WO2020240077A1 - Nanoagrégats d'or - Google Patents

Nanoagrégats d'or Download PDF

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Publication number
WO2020240077A1
WO2020240077A1 PCT/FI2020/050294 FI2020050294W WO2020240077A1 WO 2020240077 A1 WO2020240077 A1 WO 2020240077A1 FI 2020050294 W FI2020050294 W FI 2020050294W WO 2020240077 A1 WO2020240077 A1 WO 2020240077A1
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WO
WIPO (PCT)
Prior art keywords
gold
polymer matrix
light
fluorescent
nanoclusters
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.)
Ceased
Application number
PCT/FI2020/050294
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English (en)
Inventor
Mohammad H. BITARAFAN
Sofia SUOMALA
Juha Toivonen
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Tampere University Foundation SR
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Tampere University Foundation SR
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Filing date
Publication date
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Publication of WO2020240077A1 publication Critical patent/WO2020240077A1/fr
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/305—Associated digital information
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • B42D25/373—Metallic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/40—Manufacture
    • B42D25/405—Marking
    • B42D25/41—Marking using electromagnetic radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the present invention relates to processes for producing gold nanoclusters. More specifically the processes enable very precise and discrete patterning of fluorescent features in polymer films and products thereof. Especially interesting is the process for production of fluorescent gold nanoclusters and applications thereof, such as anti-counterfeiting.
  • noble metal nanoparticles or nanoclusters have been prepared either as a“top- down” or as a“bottom-up” approach. In the former, large particles are etched to form smaller nanoclusters.
  • the bottom-up approach comprises various synthetic methods, including thermal reduction, microwave heating, photoreduction, ligand-induced etching, sonochemistry and template-assisted synthesis.
  • Fluorescent noble metal nanoclusters are usually formed in the presence of the correct stabilizing templates or ligands and have a ligand shell-metal core structure.
  • the ligand shell typically consists of proteins, DNA, polymers, dendrimers, thiolates or other small molecules.
  • the ligand shell of noble metal nanoclusters and the surface of the core could significantly contribute to their chemical and physical properties and influence further applications of fluorescent noble metal nanoclusters.
  • An object of the present invention is to provide a process and means to alleviate the disadvantages discussed above.
  • the present invention relates to a process of producing fluorescent gold nanoclusters according to claim 1 , composition according to claim 13 and polymer matrix according to claim 16.
  • DMDs digital micromirror devices
  • SLMs spatial light modulators
  • the light induces simultaneous photo-reduction and agglomeration of reduced neutral-state gold, leading to the formation and stabilization of fluorescent gold nanoclusters.
  • Solidifying the intermediate contributes to localizing the gold nanoclusters.
  • the polymer ensures the further gold nanoclusters growth.
  • fluorescent gold nanoclusters at a solid polymer matrix are produced.
  • light having wavelength from 200 to 700 nm, preferably from 300 to 500 nm and most preferably from 350 to 490 nm is used in step c.
  • the gold nanocluster formation is also referred to as gold nanocluster generation. It is understood, that during gold nanocluster formation, the exposure to light also excites the fluorescent gold nanoclusters formed. Hence, immediately after formation of nanoclusters in the polymer matrix, said nanoclusters emit light. However, they can be excited later on under desired conditions for reading the fluorescent pattern coded to the gold nanocluster containing polymer matrix.
  • Patterning to solid polymer matrix is formed by exposing a predetermined part of the solid polymer matrix to light.
  • the exposure in step c) follows a predetermined pattern, wherein at least part of the solid polymer matrix remains non-exposed and hence non- fluorescent as in figure 7.
