
  • the silk fibroin fills a plurality of pores of the bow hair.
  • a method includes applying a regenerated silk fibroin solution to bow hair for a bow for a string musical instrument on at least a portion of the bow hair, and drying the regenerated silk fibroin solution on the bow hair to form a silk fibroin coating.
  • a method includes contacting at least a portion of bow hair for a bow for a stringed musical instrument with a regenerated silk fibroin solution, wherein contacting delivers the regenerated silk fibroin solution into the portion of bow hair, and drying the regenerated silk fibroin solution to impregnate the portion of bow hair with an impregnated silk fibroin.
  • Drying can be overnight, at least 4 hours, at least 8 hours, at least 12 hours, at least 18 hours, or at least 24 hours. Drying can proceed at a pressure of at most 15 psi, at most 14 psi, at most 13 psi, at most 12 psi, or at atmospheric pressure. Applying includes at least one of dipping, spraying, wiping, smearing, permeating, infiltrating, or spreading at least one of a surface, an edge, or a tip of the bow hair. The silk fibroin fills a plurality of pores of the bow hair.
  • a method of augmenting a musical instrument having a resonating portion with at least one natural frequency includes applying uncured silk fibroin, or other version of silk fibroin that is capable of permeating a material, to the resonating portion, and while maintaining application of an acoustic frequency to the resonating portion, curing the uncured silk fibroin to form a silk fibroin modified portion. Resonance will be throughout the material, so silk fibroin that permeates the resonating portion will also follow the waveform.
  • the uncured silk fibroin is applied to the resonating portion in a way that the uncured silk fibroin maps onto a shape of the resonant frequency propagating in the resonant portion.
  • the resonating portion includes a portion of the body of a stringed instrument. In some cases, the resonating portion includes the strings of a stringed instrument. In some cases, the resonating portion includes the rigid portion of a stringed instrument bow. In some cases, the resonating portion includes the body of a woodwind instrument. In some cases, the resonating portion is a part of a percussion instrument. In some cases, the resonating portion is a portion of a mouthpiece.
  • the resonating portion of the musical instrument can be composed of a natural material, such as wood.
  • the resonating portion is composed of one of the materials disclosed above with respect to stringed instruments.
  • the resonating portion is composed of wood, such as mahogany, maple, rosewood, koa, spruce, walnut, alder, basswood, ebony, cocobolo, asapele, Brazilian rosewood, cherry, Dalbergia melanoxylon, Engelmann spruce, Malaysian Blackwood, Sitka spruce, ash, cedar, acacia, padouk, yew, Douglas-fir, or the like.
  • the resonating portion can be composed of tonewood. Without wishing to be bound by any particular theory, it is believed that these materials can be altered to produce new tonal capabilities.
  • the acoustic frequency may be selected in response to or to modify at least one of an overtone, a sustain, a timbre, a durability, a responsiveness, a strength, or an attack of the resonating portion.
  • the acoustic frequency is a resonant frequency of the resonating portion, In some cases, the acoustic frequency is a harmonic of a resonant frequency of the resonating portion.
  • the acoustic frequency is an integer multiple of the resonant frequency or a harmonic of the resonant frequency. In some cases, the acoustic frequency is particularly selected to have a mismatch with a natural resonance of the resonating portion. In some cases, the acoustic frequency is non-harmonic with the resonant frequency.
  • the applying and curing can be a multiple step process, with multiple alternating application and curing steps. In these cases, the resonant frequency of the resonating portion can change after a particular application, such that applying a resonant frequency to the resonating portion requires application of a different frequency than a previous iteration. In other words, in a multiple step process, the resonant frequency can change over time and the method can be adjusted to either maintain the applied frequency or correspondingly change the resonant frequency over time.
  • multiple frequencies can be simultaneously applied.
  • the multiple frequencies include a resonant frequency and one or more harmonic frequencies.
  • the silk fibroin modified portion has a density that is at least three times, at least twice, at least 1.75 times, at least 1.5 times, or at least 1.25 times the density of a comparison resonating portion that lacks the silk fibroin modification.
  • the silk fibroin modified portion has a strength that is at least three times, at least twice, at least 1.75 times, at least 1.5 times, or at least 1.25 times the strength of a comparison resonating portion that lacks the silk fibroin modification.
  • the silk fibroin modified portion has a timbre that is at least three times, at least twice, at least 1.75 times, at least 1.5 times, or at least 1.25 times the timbre of a comparison resonating portion that lacks the silk fibroin modification.
  • the silk fibroin modified portion has a responsiveness that is at least three times, at least twice, at least 1.75 times, at least 1.5 times, or at least 1.25 times the responsiveness of a comparison resonating portion that lacks the silk fibroin modification.
  • the silk fibroin modified portion has a durability that is at least three times, at least twice, at least 1.75 times, at least 1.5 times, or at least 1.25 times the durability of a comparison resonating portion that lacks the silk fibroin modification.
  • Applying includes at least one of dipping, spraying, wiping, smearing, permeating, infiltrating, or spreading at least one of a surface, an edge, or a tip of the resonating portion.
  • the silk fibroin or silk fibroin coating are from a regenerated silk fibroin solution.
  • the regenerated silk fibroin solution includes a silk fibroin concentration by weight within a range of 0.1% to 50%.
  • the regenerated silk fibroin solution includes a silk fibroin concentration by weight within a range of 1 % to 5%.
  • the regenerated silk fibroin solution includes silk fibroin having an average molecular weight in a range between 3.5 kDa and 200 kDa.
  • the regenerated silk fibroin solution can further include at least one of a flavorant, a colorant, or a functionalizing agent.
  • the regenerated silk fibroin solution is prepared by a process that includes boiling for a period of time within a range of 1 minute to and 120 minutes, such as at an atmospheric boiling pressure and at a temperature within a range of 30° C and 120° C.
  • the coating may be applied at a temperature of at most 60°F, at most 65°F, at most 70°F, at most 80°F, or at most 90°F, it may be applied at atmospheric pressure, and/or it may be applied at a pressure of at most 15 psi, at most 14 psi, at most 13 psi, or at most 12 psi.
  • a variety of functionalizing agents may be used with the silk-containing embodiments described herein (e.g., silk membrane, silk composition, silk articles, silk matrix, silk foam, silk microsphere, liquid composition, whipped silk cream, silk meringue, compressed silk meringue, hot-pressed silk meringue, silk leather, silk powder, silk toner, edible silkbased films, etc.). It should be understood that the examples herein may recite one or a few silkcontaining embodiments but are applicable to any silk-containing embodiment, as applicable.
  • any application-appropriate amount of one or more functionalizing agents may be used.
  • the amount of an individual functionalizing agent may be between about 1 pg/ml and 1,000 pg/ml (e.g., between about 2 and 1,000, 5 and 1,000, 10 and 1,000, 10 and 500, 10 and 100 pg/ml).
  • the amount of an individual functionalizing agent may be at least 1 pg/ml (e.g., at least 5, 10, 15, 20 25, 50, 100, 200, 300 400, 500, 600, 700, 800, or 900 pg/ml ).
  • the amount of an individual functionalizing agent is at most 1,000 pg/ml (e.g., 900, 800, 700, 600, 500, 400, 300 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, or 5 pg/ml ).
  • the composition comprises one or more sensing agents, such as a sensing dye.
  • the sensing agents/sensing dyes are environmentally sensitive and produce a measurable response to one or more environmental factors.
  • the environmentally- sensitive agent or dye may be present in the composition in an effective amount to alter the composition from a first chemical -physical state to a second chemical -physical state in response to an environmental parameter (e.g., a change in pH, light intensity or exposure, temperature, pressure or strain, voltage, physiological parameter of a subject, and/or concentration of chemical species in the surrounding environment) or an externally applied stimulus (e.g., optical interrogation, acoustic interrogation, and/or applied heat).
  • an environmental parameter e.g., a change in pH, light intensity or exposure, temperature, pressure or strain, voltage, physiological parameter of a subject, and/or concentration of chemical species in the surrounding environment
  • an externally applied stimulus e.g., optical interrogation, acoustic interrogation, and/or applied heat.
  • the sensing dye is present to provide one optical appearance under one given set of environmental conditions and a second, different optical appearance under a different given set of environmental conditions.
  • Suitable concentrations for the sensing agents described herein can be the concentrations for the colorants and additives described elsewhere herein.
  • a person having ordinary skill in the chemical sensing arts can determine a concentration that is appropriate for use in a sensing application of the inks described herein.
  • the first and second chemical-physical state may be a physical property of the composition, such as mechanical property, a chemical property, an acoustical property, an electrical property, a magnetic property, an optical property, a thermal property, a radiological property, or an organoleptic property.
  • exemplary sensing dyes or agents include, but are not limited to, a pH sensitive agent, a thermal sensitive agent, a pressure or strain sensitive agent, a light sensitive agent, or a potentiometric agent.
  • Exemplary pH sensitive dyes or agents include, but are not limited to, cresol red, methyl violet, crystal violet, ethyl violet, malachite green, methyl green, 2-(p- dimethylaminophenylazo) pyridine, paramethyl red, metanil yellow, 4-phenylazodiphenylamine, thymol blue, metacresol purple, orange IV, 4-o-Tolylazo-o-toluindine, quinaldine red, 2,4- dinitrophenol, erythrosine disodium salt, benzopurpurine 4B, N,N-dimethyl-p-(m-tolylazo) aniline, p- dimethylaminoazobenene, 4,4’-bis(2-amino-l-naphthylazo)-2,2’-stilbenedisulfonic acid, tetrabromophenolphthalein ethyl ester, bromophenol blue, Congo red, methyl orange, ethyl orange, 4-
  • Exemplary light responsive dyes or agents include, but are not limited to, photochromic compounds or agents, such as triarylmethanes, stilbenes, azasilbenes, nitrones, fulgides, spiropyrans, napthopyrans, spiro-oxzines, quinones, derivatives and combinations thereof.
  • photochromic compounds or agents such as triarylmethanes, stilbenes, azasilbenes, nitrones, fulgides, spiropyrans, napthopyrans, spiro-oxzines, quinones, derivatives and combinations thereof.
  • Exemplary potentiometric dyes include, but are not limited to, substituted amiononaphthylehenylpridinium (ANEP) dyes, such as di-4-ANEPPS, di-8-ANEPPS, and N-(4- Sulfobutyl)-4-(6-(4-(Dibutylamino)phenyl)hexatrienyl)Pyridinium (RH237).
  • ANEP substituted amiononaphthylehenylpridinium
  • Exemplary temperature sensitive dyes or agents include, but are not limited to, thermochromic compounds or agents, such as thermochromic liquid crystals, leuco dyes, fluoran dyes, octadecylphosphonic acid.
  • Exemplary pressure or strain sensitive dyes or agents include, but are not limited to, spiropyran compounds and agents.
  • chemi-sensitive dyes or agents include, but are not limited to, antibodies such as immunoglobulin G (IgG) which may change color from blue to red in response to bacterial contamination.
  • IgG immunoglobulin G
  • the compositions comprise one or more additive, dopant, or biologically active agent suitable for a desired intended purpose.
  • the additive or dopant may be present in the composition in an amount effective to impart an optical or organoleptic property to the composition.
  • Exemplary additives or dopants that impart optical or organoleptic properties include, but are not limited to, dyes/pigments, flavorants, aroma compounds, granular or fibrous fillers.
  • the additive, dopant, or biologically active agent may be present in the composition in an amount effective to "functionalize” the composition to impart a desired mechanical property or added functionality to the composition.
  • exemplary additive, dopants, or biologically active agent that impart the desired mechanical property or added functionality include, but are not limited to: environmentally sensitive/sensing dyes; active biomolecules; conductive or metallic particles; micro and nanofibers (e.g., silk nanofibers for reinforcement, carbon nanofibers); nanotubes; inorganic particles (e.g., hydroxyapatite, tricalcium phosphate, bioglasses); drugs (e.g., antibiotics, small molecules or low molecular weight organic compounds); proteins and fragments or complexes thereof (e.g., enzymes, antigens, antibodies and antigen-binding fragments thereof);
  • DNA/RNA e.g., siRNA, miRNA, mRNA
  • cells and fractions thereof viruseses and viral particles; prokaryotic cells such as bacteria; eukaryotic cells such as mammalian cells and plant cells; fungi).
  • the additive or dopant comprises a flavoring agent or flavorant.
  • Exemplary flavorants include ester flavorants, amino acid flavorants, nucleic acid flavorants, organic acid flavorants, and inorganic acid flavorants, such as, but not limited to, diacetyl, acetylpropionyl, acetoin, isoamyl acetate, benzaldehyde, cinnamaldehyde, ethyl propionate, methyl anthranilate, limonene, ethyl decadienoate, allyl hexanoate, ethyl maltol, ethylvanillin, methyl salicylate, manzanate, glutamic acid salts, glycine salts, guanylic acids salts, inosinic acid salts, acetic acid, ascorbic acid, citric acid, fumaric acid, lactic acid, malic acid, phosphoric acid, tartaric acid, derivatives, and mixtures thereof.
  • diacetyl acetylpropion
  • the additive or dopant comprises an aroma compound.
  • aroma compounds include ester aroma compounds, terpene aroma compounds, cyclic terpenes, and aromatic aroma compounds, such as, but not limited to, geranyl acetate, methyl formate, metyl acetate, methyl propionate, methyl butyrate, ethyl acetate, ethyl butyrate, isoamyl acetate, pentyl butrate, pentyl pentanoate, octyl acetate, benzyl acetate, methyl anthranilate, myrecene, geraniol, nerol, citral, cironellal, cironellol, linalool, nerolidol, limonene, camphor, menthol, carone, terpineol, alpha-lonone, thujone, eucalyptol, benzaldehy
  • the additive or dopant comprises a colorant, such as a dye or pigment.
  • the dye or pigment imparts a color or grayscale to the composition.
  • the colorant can be different than the sensing agents and/or sensing dyes below. Any organic and/or inorganic pigments and dyes can be included in the inks.
  • Exemplary pigments suitable for use in the present disclosure include International Color Index or C.I. Pigment Black Numbers 1 , 7, 1 1 and 31 , C.I. Pigment Blue Numbers 15, 15 : 1 , 15 :2, 15 :3, 15 :4, 15 :6, 16, 27, 29, 61 and 62, C.I. Pigment Green Numbers 7, 17, 18 and 36, C.I.
  • carbon black pigment such as Regal 330, Cabot Corporation
  • quinacridone pigments Quinacridone Magenta (228-0122), available from Sun Chemical Corporation, Fort Lee, N.J.
  • diarylide yellow pigment such as AAOT Yellow (274- 1788) available from Sun
  • the classes of dyes suitable for use in present invention can be selected from acid dyes, natural dyes, direct dyes (either cationic or anionic), basic dyes, and reactive dyes.
  • the acid dyes also regarded as anionic dyes, are soluble in water and mainly insoluble in organic solvents and are selected, from yellow acid dyes, orange acid dyes, red acid dyes, violet acid dyes, blue acid dyes, green acid dyes, and black acid dyes.
  • European Patent 0745651 incorporated herein by reference, describes a number of acid dyes that are suitable for use in the present disclosure.
  • Exemplary yellow acid dyes include Acid Yellow 1 International Color Index or C.I. 10316); Acid Yellow 7 (C.I. 56295); Acid Yellow 17 (C.I.
  • Exemplary orange acid dyes include Acid Orange 1 (C.I. 13090/1); Acid Orange 10 (C.I. 16230); Acid Orange 20 (C.I. 14603); Acid Orange 76 (C.I. 18870); Acid Orange 142; Food Orange 2 (C.I. 15980); and Orange B. [0055] Exemplary red acid dyes include Acid Red 1. (C.I. 19140); Acid Yellow 29 (C.I. 18900); Acid Yellow 36 (C.I. 13065); Acid Yellow 42 (C.I. 22910); Acid Yellow 73 (C.I. 45350); Acid Yellow 99 (C.I. 13908); Acid Yellow 194; and Food Yellow 3 (C.I. 15985).
  • Exemplary orange acid dyes include Acid Orange 1 (C.I. 13090/1); Acid Orange 10 (C.I. 16230); Acid Orange 20 (C.I. 14603); Acid Orange 76 (C.I. 18870); Acid Orange 142; Food Orange 2 (C.I. 15980); and Orange B. [00
  • Acid Red 4 C.I. 14710
  • Acid Red 18 C.I. 16255
  • Acid Red 26 C.I. 16150
  • Acid Red 2.7 C.I. as Acid Red 51 (C.I. 45430, available from BASF Corporation, Mt. Olive, N.J.)
  • Acid Red 52 C.I. 45100
  • Acid Red 73 C.I. 27290
  • Acid Red 87 C. I. 45380
  • Acid Red 94 C.I. 45440
  • Acid Red 194 C.I. 14700
  • Exemplary violet acid dyes include Acid Violet 7 (C.I. 18055); and Acid Violet 49 (C.I. 42640).
  • Exemplary blue acid dyes include Acid Blue 1 (C.I.
  • Exemplary green acid dyes include Acid Green 1 (C.I. 10028); Acid Green 3 (C.I. 42085); Acid Green 5 (C.I. 42095); Acid Green 26 (C.I. 44025); and Food Green 3 (C.I. 42053).
  • Exemplary black acid dyes include Acid Black 1 (C.I. 20470); Acid Black 194 (Basantol® X80, available from BASF Corporation, an azo/1 :2 CR-complex.
  • Exemplary direct dyes for use in the present disclosure include Direct Blue 86 (C.I. 74180); Direct Blue 199; Direct Black 168; Direct Red 253; and Direct Yellow 107/132 (C.I. Not Assigned).
  • Exemplary natural dyes for use in the present disclosure include Alkanet (C.I. 75520,75530); Annafto (C.I. 75120); Carotene (C.I. 75130); Chestnut; Cochineal (C.I.75470); Cutch (C.I. 75250, 75260); Divi-Divi; Fustic (C.I. 75240); Hypemic (C.I. 75280); Logwood (C.I. 75200); Osage Orange (C.I.
  • Exemplary reactive dyes for use in the present disclosure include Reactive Yellow 37 (monoazo dye); Reactive Black 31 (disazo dye); Reactive Blue 77 (phthalo cyanine dye) and Reactive Red 180 and Reactive Red 108 dyes. Suitable also are the colorants described in The Printing Ink Manual (5th ed., Leach et al. eds. (2007), pages 289-299. Other organic and inorganic pigments and dyes and combinations thereof can be used to achieve the colors desired.
  • compositions provided herein can contain ETV fluorophores that are excited in the ETV range and emit light at a higher wavelength (typically 400 nm and above).
  • ETV fluorophores include but are not limited to materials from the coumarin, benzoxazole, rhodamine, napthalimide, perylene, benzanthrones, benzoxanthones or benzothia- xanthones families.
  • a UV fluorophore such as an optical brightener for instance
  • the amount of colorant, when present, generally is between 0.05% to 5% or between 0.1% and 1% based on the weight of the composition.
  • the amount of pigment/dye generally is present in an amount of from at or about 0.1 wt% to at or about 20 wt% based on the weight of the composition.
  • a non-white ink can include 15 wt% or less pigment/dye, or 10 wt% or less pigment/dye or 5 wt% pigment/dye, or 1 wt% pigment/dye based on the weight of the composition.
  • a non-white ink can include 1 wt% to 10 wt%, or 5 wt% to 15 wt%, or 10 wt% to 20 wt% pigment/dye based on the weight of the composition.
  • a non-white ink can contain an amount of dye/pigment that is 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15%, 16 wt%, 17 wt%, 18 wt%, 19 wt% or 20 wt% based on the weight of the composition.
  • the amount of white pigment generally is present in an amount of from at or about 1 wt% to at or about 60 wt% based on the weight of the composition. In some applications, greater than 60 wt% white pigment can be present.