  • the process may further comprise a step of detection of said polymer matrix by collecting fluorescent light from said polymer matrix.
  • fluorescent gold nanoclusters at a solid polymer matrix such as labels
  • microscope objectives with high numerical aperture are required to collect fluorescent light and detect labeling.
  • the step a. further comprises providing a solvent
  • step b. further comprises removing at least part of the solvent from said intermediate to initiate solidification.
  • the process for producing fluorescent gold nanoclusters can then be described comprising a. providing a polymer, a gold cation source, and a solvent, and admixing to provide an intermediate, b. removing at least part of the solvent from said intermediate to solidify the polymer and gold cations therein, to obtain solid polymer matrix, c. exposing a predetermined part of the solid polymer matrix, for an exposure time from 0.0001 to 1 s, to light having intensity from 1 to 1000 W/cm 2 , preferably from 10 to 500 W/cm 2 to produce fluorescent gold nanoclusters.
  • Fluorescence is a form of luminescence and one of special characteristics of gold nanoclusters. Consequently, “fluorescent” refers to an entity which emits light upon appropriate excitation. Fluorescent gold nanoclusters emit detectable light when exposed to excitation light. Further growth, that is growth beyond the largest diameter of 2 nm is undesirable. With“bleaching” is here referred to decrease of the fluorescence, caused by excessive growth of the gold nanoclusters and loss of fluorescent characteristics through said growth.
  • the light source comprises continuous wave laser irradiation.
  • Continuous wave laser was used in the experimental part, since it provides precise means for light exposure, as so-called laser writing. Intensity may vary from 1 to 1000, preferably from 10 to 500 W/cm 2 to produce said gold nanoclusters.
  • the wavelength used for light patterning can vary between 200 and 700 nm, preferably between 300 and 500 nm, and more preferably between 350 - 490 nm. Continuous wave lasers operating within this wavelength are common and readily available commercially. Use of such common laser enables applications where exciting takes place distinctly from nanocluster formation process.
  • the formation of gold nanoclusters by photoreduction from Au 3+ in polymer matrix requires set amount of energy.
  • the codependence of intensity, exposure time and wavelength can be calculated based on common general knowledge. If the energy is too low, no nanocluster formation occurs or said formation is too slow for industrial applications. However, exposure to the light at an intensity too high or for an excessive time, leads to photobleaching. This is known to relate to growth of the nanoclusters to reach dimensions in the range of nanoparticles, where characteristics typical for nanoclusters, such as fluorescence, are gradually lost.
  • the intensity required for gold nanocluster formation was surprisingly low in the experiments herein conducted.
  • shorter wavelengths are more appropriate, such as wavelengths from 400 to 440 nm, preferably 430 nm.
  • the experiments conducted here showed how nanoclusters were generated much faster at wavelength of 430 nm. This is demonstrated in Fig. 3.
  • a focused light beam is used to enable forming spots.
  • the solid polymer matrix, mounted on a computer-controlled 3D translation stage, is then scanned against the laser beam to generate desired fluorescent patterns. Even with relatively simple experimental setting, surprisingly sophisticated fluorescent patterns were produced on the solid polymer matrix in the experiments conducted.
  • the gold cations are provided to the intermediate as gold salts, typically as Au 3+ or gold(lll) derivatives, or as Au + or gold(l) derivatives.
  • Terms“gold cations” and“Au + or Au 3+ “ are used herein interchangeably. More specifically, these comprise gold(lll) bromide, gold(lll) hydroxide, gold(l) iodide and gold chlorides.
  • Gold chlorides commercially available comprise AuCI, AuC , HAuCU and hydrates HAuCU * xhhO thereof, such as Gold(lll) chloride trihydrate HAuCU * 3H2O.
  • gold(l) chloride also gold(l) iodide, Aul, is available.
  • the gold cation is Au + .
  • Reagents comprising further elements to gold and chlorine are also known, and for similar purposes as herein described, for example «(AuCU) has been recommended.
  • Commercial products comprise both powders and solutions, such as 30 wt. % HAuCU in dilute HCI.