  • Preferred white pigments include titanium dioxide (anatase and rutile), zinc oxide, lithopone (calcined coprecipitate of barium sulfate and zinc sulfide), zinc sulfide, blanc fixe and alumina hydrate and combinations thereof, although any of these can be combined with calcium carbonate.
  • a white ink can include 60 wt% or less white pigment, or 55 wt% or less white pigment, or 50 wt% white pigment, or 45 wt% white pigment, or 40 wt% white pigment, or 35 wt% white pigment, or 30 wt% white pigment, or 25 wt% white pigment, or 20 wt% white pigment, or 15 wt% white pigment, or 10 wt% white pigment, based on the weight of the composition.
  • a white ink can include 5 wt% to 60 wt%, or 5 wt% to 55 wt%, or 10 wt% to 50 wt%, or 10 wt% to 25 wt%, or 25 wt% to 50 wt%, or 5 wt% to 15 wt%, or 40 wt% to 60 wt% white pigment based on the weight of the composition.
  • a non-white ink can an amount of dye/pigment that is 5%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, 45%, 46 wt%
  • the additive or dopant comprises a conductive additive.
  • exemplary conductive additives include, but are not limited to graphite, graphite powder, carbon nanotubes, and metallic particles or nanoparticles, such as gold nanoparticles.
  • the conductive additive is biocompatible and non-toxic.
  • the terms “include” and “including” have the same meaning as the terms “comprise” and “comprising.”
  • the terms “comprise” and “comprising” should be interpreted as being “open” transitional terms that permit the inclusion of additional components further to those components recited in the claims.
  • the terms “consist” and “consisting of’ should be interpreted as being “closed” transitional terms that do not permit the inclusion of additional components other than the components recited in the claims.
  • the term “consisting essentially of’ should be interpreted to be partially closed and allowing the inclusion only of additional components that do not fundamentally alter the nature of the claimed subject matter.
  • Lower molecular weight silk solutions can be prepared using a method that is similar to the methods described in International Patent Application Pub. No. WO 2014/145002, which is incorporated herein in its entirety by reference.
  • Provided herein is an exemplary protocol to produce a composition of low molecular weight silk fibroin.
  • Silk fibroin solution 1) Silkworm Bombyx mori cocoons were degummed through a modified extraction process as described in Sofia S et al. (2001) Journal of Biomedical Materials Research, 54, 139-148.; 2) Cut cocoons and remove the pupae, pupae skins and any other dirt from the inside of the cocoon; 3) Degum the cocoon pieces in a ⁇ 0.02M boiling sodium carbonate (NazCCF) solution using a degumming time of about 60 minutes or more; 4) Rinse the degummed silk fibroin in water (e.g., Milli-Q water) at least thrice, for at least half an hour each time.; 5) Air dry the rinsed silk fibroin.; 6) Dissolve the silk fibroin in a 9.3 M lithium bromide solution (Sigma Aldrich, MO, USA, ReagentPlus > 99%) at 60 °C and dialyze against water (e.g., Milli-Q water), e
  • the resulting aqueous low molecular weight silk fibroin solution has a concentration between 7% wt/vol and 9% wt/vol silk fibroin. Up to this point, the silk fibroin solution is called an as- purified solution.
  • the as-purified silk fibroin solution can be further subjected to an autoclaving step, and the silk fibroin solution is then called an autoclaved solution. Store the silk fibroin solution at 4 °C.
  • a total boil time of 60 minutes can be used to prepare an aqueous silk solution with a desired molecular weight distribution.
  • the concentration of silk fibroin can be adjusted to 1 wt% and bow hair may be immersed in the solution for 1 hour, removed, and dried overnight at room temperature.
  • the impregnation process may also provide a coating of some degree or a complete coating.
  • a higher molecular weight silk solution may be prepared, using the same method as described in Example 1, with a total boil time throughout the degumming process of 30 minutes to prepare an aqueous silk solution with a desired molecular weight distribution.
  • the concentration of the silk fibroin may be adjusted to 3 wt%.
  • Bow hair may be dipped into the solution, removed, and dried overnight at room temperature.
  • the coating process may also provide a small degree of impregnation, though it is expected to produce principally a coating.

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Abstract

The disclosure herein concerns stringed instruments, string picking implements, bows, silk-coated bows, and related methods. Musical instrument component properties can be influenced by a number of factors that result in the alteration of the component's behavior (e.g., vibrational) which determines its playing characteristics and tone richness. One such factor is its coating or impregnation with silk fibroin.

Description

SILK COATING OF MUSICAL INSTRUMENTS AND MUSICAL INSTRUMENT COMPONENTS AND ACCESSORIES
CLAIM TO PRIORITY
[0001] This application relates to, incorporates by reference for all purposes, and claims priority to United States Provisional Application Serial Number 63/632,350 filed April 10, 2024.
BACKGROUND
[0002] Musical instrument component properties can be influenced by a number of factors that result in the alteration of the component’s behavior (e.g., vibrational) which determines its playing characteristics and tone richness. A need exists for new and improved compositions and methods for modulating these musician instrument component properties.
SUMMARY
[0003] In some aspects, the disclosure herein relates to a stringed instrument having at least one of a nut, peg, bridge, saddle, string post, tuner, machine head, tuning key, fret, fretboard, fingerboard, guitar slide, or capstan located on at least one of a neck or a headstock for engaging a string to adjust pitch, the at least one of a nut, peg, bridge, saddle, string post, tuner, machine head, tuning key, fret, fretboard, fingerboard, guitar slide, or capstan including a silk fibroin coating of at least a portion of the at least one of a nut, peg, bridge, saddle, string post, tuner, machine head, tuning key, guitar slide, or capstan.
[0004] In some aspects, the disclosure herein relates to a string picking implement (e.g., a guitar pick/plectrum) for a stringed musical instrument (e.g., a guitar), the string picking implement including: a pick body having a tip adapted for audibly engaging strings of the stringed musical instrument, and the strings configured to vibrate in response to the audibly engaging; and a silk fibroin coating of at least a portion of the pick body.
[0005] In some aspects, the disclosure herein relates to a bow for a stringed musical instrument (e.g., a violin, a viola, a cello, a contrabass, etc.), the bow including: a stick; a frog; bow hair adapted for audibly engaging strings of the musical instrument and configured to vibrate in response to the audibly engaging; and a silk fibroin coating of at least a portion of the bow hair.
[0006] In some aspects, the disclosure herein relates to a silk-coated bow for a stringed musical instrument, the silk-coated bow including: a stick; a frog; natural animal bow hair adapted for audibly engaging strings of the musical instrument and configured to vibrate in response to the audibly engaging; and a silk fibroin coating of the natural animal bow hair to form a silk-coated bow hair, wherein the natural animal bow hair possesses at least one bow hair characteristic that is inferior to a corresponding bow hair characteristic of the silk-coated bow hair. [0007] In some aspects, the disclosure herein relates to a bow for stringed musical instruments, the bow including: a stick; a frog; and bow hair adapted for audibly engaging strings of the musical instrument and configured to vibrate in response to the audibly engaging; wherein at least a portion of the bow hair is impregnated with a silk fibroin.
[0008] In some aspects, the disclosure herein relates to a method, including: applying a regenerated silk fibroin solution to bow hair for a bow for a string musical instrument on at least a portion of the bow hair; and drying the regenerated silk fibroin solution on the bow hair to form a silk fibroin coating.
[0009] In some aspects, the disclosure herein relates to a method, including: contacting at least a portion of bow hair for a bow for a stringed musical instrument with a regenerated silk fibroin solution, wherein contacting delivers the regenerated silk fibroin solution into the portion of bow hair; and drying the regenerated silk fibroin solution to impregnate the portion of bow hair with an impregnated silk fibroin.
[0010] In some aspects, the disclosure herein relates to a method of augmenting a musical instrument having a resonating portion with at least one natural frequency, the method including: applying uncured silk fibroin to the resonating portion; and while maintaining application of an acoustic frequency to the resonating portion, curing the uncured silk fibroin to form a silk fibroin modified portion.
[0011] These and other systems, methods, objects, features, and advantages of the present disclosure will be apparent to those skilled in the art from the following detailed description of the preferred embodiment and the drawings.
[0012] All documents mentioned herein are hereby incorporated in their entirety by reference. References to items in the singular should be understood to include items in the plural, and vice versa, unless explicitly stated otherwise or clear from the text. Grammatical conjunctions are intended to express any and all disjunctive and conjunctive combinations of conjoined clauses, sentences, words, and the like, unless otherwise stated or clear from the context.
DETAILED DESCRIPTION
[0013] Before the present disclosure is described in further detail, it is to be understood that the disclosure is not limited to the particular embodiments described. It is also understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting. The scope of the present disclosure will be limited only by the claims. As used herein, the singular forms "a", "an", and "the" include plural embodiments unless the context clearly dictates otherwise. [0014] In this application, unless otherwise clear from context, (i) the term “a” may be understood to mean “at least one”; (ii) the term “or” may be understood to mean “and/or”; (iii) the terms “comprising” and “including” may be understood to encompass itemized components or steps whether presented by themselves or together with one or more additional components or steps; and (iv) the terms “about” and “approximately” are used as equivalents and may be understood to permit standard variation as would be understood by those of ordinary skill in the art; and (v) where ranges are provided, endpoints are included.
[0015] Approximately: as used herein, the term “approximately” or “about,” as applied to one or more values of interest, refers to a value that is similar to a stated reference value. In certain embodiments, the term “approximately” or “about” refers to a range of values that fall within 25%, 20%, 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, or less in either direction (greater than or less than) of the stated reference value unless otherwise stated or otherwise evident from the context (except where such number would exceed 100% of a possible value).
[0016] Composition: as used herein, may be used to refer to a discrete physical entity that comprises one or more specified components. In general, unless otherwise specified, a composition may be of any form - e.g., gas, gel, liquid, solid, etc. In some embodiments, “composition” may refer to a combination of two or more entities for use in a single embodiment or as part of the same article. It is not required in all embodiments that the combination of entities result in physical admixture, that is, combination as separate co-entities of each of the components of the composition is possible; however many practitioners in the field may find it advantageous to prepare a composition that is an admixture of two or more of the ingredients in a pharmaceutically acceptable carrier, diluent, or excipient, making it possible to administer the component ingredients of the combination at the same time.
[0017] Improve, increase, or reduce: as used herein or grammatical equivalents thereof, indicate values that are relative to a baseline measurement, such as a measurement in a similar composition made according to previously known methods.
[0018] Substantially: as used herein, the term “substantially” refers to the qualitative condition of exhibiting total or near-total extent or degree of a characteristic or property of interest. One of ordinary skill in the biological arts will understand that biological and chemical phenomena rarely, if ever, go to completion and/or proceed to completeness or achieve or avoid an absolute result. The term “substantially” is therefore used herein to capture the potential lack of completeness inherent in many biological and chemical phenomena. [0019] It should be apparent to those skilled in the art that many additional modifications beside those already described are possible without departing from the inventive concepts. In interpreting this disclosure, all terms should be interpreted in the broadest possible manner consistent with the context. Variations of the term "comprising" should be interpreted as referring to elements, components, or steps in a non-exclusive manner, so the referenced elements, components, or steps may be combined with other elements, components, or steps that are not expressly referenced. Embodiments referenced as "comprising" certain elements are also contemplated as "consisting essentially of" and "consisting of" those elements. When two or more ranges for a particular value are recited, this disclosure contemplates all combinations of the upper and lower bounds of those ranges that are not explicitly recited. For example, recitation of a value of between 1 and 10 or between 2 and 9 also contemplates a value of between 1 and 9 or between 2 and 10.
[0020] As used herein, "silk fibroin" refers to silk fibroin protein whether produced by silkworm, spider, or other insect, or otherwise generated (Lucas et al., Adv. Protein Chem., 13: 107-242 (1958)). Any type of silk fibroin can be used in different embodiments described herein. Silk fibroin produced by silkworms, such as Bombyx inori, is the most common and represents an earth-friendly, renewable resource. For instance, silk fibroin used in a silk film may be attained by extracting sericin from the cocoons of B. mori. Organic silkworm cocoons are also commercially available. There are many different silks, however, including spider silk (e.g., obtained from Nephila clavipes), transgenic silks, genetically engineered silks, such as silks from bacteria, yeast, mammalian cells, transgenic animals, or transgenic plants, and variants thereof, that can be used. See, e.g., WO 97/08315 and U.S. Pat. No. 5,245,012, each of which is incorporated herein by reference in their entireties.
[0021] Coating and impregnating bow hair or other portions of musical instruments with a silk fibroin solution is a sustainable route to increase the durability /strength of the portions (e.g., by slowing degradation of natural products, such as natural bow hair), provide improved durability and playability, improve or alter the sound quality or vibrational behavior, or generate specific acoustic capabilities in the instruments.
[0022] The variability of the raw material of natural animal bow hair and their durability urged inventors to propose solutions to these problems, such as synthetic bow hair or other coatings for natural animal hair that require complex drying/curing steps (e.g., under pressure, radiation, vacuum or at high temperature) which are not sustainable and not needed for the silk fibroin coating. Furthermore, silk fibroin is a natural polymer and does not alter the biodegradability of natural animal bow hair. Silk fibroin coated or impregnated musical instrument portions, including resonating portions, may exhibit characteristics and/or have features that are different from musical instrument portions lacking a silk fibroin coating/impregnation.
[0023] Regenerated silk fibroin solution is disclosed throughout this specification in various embodiments and methods, and may be used for either coating, application, or impregnation of bow hair, resonating portions, or other portions of musical instruments. The regenerated silk fibroin solution may be as described in International Patent Application Pubs. No. WO 2014/145002 and WO 2014/011644, both of which are incorporated by reference herein in their entirety. The regenerated silk fibroin solution may include a silk fibroin concentration by weight within a range of 0.1% to 50%, or within a range of 1% to 5%. The regenerated silk fibroin solution may include silk fibroin having an average molecular weight in a range between 3.5 kDa and 200 kDa. The regenerated silk fibroin solution may further include at least one of a flavorant, a colorant, or a functionalizing agent. The regenerated silk fibroin solution may be prepared by a process that includes boiling for a period of time within a range of 1 minute to and 120 minutes. In some embodiments, boiling may be at an atmospheric boiling pressure. In some embodiments, boiling may be at a temperature within a range of 30° C and 120° C.
[0024] Musical terms, instruments, and parts are used throughout this disclosure in line with their definitions as described in the Oxford Dictionary of Music 6th edition, which is incorporated by reference in its entirety herein for all purposes.
[0025] In an aspect, a stringed instrument (e.g., a guitar, a bass, a violin, a viola, a cello, a contrabass, etc.) includes many different components, such as a nut, peg, bridge, saddle, string post, tuner, machine head, tuning key, fret, fretboard, fingerboard, a guitar slide, or capstan, which are located on at least one of a neck or a headstock of the stringed instrument. The components engage a string to adjust pitch and any of the components can include a silk fibroin coating of at least a portion of the component. Throughout this disclosure, any of the components of embodiments of the stringed instrument, string picking implement, bow, or silk-coated bow may include or be formed from a cane material, a natural porous material, a cane material, a natural material, a wood material, padouk, rosewood, a spruce material, a coconut material, a beech material, an oak material, a flax material, a sisal material, a Miscanthus material, a hemp material, a cellulose material, Brazilwood, sandalwood, pernambuco, or ipe. The stringed instruments may be as described in U.S. Pat. No. 8,110,729, which is incorporated herein by reference in entirety for all purposes.
[0026] In an aspect, a string picking implement, such as a guitar pick or plectrum, for a stringed musical instrument (e.g., a guitar) includes a pick body having a tip adapted for audibly engaging strings of the stringed musical instrument. The strings are configured to vibrate in response to the audibly engaging. At least a portion of the pick body, such as the tip, includes a silk fibroin coating. [0027] In an aspect, a bow for a stringed musical instrument (e.g., a violin, a viola, a cello, a contrabass, etc.) includes a stick, a frog, bow hair adapted for audibly engaging strings of the musical instrument and configured to vibrate in response to the audibly engaging, and a silk fibroin coating of at least a portion of the bow hair. The silk fibroin fills a plurality of pores of the bow hair. [0028] In an aspect, a silk-coated bow for a stringed musical instrument includes a stick, a frog, natural animal bow hair adapted for audibly engaging strings of the musical instrument and configured to vibrate in response to the audibly engaging, and a silk fibroin coating of the natural animal bow hair to form a silk-coated bow hair. The natural animal bow hair possesses at least one bow hair characteristic that is inferior to a corresponding bow hair characteristic of the silk-coated bow hair. The at least one bow hair characteristic is a timbre characteristic, a resonant frequency characteristic, a dynamics characteristic, an articulation characteristic, an envelope characteristic, a springiness characteristic, a durability characteristic, a flexibility characteristic, a vibratory characteristic, a tonal characteristic, or a spectral characteristic. For example, the silk-coated bow hair has a resonant frequency that is within 10%, within 5%, within 1%, or within 0. 1% of a comparison resonant frequency of a comparison natural animal bow hair that lacks the silk fibroin coating. In another example, a spectral centroid of a tone played on the silk-coated bow hair is at least 1%, at least 2%, at least 5%, or at least 10% higher than a comparison spectral centroid of the tone played on a comparison natural animal bow hair that lacks the silk fibroin coating. In yet another example, the silk-coated bow hair has a timbre that is within 10%, within 5%, within 1%, or within 0. 1 % of a comparison timbre of a comparison natural animal bow hair that lacks the silk fibroin coating. In still another example, the silk-coated bow hair has a springiness that is within 10%, within 5%, within 1%, or within 0.1% of a comparison springiness of a comparison natural animal bow hair that lacks the silk fibroin coating. In another example, the silk-coated bow hair is playable for at least three times, at least twice, at least 1.75 times, at least 1.5 times, or at least 1.25 times as many hours as a comparison natural animal bow hair that lacks the silk fibroin coating. In a further example, the silk-coated bow hair exhibits playability at a defined timbre for at least three times, at least twice, at least 1.75 times, at least 1.5 times, or at least 1.25 times as many hours as a comparison natural animal bow hair that lacks the silk fibroin coating. In embodiments, the silk- coated bow hair comprises at least one of increased durability, resistance to changes with humidity /moisture, increased lifespan, reduced degradation, improved sound quality, improved responsiveness, or improved playing characteristics. The silk fibroin fills a plurality of pores of the bow hair.
[0029] In an aspect, a bow for stringed musical instruments includes a stick, a frog, and bow hair adapted for audibly engaging strings of the musical instrument and configured to vibrate in response to the audibly engaging, wherein at least a portion of the bow hair is impregnated with a silk fibroin. The silk fibroin fills a plurality of pores of the bow hair.
[0030] In an aspect, a method includes applying a regenerated silk fibroin solution to bow hair for a bow for a string musical instrument on at least a portion of the bow hair, and drying the regenerated silk fibroin solution on the bow hair to form a silk fibroin coating. In an aspect, a method includes contacting at least a portion of bow hair for a bow for a stringed musical instrument with a regenerated silk fibroin solution, wherein contacting delivers the regenerated silk fibroin solution into the portion of bow hair, and drying the regenerated silk fibroin solution to impregnate the portion of bow hair with an impregnated silk fibroin. Drying can be overnight, at least 4 hours, at least 8 hours, at least 12 hours, at least 18 hours, or at least 24 hours. Drying can proceed at a pressure of at most 15 psi, at most 14 psi, at most 13 psi, at most 12 psi, or at atmospheric pressure. Applying includes at least one of dipping, spraying, wiping, smearing, permeating, infiltrating, or spreading at least one of a surface, an edge, or a tip of the bow hair. The silk fibroin fills a plurality of pores of the bow hair.
[0031] In an aspect, a method of augmenting a musical instrument having a resonating portion with at least one natural frequency includes applying uncured silk fibroin, or other version of silk fibroin that is capable of permeating a material, to the resonating portion, and while maintaining application of an acoustic frequency to the resonating portion, curing the uncured silk fibroin to form a silk fibroin modified portion. Resonance will be throughout the material, so silk fibroin that permeates the resonating portion will also follow the waveform. The uncured silk fibroin is applied to the resonating portion in a way that the uncured silk fibroin maps onto a shape of the resonant frequency propagating in the resonant portion.
[0032] Many musical instruments include resonating portions to which this method is applicable. In some cases, the resonating portion includes a portion of the body of a stringed instrument. In some cases, the resonating portion includes the strings of a stringed instrument. In some cases, the resonating portion includes the rigid portion of a stringed instrument bow. In some cases, the resonating portion includes the body of a woodwind instrument. In some cases, the resonating portion is a part of a percussion instrument. In some cases, the resonating portion is a portion of a mouthpiece.
[0033] In some cases, the resonating portion of the musical instrument can be composed of a natural material, such as wood. In some cases, the resonating portion is composed of one of the materials disclosed above with respect to stringed instruments. In some cases, the resonating portion is composed of wood, such as mahogany, maple, rosewood, koa, spruce, walnut, alder, basswood, ebony, cocobolo, asapele, Brazilian rosewood, cherry, Dalbergia melanoxylon, Engelmann spruce, Malaysian Blackwood, Sitka spruce, ash, cedar, acacia, padouk, yew, Douglas-fir, or the like. In general, the resonating portion can be composed of tonewood. Without wishing to be bound by any particular theory, it is believed that these materials can be altered to produce new tonal capabilities. [0034] The acoustic frequency may be selected in response to or to modify at least one of an overtone, a sustain, a timbre, a durability, a responsiveness, a strength, or an attack of the resonating portion. In some cases, the acoustic frequency is a resonant frequency of the resonating portion, In some cases, the acoustic frequency is a harmonic of a resonant frequency of the resonating portion. In some cases, the acoustic frequency is an integer multiple of the resonant frequency or a harmonic of the resonant frequency. In some cases, the acoustic frequency is particularly selected to have a mismatch with a natural resonance of the resonating portion. In some cases, the acoustic frequency is non-harmonic with the resonant frequency. It should be appreciated that the applying and curing can be a multiple step process, with multiple alternating application and curing steps. In these cases, the resonant frequency of the resonating portion can change after a particular application, such that applying a resonant frequency to the resonating portion requires application of a different frequency than a previous iteration. In other words, in a multiple step process, the resonant frequency can change over time and the method can be adjusted to either maintain the applied frequency or correspondingly change the resonant frequency over time.
[0035] In some cases, multiple frequencies can be simultaneously applied. In some cases, the multiple frequencies include a resonant frequency and one or more harmonic frequencies.
[0036] In an example, the silk fibroin modified portion has a density that is at least three times, at least twice, at least 1.75 times, at least 1.5 times, or at least 1.25 times the density of a comparison resonating portion that lacks the silk fibroin modification. In another example, the silk fibroin modified portion has a strength that is at least three times, at least twice, at least 1.75 times, at least 1.5 times, or at least 1.25 times the strength of a comparison resonating portion that lacks the silk fibroin modification. In yet another example, the silk fibroin modified portion has a timbre that is at least three times, at least twice, at least 1.75 times, at least 1.5 times, or at least 1.25 times the timbre of a comparison resonating portion that lacks the silk fibroin modification. In still another example, the silk fibroin modified portion has a responsiveness that is at least three times, at least twice, at least 1.75 times, at least 1.5 times, or at least 1.25 times the responsiveness of a comparison resonating portion that lacks the silk fibroin modification. In a further example, the silk fibroin modified portion has a durability that is at least three times, at least twice, at least 1.75 times, at least 1.5 times, or at least 1.25 times the durability of a comparison resonating portion that lacks the silk fibroin modification. Applying includes at least one of dipping, spraying, wiping, smearing, permeating, infiltrating, or spreading at least one of a surface, an edge, or a tip of the resonating portion.
[0037] With respect to any of the embodiments disclosed herein, including the stringed instrument (and components thereof), string picking implement, bow, silk-coated bow, or method, the silk fibroin or silk fibroin coating are from a regenerated silk fibroin solution. The regenerated silk fibroin solution includes a silk fibroin concentration by weight within a range of 0.1% to 50%. The regenerated silk fibroin solution includes a silk fibroin concentration by weight within a range of 1 % to 5%. The regenerated silk fibroin solution includes silk fibroin having an average molecular weight in a range between 3.5 kDa and 200 kDa. The regenerated silk fibroin solution can further include at least one of a flavorant, a colorant, or a functionalizing agent. The regenerated silk fibroin solution is prepared by a process that includes boiling for a period of time within a range of 1 minute to and 120 minutes, such as at an atmospheric boiling pressure and at a temperature within a range of 30° C and 120° C.
[0038] In some embodiments disclosed herein where the silk fibroin coating is applied, the coating may be applied at a temperature of at most 60°F, at most 65°F, at most 70°F, at most 80°F, or at most 90°F, it may be applied at atmospheric pressure, and/or it may be applied at a pressure of at most 15 psi, at most 14 psi, at most 13 psi, or at most 12 psi.
[0039] According to various embodiments, a variety of functionalizing agents may be used with the silk-containing embodiments described herein (e.g., silk membrane, silk composition, silk articles, silk matrix, silk foam, silk microsphere, liquid composition, whipped silk cream, silk meringue, compressed silk meringue, hot-pressed silk meringue, silk leather, silk powder, silk toner, edible silkbased films, etc.). It should be understood that the examples herein may recite one or a few silkcontaining embodiments but are applicable to any silk-containing embodiment, as applicable.
[0040] According to various embodiments, any application-appropriate amount of one or more functionalizing agents may be used. In some embodiments, the amount of an individual functionalizing agent may be between about 1 pg/ml and 1,000 pg/ml (e.g., between about 2 and 1,000, 5 and 1,000, 10 and 1,000, 10 and 500, 10 and 100 pg/ml). In some embodiments, the amount of an individual functionalizing agent may be at least 1 pg/ml (e.g., at least 5, 10, 15, 20 25, 50, 100, 200, 300 400, 500, 600, 700, 800, or 900 pg/ml ). In some embodiments, the amount of an individual functionalizing agent is at most 1,000 pg/ml (e.g., 900, 800, 700, 600, 500, 400, 300 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, or 5 pg/ml ).
[0041] In some aspects, the composition comprises one or more sensing agents, such as a sensing dye. The sensing agents/sensing dyes are environmentally sensitive and produce a measurable response to one or more environmental factors. In some aspects, the environmentally- sensitive agent or dye may be present in the composition in an effective amount to alter the composition from a first chemical -physical state to a second chemical -physical state in response to an environmental parameter (e.g., a change in pH, light intensity or exposure, temperature, pressure or strain, voltage, physiological parameter of a subject, and/or concentration of chemical species in the surrounding environment) or an externally applied stimulus (e.g., optical interrogation, acoustic interrogation, and/or applied heat). In some cases, the sensing dye is present to provide one optical appearance under one given set of environmental conditions and a second, different optical appearance under a different given set of environmental conditions. Suitable concentrations for the sensing agents described herein can be the concentrations for the colorants and additives described elsewhere herein. A person having ordinary skill in the chemical sensing arts can determine a concentration that is appropriate for use in a sensing application of the inks described herein.
[0042] In some aspects, the first and second chemical-physical state may be a physical property of the composition, such as mechanical property, a chemical property, an acoustical property, an electrical property, a magnetic property, an optical property, a thermal property, a radiological property, or an organoleptic property. Exemplary sensing dyes or agents include, but are not limited to, a pH sensitive agent, a thermal sensitive agent, a pressure or strain sensitive agent, a light sensitive agent, or a potentiometric agent.
[0043] Exemplary pH sensitive dyes or agents include, but are not limited to, cresol red, methyl violet, crystal violet, ethyl violet, malachite green, methyl green, 2-(p- dimethylaminophenylazo) pyridine, paramethyl red, metanil yellow, 4-phenylazodiphenylamine, thymol blue, metacresol purple, orange IV, 4-o-Tolylazo-o-toluindine, quinaldine red, 2,4- dinitrophenol, erythrosine disodium salt, benzopurpurine 4B, N,N-dimethyl-p-(m-tolylazo) aniline, p- dimethylaminoazobenene, 4,4’-bis(2-amino-l-naphthylazo)-2,2’-stilbenedisulfonic acid, tetrabromophenolphthalein ethyl ester, bromophenol blue, Congo red, methyl orange, ethyl orange, 4-(4-dimethylamino-l-naphylazo)-3-methoxybenesulfonic acid, bromocresol green, resazurin, 4- phenylazo-l-napthylamine, ethyl red 2-(l-dimethylaminophenyazo) pyridine, 4-(p- ethoxypehnylazo)-m-phenylene-diamine monohydrochloride, resorcin blue, alizarin red S, methyl red, propyl red, bromocresol purple, chlorophenol red, p-nitrophenol, alizarin 2-(2,4- dinitrophenylazo) l-napthol-3,6-disulfonic acid, bromothymol blue, 6,8-dinitro-2,4-(lH) quinazolinedione, brilliant yellow, phenol red, neutral red, m-nitrophenol, cresol red, turmeric, metacresol purple, 4,4’-bis(3-amino-l-naphthylazo)-2,2’-stilbenedisulfonic acid, thymol blue, p- naphtholbenzein, phenolphthalein, o-cresolphthalein, ethyl bis(2,4-dimethylphenyl) ethanoate, thymolphthalein, nitrazine yellow, alizarin yellow R, alizarin, p-(2,4-dihydroxyphenylazo) benzenesulfonic acid, 5,5'-indigodisulfonic acid, 2,4,6-trinitrotoluene, 1,3,5-trinitrobenezne, and clayton yellow.
[0044] Exemplary light responsive dyes or agents include, but are not limited to, photochromic compounds or agents, such as triarylmethanes, stilbenes, azasilbenes, nitrones, fulgides, spiropyrans, napthopyrans, spiro-oxzines, quinones, derivatives and combinations thereof.
[0045] Exemplary potentiometric dyes include, but are not limited to, substituted amiononaphthylehenylpridinium (ANEP) dyes, such as di-4-ANEPPS, di-8-ANEPPS, and N-(4- Sulfobutyl)-4-(6-(4-(Dibutylamino)phenyl)hexatrienyl)Pyridinium (RH237).
[0046] Exemplary temperature sensitive dyes or agents include, but are not limited to, thermochromic compounds or agents, such as thermochromic liquid crystals, leuco dyes, fluoran dyes, octadecylphosphonic acid.
[0047] Exemplary pressure or strain sensitive dyes or agents include, but are not limited to, spiropyran compounds and agents.
[0048] Exemplary chemi-sensitive dyes or agents include, but are not limited to, antibodies such as immunoglobulin G (IgG) which may change color from blue to red in response to bacterial contamination.
[0049] In some aspects, the compositions comprise one or more additive, dopant, or biologically active agent suitable for a desired intended purpose. In some aspects, the additive or dopant may be present in the composition in an amount effective to impart an optical or organoleptic property to the composition. Exemplary additives or dopants that impart optical or organoleptic properties include, but are not limited to, dyes/pigments, flavorants, aroma compounds, granular or fibrous fillers.
[0050] Additionally or alternatively, the additive, dopant, or biologically active agent may be present in the composition in an amount effective to "functionalize" the composition to impart a desired mechanical property or added functionality to the composition. Exemplary additive, dopants, or biologically active agent that impart the desired mechanical property or added functionality include, but are not limited to: environmentally sensitive/sensing dyes; active biomolecules; conductive or metallic particles; micro and nanofibers (e.g., silk nanofibers for reinforcement, carbon nanofibers); nanotubes; inorganic particles (e.g., hydroxyapatite, tricalcium phosphate, bioglasses); drugs (e.g., antibiotics, small molecules or low molecular weight organic compounds); proteins and fragments or complexes thereof (e.g., enzymes, antigens, antibodies and antigen-binding fragments thereof);
DNA/RNA (e.g., siRNA, miRNA, mRNA); cells and fractions thereof (viruses and viral particles; prokaryotic cells such as bacteria; eukaryotic cells such as mammalian cells and plant cells; fungi). [0051] In some aspects, the additive or dopant comprises a flavoring agent or flavorant. [0052] Exemplary flavorants include ester flavorants, amino acid flavorants, nucleic acid flavorants, organic acid flavorants, and inorganic acid flavorants, such as, but not limited to, diacetyl, acetylpropionyl, acetoin, isoamyl acetate, benzaldehyde, cinnamaldehyde, ethyl propionate, methyl anthranilate, limonene, ethyl decadienoate, allyl hexanoate, ethyl maltol, ethylvanillin, methyl salicylate, manzanate, glutamic acid salts, glycine salts, guanylic acids salts, inosinic acid salts, acetic acid, ascorbic acid, citric acid, fumaric acid, lactic acid, malic acid, phosphoric acid, tartaric acid, derivatives, and mixtures thereof.
[0053] In some aspects, the additive or dopant comprises an aroma compound. Exemplary aroma compounds include ester aroma compounds, terpene aroma compounds, cyclic terpenes, and aromatic aroma compounds, such as, but not limited to, geranyl acetate, methyl formate, metyl acetate, methyl propionate, methyl butyrate, ethyl acetate, ethyl butyrate, isoamyl acetate, pentyl butrate, pentyl pentanoate, octyl acetate, benzyl acetate, methyl anthranilate, myrecene, geraniol, nerol, citral, cironellal, cironellol, linalool, nerolidol, limonene, camphor, menthol, carone, terpineol, alpha-lonone, thujone, eucalyptol, benzaldehyde, eugenol, cinnamaldehyde, ethyl maltol, vanillin, anisole, anethole, estragole, thymol.
[0054] In some aspects, the additive or dopant comprises a colorant, such as a dye or pigment. In some aspects, the dye or pigment imparts a color or grayscale to the composition. The colorant can be different than the sensing agents and/or sensing dyes below. Any organic and/or inorganic pigments and dyes can be included in the inks. Exemplary pigments suitable for use in the present disclosure include International Color Index or C.I. Pigment Black Numbers 1 , 7, 1 1 and 31 , C.I. Pigment Blue Numbers 15, 15 : 1 , 15 :2, 15 :3, 15 :4, 15 :6, 16, 27, 29, 61 and 62, C.I. Pigment Green Numbers 7, 17, 18 and 36, C.I. Pigment Orange Numbers 5, 13, 16, 34 and 36, C.I. Pigment Violet Numbers 3, 19, 23 and 27, C.I. Pigment Red Numbers 3, 17, 22, 23, 48: 1 , 48:2, 57: 1 , 81 : 1 , 81 :2, 81 :3, 81 :5, 101 , 1 14, 122, 144, 146, 170, 176, 179, 181 , 185, 188, 202, 206, 207, 210 and 249, C.I. Pigment Yellow Numbers 1 , 2, 3, 12, 13, 14, 17, 42, 65, 73, 74, 75, 83, 30, 93, 109, 1 10, 128, 138, 139, 147, 142, 151 , 154 and 180, D&C Red No. 7, D&C Red No. 6 and D&C Red No. 34, carbon black pigment (such as Regal 330, Cabot Corporation), quinacridone pigments (Quinacridone Magenta (228-0122), available from Sun Chemical Corporation, Fort Lee, N.J.), diarylide yellow pigment (such as AAOT Yellow (274- 1788) available from Sun Chemical Corporation); and phthalocyanine blue pigment (such as Blue 15 :3 (294-1298) available from Sun Chemical Corporation). The classes of dyes suitable for use in present invention can be selected from acid dyes, natural dyes, direct dyes (either cationic or anionic), basic dyes, and reactive dyes. The acid dyes, also regarded as anionic dyes, are soluble in water and mainly insoluble in organic solvents and are selected, from yellow acid dyes, orange acid dyes, red acid dyes, violet acid dyes, blue acid dyes, green acid dyes, and black acid dyes. European Patent 0745651, incorporated herein by reference, describes a number of acid dyes that are suitable for use in the present disclosure. Exemplary yellow acid dyes include Acid Yellow 1 International Color Index or C.I. 10316); Acid Yellow 7 (C.I. 56295); Acid Yellow 17 (C.I. 18965); Acid Yellow 23 (C.I. 19140); Acid Yellow 29 (C.I. 18900); Acid Yellow 36 (C.I. 13065); Acid Yellow 42 (C.I. 22910); Acid Yellow 73 (C.I. 45350); Acid Yellow 99 (C.I. 13908); Acid Yellow 194; and Food Yellow 3 (C.I. 15985). Exemplary orange acid dyes include Acid Orange 1 (C.I. 13090/1); Acid Orange 10 (C.I. 16230); Acid Orange 20 (C.I. 14603); Acid Orange 76 (C.I. 18870); Acid Orange 142; Food Orange 2 (C.I. 15980); and Orange B. [0055] Exemplary red acid dyes include Acid Red 1. (C.I. 18050); Acid Red 4 (C.I. 14710); Acid Red 18 (C.I. 16255), Acid Red 26 (C.I. 16150); Acid Red 2.7 (C.I. as Acid Red 51 (C.I. 45430, available from BASF Corporation, Mt. Olive, N.J.) Acid Red 52 (C.I. 45100); Acid Red 73 (C.I. 27290); Acid Red 87 (C. I. 45380); Acid Red 94 (C.I. 45440) Acid Red 194; and Food Red 1 (C.I. 14700). Exemplary violet acid dyes include Acid Violet 7 (C.I. 18055); and Acid Violet 49 (C.I. 42640). Exemplary blue acid dyes include Acid Blue 1 (C.I. 42045); Acid Blue 9 (C.I. 42090); Acid Blue 22 (C.I. 42755); Acid Blue 74 (C.I. 73015); Acid Blue 93 (C.I. 42780); and Acid Blue 158A (C.I. 15050). Exemplary green acid dyes include Acid Green 1 (C.I. 10028); Acid Green 3 (C.I. 42085); Acid Green 5 (C.I. 42095); Acid Green 26 (C.I. 44025); and Food Green 3 (C.I. 42053). Exemplary black acid dyes include Acid Black 1 (C.I. 20470); Acid Black 194 (Basantol® X80, available from BASF Corporation, an azo/1 :2 CR-complex.
[0056] Exemplary direct dyes for use in the present disclosure include Direct Blue 86 (C.I. 74180); Direct Blue 199; Direct Black 168; Direct Red 253; and Direct Yellow 107/132 (C.I. Not Assigned). [0057] Exemplary natural dyes for use in the present disclosure include Alkanet (C.I. 75520,75530); Annafto (C.I. 75120); Carotene (C.I. 75130); Chestnut; Cochineal (C.I.75470); Cutch (C.I. 75250, 75260); Divi-Divi; Fustic (C.I. 75240); Hypemic (C.I. 75280); Logwood (C.I. 75200); Osage Orange (C.I. 75660); Paprika; Quercitron (C.I. 75720); Sanrou (C.I. 75100) ; Sandal Wood (C.I. 75510, 75540, 75550, 75560); Sumac; and Tumeric (C.I. 75300). Exemplary reactive dyes for use in the present disclosure include Reactive Yellow 37 (monoazo dye); Reactive Black 31 (disazo dye); Reactive Blue 77 (phthalo cyanine dye) and Reactive Red 180 and Reactive Red 108 dyes. Suitable also are the colorants described in The Printing Ink Manual (5th ed., Leach et al. eds. (2007), pages 289-299. Other organic and inorganic pigments and dyes and combinations thereof can be used to achieve the colors desired.
[0058] In addition to or in place of visible colorants, compositions provided herein can contain ETV fluorophores that are excited in the ETV range and emit light at a higher wavelength (typically 400 nm and above). Examples of ETV fluorophores include but are not limited to materials from the coumarin, benzoxazole, rhodamine, napthalimide, perylene, benzanthrones, benzoxanthones or benzothia- xanthones families. The addition of a UV fluorophore (such as an optical brightener for instance) can help maintain maximum visible light transmission. The amount of colorant, when present, generally is between 0.05% to 5% or between 0.1% and 1% based on the weight of the composition.
[0059] For non-white compositions, the amount of pigment/dye generally is present in an amount of from at or about 0.1 wt% to at or about 20 wt% based on the weight of the composition. In some applications, a non-white ink can include 15 wt% or less pigment/dye, or 10 wt% or less pigment/dye or 5 wt% pigment/dye, or 1 wt% pigment/dye based on the weight of the composition. In some applications, a non-white ink can include 1 wt% to 10 wt%, or 5 wt% to 15 wt%, or 10 wt% to 20 wt% pigment/dye based on the weight of the composition. In some applications, a non-white ink can contain an amount of dye/pigment that is 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15%, 16 wt%, 17 wt%, 18 wt%, 19 wt% or 20 wt% based on the weight of the composition.
[0060] For white compositions, the amount of white pigment generally is present in an amount of from at or about 1 wt% to at or about 60 wt% based on the weight of the composition. In some applications, greater than 60 wt% white pigment can be present. Preferred white pigments include titanium dioxide (anatase and rutile), zinc oxide, lithopone (calcined coprecipitate of barium sulfate and zinc sulfide), zinc sulfide, blanc fixe and alumina hydrate and combinations thereof, although any of these can be combined with calcium carbonate. In some applications, a white ink can include 60 wt% or less white pigment, or 55 wt% or less white pigment, or 50 wt% white pigment, or 45 wt% white pigment, or 40 wt% white pigment, or 35 wt% white pigment, or 30 wt% white pigment, or 25 wt% white pigment, or 20 wt% white pigment, or 15 wt% white pigment, or 10 wt% white pigment, based on the weight of the composition. In some applications, a white ink can include 5 wt% to 60 wt%, or 5 wt% to 55 wt%, or 10 wt% to 50 wt%, or 10 wt% to 25 wt%, or 25 wt% to 50 wt%, or 5 wt% to 15 wt%, or 40 wt% to 60 wt% white pigment based on the weight of the composition. In some applications, a non-white ink can an amount of dye/pigment that is 5%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, 45%, 46 wt%, 47 wt%, 48 wt%, 49 wt%, 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55%, 56 wt%, 57 wt%, 58 wt%, 59 wt% or 60 wt% based on the weight of the composition. [0061] In some aspects, the additive or dopant comprises a conductive additive. Exemplary conductive additives include, but are not limited to graphite, graphite powder, carbon nanotubes, and metallic particles or nanoparticles, such as gold nanoparticles. In some aspects, the conductive additive is biocompatible and non-toxic.
[0062] Unless otherwise specified or indicated by context, the terms “a”, “an”, and “the” mean “one or more.” For example, “a molecule” should be interpreted to mean “one or more molecules.” [0063] As used herein, “about”, “approximately,” “substantially,” and “significantly” will be understood by persons of ordinary skill in the art and will vary to some extent on the context in which they are used. If there are uses of the term which are not clear to persons of ordinary skill in the art given the context in which it is used, “about” and “approximately” will mean plus or minus <10% of the particular term and “substantially” and “significantly” will mean plus or minus >10% of the particular term.
[0064] As used herein, the terms “include” and “including” have the same meaning as the terms “comprise” and “comprising.” The terms “comprise” and “comprising” should be interpreted as being “open” transitional terms that permit the inclusion of additional components further to those components recited in the claims. The terms “consist” and “consisting of’ should be interpreted as being “closed” transitional terms that do not permit the inclusion of additional components other than the components recited in the claims. The term “consisting essentially of’ should be interpreted to be partially closed and allowing the inclusion only of additional components that do not fundamentally alter the nature of the claimed subject matter.
[0065] All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.
[0066] All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.
[0067] Preferred aspects of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Variations of those preferred aspects may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect a person having ordinary skill in the art to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.
[0068] While the invention has been illustrated and described in detail in the foregoing drawings and description, the same is to be considered as illustrative and not restrictive in character, it being understood that only illustrative embodiments thereof have been shown and described and that all changes and modifications that come within the spirit of the invention are desired to be protected. For example, any of the features or functions of any of the embodiments disclosed herein may be incorporated into any of the other embodiments disclosed herein.
[0069] The following examples illustrate some embodiments and aspects of the invention. It will be apparent to those skilled in the relevant art that various modifications, additions, substitutions, and the like can be performed without altering the spirit or scope of the invention, and such modifications and variations are encompassed within the scope of the invention as defined in the claims which follow. The following examples do not in any way limit the invention.
[0070] EXAMPLES
[0071] Example 1
[0072] Lower molecular weight silk solutions can be prepared using a method that is similar to the methods described in International Patent Application Pub. No. WO 2014/145002, which is incorporated herein in its entirety by reference. Provided herein is an exemplary protocol to produce a composition of low molecular weight silk fibroin.
[0073] Silk fibroin solution: 1) Silkworm Bombyx mori cocoons were degummed through a modified extraction process as described in Sofia S et al. (2001) Journal of Biomedical Materials Research, 54, 139-148.; 2) Cut cocoons and remove the pupae, pupae skins and any other dirt from the inside of the cocoon; 3) Degum the cocoon pieces in a ~0.02M boiling sodium carbonate (NazCCF) solution using a degumming time of about 60 minutes or more; 4) Rinse the degummed silk fibroin in water (e.g., Milli-Q water) at least thrice, for at least half an hour each time.; 5) Air dry the rinsed silk fibroin.; 6) Dissolve the silk fibroin in a 9.3 M lithium bromide solution (Sigma Aldrich, MO, USA, ReagentPlus > 99%) at 60 °C and dialyze against water (e.g., Milli-Q water), e.g., with Slide-a-Lyzer dialysis cassettes (Thermo Scientific, IL, USA, MWCO 3,500) for about 2 days, regularly changing the water, e.g., every 6 hours.; 7) Centrifuge the resulting aqueous silk solution twice, at approximately 1 ,000 rpm, for 20 minutes each time.
[0074] The resulting aqueous low molecular weight silk fibroin solution has a concentration between 7% wt/vol and 9% wt/vol silk fibroin. Up to this point, the silk fibroin solution is called an as- purified solution. The as-purified silk fibroin solution can be further subjected to an autoclaving step, and the silk fibroin solution is then called an autoclaved solution. Store the silk fibroin solution at 4 °C.
[0075] Throughout the degumming process, a total boil time of 60 minutes can be used to prepare an aqueous silk solution with a desired molecular weight distribution. The concentration of silk fibroin can be adjusted to 1 wt% and bow hair may be immersed in the solution for 1 hour, removed, and dried overnight at room temperature. Without wishing to be bound by any particular theory, it is believed that the impregnation process may also provide a coating of some degree or a complete coating.
[0076] Example 2
[0077] A higher molecular weight silk solution may be prepared, using the same method as described in Example 1, with a total boil time throughout the degumming process of 30 minutes to prepare an aqueous silk solution with a desired molecular weight distribution. The concentration of the silk fibroin may be adjusted to 3 wt%. Bow hair may be dipped into the solution, removed, and dried overnight at room temperature. Without wishing to be bound by any particular theory, it is believed that the coating process may also provide a small degree of impregnation, though it is expected to produce principally a coating.
[0078] EQUIVALENTS AND SCOPE
[0079] The recitation of a listing of elements in any definition of a variable herein includes definitions of that variable as any single element or combinations (or subcombinations) of listed elements. The recitation of an embodiment herein includes that embodiment as any single embodiment or in combination with any other embodiments or portions thereof. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. The scope of the present invention is not intended to be limited to the above Description, but rather is as set forth in the following claims:

Claims

CLAIMS What is claimed is:
1. A stringed instrument having at least one of a nut, peg, bridge, saddle, string post, tuner, machine head, tuning key, fret, fretboard, fingerboard, guitar slide, or capstan located on at least one of a neck or a headstock for engaging a string to adjust pitch, the at least one of a nut, peg, bridge, saddle, string post, tuner, machine head, tuning key, fret, fretboard, fingerboard, guitar slide, or capstan comprising a silk fibroin coating of at least a portion of the at least one of a nut, peg, bridge, saddle, string post, tuner, machine head, tuning key, guitar slide, or capstan.
2. A string picking implement (e.g., a guitar pick/plectrum) for a stringed musical instrument (e.g., a guitar), the string picking implement comprising: a pick body having a tip adapted for audibly engaging strings of the stringed musical instrument, and the strings configured to vibrate in response to the audibly engaging; and a silk fibroin coating of at least a portion of the pick body.
3. The string picking implement of claim 2. wherein the portion is the tip.
4. A bow for a stringed musical instrument (e.g., a violin, a viola, a cello, a contrabass, etc.), the bow comprising: a stick; a frog; bow hair adapted for audibly engaging strings of the musical instrument and configured to vibrate in response to the audibly engaging; and a silk fibroin coating of at least a portion of the bow hair.
5. A silk-coated bow for a stringed musical instrument, the silk-coated bow comprising: a stick; a frog; natural animal bow hair adapted for audibly engaging strings of the musical instrument and configured to vibrate in response to the audibly engaging; and a silk fibroin coating of the natural animal bow hair to form a silk-coated bow hair, wherein the natural animal bow hair possesses at least one bow hair characteristic that is inferior to a corresponding bow hair characteristic of the silk-coated bow hair.
6. The silk-coated bow of claim 5, wherein the at least one bow hair characteristic is a timbre characteristic, a resonant frequency characteristic, a dynamics characteristic, an articulation characteristic, an envelope characteristic, a springiness characteristic, a durability characteristic, a flexibility characteristic, a vibratory characteristic, a tonal characteristic, or a spectral characteristic.
7. The silk-coated bow of claim 5, wherein the silk-coated bow hair has a resonant frequency that is within 10%, within 5%, within 1 %, or within 0.1 % of a comparison resonant frequency of a comparison natural animal bow hair that lacks the silk fibroin coating.
8. The silk-coated bow of claim 5, wherein the silk-coated bow hair comprises at least one of increased durability, resistance to changes with humidity /moisture, increased lifespan, reduced degradation, improved sound quality, improved responsiveness, or improved playing characteristics.
9. The silk-coated bow of claim 5, wherein a spectral centroid of a tone played on the silk-coated bow hair is at least 1%, at least 2%, at least 5%, or at least 10% higher than a comparison spectral centroid of the tone played on a comparison natural animal bow hair that lacks the silk fibroin coating.
10. The silk-coated bow of claim 5, wherein the silk-coated bow hair has a timbre that is within 10%, within 5%, within 1 %, or within 0.1% of a comparison timbre of a comparison natural animal bow hair that lacks the silk fibroin coating.
11. The silk-coated bow of claim 5, wherein the silk-coated bow hair has a springiness that is within 10%, within 5%, within 1%, or within 0.1% of a comparison springiness of a comparison natural animal bow hair that lacks the silk fibroin coating.
12. The silk-coated bow of claim 5, wherein the silk-coated bow hair is playable for at least three times, at least twice, at least 1.75 times, at least 1.5 times, or at least 1.25 times as many hours as a comparison natural animal bow hair that lacks the silk fibroin coating.
13. The silk-coated bow of claim 5, wherein the silk-coated bow hair exhibits playability at a defined timbre for at least three times, at least twice, at least 1.75 times, at least 1.5 times, or at least 1.25 times as many hours as a comparison natural animal bow hair that lacks the silk fibroin coating.
14. A bow for stringed musical instruments, the bow comprising: a stick; a frog; and bow hair adapted for audibly engaging strings of the musical instrument and configured to vibrate in response to the audibly engaging; wherein at least a portion of the bow hair is impregnated with a silk fibroin.
15. A method, comprising: applying a regenerated silk fibroin solution to bow hair for a bow for a string musical instrument on at least a portion of the bow hair; and drying the regenerated silk fibroin solution on the bow hair to form a silk fibroin coating.
16. A method, comprising: contacting at least a portion of bow hair for a bow for a stringed musical instrument with a regenerated silk fibroin solution, wherein contacting delivers the regenerated silk fibroin solution into the portion of bow hair; and drying the regenerated silk fibroin solution to impregnate the portion of bow hair with an impregnated silk fibroin.
17. A method of augmenting a musical instrument having a resonating portion with at least one natural frequency, the method comprising: applying uncured silk fibroin to the resonating portion; and while maintaining application of an acoustic frequency to the resonating portion, curing the uncured silk fibroin to form a silk fibroin modified portion.
18. The method of claim 17, wherein the silk fibroin modified portion has a density that is at least three times, at least twice, at least 1.75 times, at least 1.5 times, or at least 1.25 times the density of a comparison resonating portion that lacks the silk fibroin modification.
19. The method of claim 17 or 0, wherein the uncured silk fibroin is applied to the resonating portion in a way that the uncured silk fibroin maps onto a shape of the resonant frequency propagating in the resonant portion.
20. The method of any one of claims 17 to the immediately preceding claim, wherein the silk fibroin modified portion has a strength that is at least three times, at least twice, at least 1.75 times, at least 1.5 times, or at least 1.25 times the strength of a comparison resonating portion that lacks the silk fibroin modification.
21. The method of any one of claims 17 to the immediately preceding claim, wherein the silk fibroin modified portion has a timbre that is at least three times, at least twice, at least 1.75 times, at least 1.5 times, or at least 1.25 times the timbre of a comparison resonating portion that lacks the silk fibroin modification.
22. The method of any one of claims 17 to the immediately preceding claim, wherein the silk fibroin modified portion has a responsiveness that is at least three times, at least twice, at least 1 .75 times, at least 1.5 times, or at least 1.25 times the responsiveness of a comparison resonating portion that lacks the silk fibroin modification.
23. The method of any one of claims 17 to the immediately preceding claim, wherein the silk fibroin modified portion has a durability that is at least three times, at least twice, at least 1.75 times, at least 1.5 times, or at least 1.25 times the durability of a comparison resonating portion that lacks the silk fibroin modification.
24. The method of any one of claims 17 to the immediately preceding claim, wherein the acoustic frequency is selected to modify at least one of an overtone, a sustain, a timbre, a durability, a responsiveness, a strength, or an attack of the resonating portion.
25. The method of any one of claims 17 to the immediately preceding claim, wherein the acoustic frequency is selected to modify an overtone of the resonating portion.
26. The method of any one of claims 17 to the immediately preceding claim, wherein the acoustic frequency is selected to modify a sustain of the resonating portion.
27. The method of any one of claims 17 to the immediately preceding claim, wherein the acoustic frequency is selected to modify a timbre of the resonating portion.
28. The method of any one of claims 17 to the immediately preceding claim, wherein the acoustic frequency is selected to modify a durability of the resonating portion.
29. The method of any one of claims 17 to the immediately preceding claim, wherein the acoustic frequency is selected to modify a responsiveness of the resonating portion.
30. The method of any one of claims 17 to the immediately preceding claim, wherein the acoustic frequency is selected to modify strength of the resonating portion.
31. The method of any one of claims 17 to the immediately preceding claim, wherein the acoustic frequency is selected to modify an attack of the resonating portion.
32. The stringed instrument, string picking implement, bow, silk-coated bow, or method of any of the preceding claims wherein the silk fibroin or silk fibroin coating are from a regenerated silk fibroin solution.
33. The stringed instrument, string picking implement, bow, silk-coated bow, or method of claim 32, wherein the regenerated silk fibroin solution comprises a silk fibroin concentration by weight within a range of 0.1% to 50%.
34. The stringed instrument, string picking implement, bow, silk-coated bow, or method of claim 32, wherein the regenerated silk fibroin solution comprises a silk fibroin concentration by weight within a range of 1% to 5%.
35. The stringed instrument, string picking implement, bow, silk-coated bow, or method of claim 32, wherein the regenerated silk fibroin solution comprises silk fibroin having an average molecular weight in a range between 3.5 kDa and 200 kDa.
36. The stringed instrument, string picking implement, bow, silk-coated bow, or method of claim 32, wherein the regenerated silk fibroin solution further comprises at least one of a flavorant, a colorant, or a functionalizing agent.
37. The stringed instrument, string picking implement, bow, silk-coated bow, or method of claim 32, wherein the regenerated silk fibroin solution is prepared by a process that includes boiling for a period of time within a range of 1 minute to and 120 minutes.
38. The stringed instrument, string picking implement, bow, silk-coated bow, or method of claim 37, wherein boiling is at an atmospheric boiling pressure.
39. The stringed instrument, string picking implement, bow, silk-coated bow, or method of claim 37, wherein boiling is at a temperature within a range of 30 °C and 120 °C.
40. The bow, silk-coated bow, or method of claims 3-8, wherein the silk fibroin fills a plurality of pores of the bow hair.
41. The stringed instrument, string picking implement, bow, or silk-coated bow of claims 1-13 comprises a cane material, a natural porous material, a cane material, a natural material, a wood material, padouk, rosewood, a spruce material, a coconut material, a beech material, an oak material, a flax material, a sisal material, a Miscanthus material, a hemp material, a cellulose material, Brazilwood, sandalwood, pemambuco, or ipe.
42. The stringed instrument, string picking implement, bow, silk-coated bow, or method of claims 1-13, 0, and 32-41, wherein the silk fibroin coating is applied at a temperature of at most 60 °F, at most 65 °F, at most 70 °F, at most 80 °F, or at most 90 °F.
43. The stringed instrument, string picking implement, bow, silk-coated bow, or method of claims 1-13, 0, and 32-42, wherein the silk fibroin coating is applied at atmospheric pressure.
44. The stringed instrument, string picking implement, bow, silk-coated bow, or method of claims 1-13, 0, and 32-42, wherein the silk fibroin coating is applied at a pressure of at most 15 psi, at most 14 psi, at most 13 psi, or at most 12 psi.
45. The method of claim 0 or 16, wherein drying is overnight.
46. The method of claim 0 or 16, wherein drying is for at least 4 hours, at least 8 hours, at least 12 hours, at least 18 hours, or at least 24 hours.
47. The method of claim 0 or 16, wherein drying proceeds at a pressure of at most 15 psi, at most 14 psi, at most 13 psi, or at most 12 psi.
48. The method of claim 0 or 16, wherein drying proceeds at atmospheric pressure.
49. The method of claims 0 or 0, wherein applying comprises at least one of dipping, spraying, wiping, smearing, permeating, infiltrating, or spreading.
50. The method of claim 49, wherein dipping is of at least one of a surface, an edge, or a tip of at least one of the bow hair or resonating portion.
51. A string sliding implement (e.g., a guitar slide) for a stringed musical instrument (e.g., a guitar), the string sliding implement comprising: a hollow tube or solid object having a surface adapted for audibly engaging strings of the stringed musical instrument, the strings configured to vibrate in response to the audibly engaging; and a silk fibroin coating of at least a portion of the hollow tube or solid object body.
PCT/US2025/024042 2024-04-10 2025-04-10 Silk coating of musical instruments and musical instrument components and accessories Pending WO2025217387A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140033905A1 (en) * 2012-08-03 2014-02-06 Gittler Instruments LLC Electric musical instrument
US20140134240A1 (en) * 2008-09-26 2014-05-15 Trustees Of Tufts College pH INDUCED SILK GELS AND USES THEREOF
WO2024081733A2 (en) * 2022-10-11 2024-04-18 Trustees Of Tufts College Silk coating of reeds of instruments

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140134240A1 (en) * 2008-09-26 2014-05-15 Trustees Of Tufts College pH INDUCED SILK GELS AND USES THEREOF
US20140033905A1 (en) * 2012-08-03 2014-02-06 Gittler Instruments LLC Electric musical instrument
WO2024081733A2 (en) * 2022-10-11 2024-04-18 Trustees Of Tufts College Silk coating of reeds of instruments

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