  • Gold provides advantages over other metals through its stability and biocompatibility. Furthermore, gold has now been found to require lower intensity for nanocluster formation.
  • polymers suitable here comprise high molecular weight acrylate and vinyl type polymers.
  • polymers suitable here comprise high molecular weight acrylate and vinyl type polymers.
  • a man skilled in the art can select a suitable matrix material.
  • the polymers usable herein comprise poly(methacrylic acid)(PMAA), poly(vinyl alcohol)(PVA), poly(methyl methacrylate) (PTMP-PMMA), poly(n-butyl methacrylate) (PTMP-PBMA), poly(tert-butyl methacrylate) (PTMP-PtBMA), poly (N-vinyl-2- pyrrolidone), Vinyl Ether Star Polymers, polycarbonate, polystyrene, SU-8.
  • the polymer matrix comprises poly(vinyl alcohol), more preferably poly(vinyl alcohol) having molecular weight, Mw from 25 000 to 125 000, specifically 89 000- 98 000.
  • the solid polymer provides the matrix for a macro-scale label.
  • a macro-scale label is visible to the naked eye or readable by hand-held devices, such as a smart phone, said macro-scale label is characterized by having two dimensions, or at least the largest dimension from 1 mm to 50 mm, preferably from 2 mm to 26 mm.
  • Gold nanoclusters embedded within such polymeric matrices provide surprisingly simple and hence controllable matrix compared to prior art nanodots in liquid matrices requiring complex systems with reducing agents, specific anions or colloid-forming agents.
  • Increasing complexity of nanoclusters as such increases the system complexity respectively limiting options with regard to i.e. solvent, stabilizer and matrix choices leading to further restriction when end uses are concerned.
  • the present process requires no specific anion source to be coupled with gold cations. Suitability to very different applications is increased through avoidance of several components.
  • figure 2a discloses a schematic arrangement for industrial scale gold nanocluster formation.
  • DMD digital micromirror
  • SLM spatial light modulator
  • photomasking systems the light exposure may be directed with high specificity to multiple points or areas of the polymer matrix containing gold cations, here label.
  • projecting the light through a spatial light modulator (SLM) or a digital micromirror device provides the exposure needed for gold nanocluster formation.
  • any light source including light emitting diode (LED), with correct said parameters can be used for light activation. Since any source other than lasers provide incoherent light, it should be firstly collimated via a single convex lens. Then the collimated light is delivered to the sample through the identical setup mentioned in the previous example for continuous wave laser. If the collimated light reflects off a DMD, then arbitrarily patterned light strikes the sample, leading to the activation of patterned fluorescent gold nanoclusters. In this way, the activation occurs in parallel by the use of a cost-effective light source, thus providing a fast and low- cost method for light patterning of fluorescent markers.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Electromagnetism (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Manufacturing & Machinery (AREA)
  • Plasma & Fusion (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne une nouvelle matrice polymère comprenant des nanoagrégats d'or fluorescents. La matrice est un polymère avec des nanoagrégats d'or fluorescents incorporés. Le procédé de production de ladite matrice polymère avec des nanoagrégats d'or incorporés implique l'exposition à la lumière.
PCT/FI2020/050294 2019-05-28 2020-05-04 Nanoagrégats d'or Ceased WO2020240077A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI20195444 2019-05-28
FI20195444 2019-05-28

Publications (1)

Publication Number Publication Date
WO2020240077A1 true WO2020240077A1 (fr) 2020-12-03

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PCT/FI2020/050294 Ceased WO2020240077A1 (fr) 2019-05-28 2020-05-04 Nanoagrégats d'or

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113466199A (zh) * 2021-07-06 2021-10-01 长春工业大学 一种铜纳米簇与硅藻土复合荧光传感器的制备用于六价铬离子的检测
CN114855366A (zh) * 2022-05-20 2022-08-05 齐齐哈尔大学 一种聚乙烯醇/金纳米簇光致发光薄膜的制备方法
CN115429902A (zh) * 2021-06-04 2022-12-06 中南大学 磁性氧化铁细胞标记材料及其制备和应用
CN117025209A (zh) * 2023-08-09 2023-11-10 湖北大学 一种检测四环素类抗生素的橙色银荧光探针及其制备方法
WO2026085291A1 (fr) * 2024-10-16 2026-04-23 The Board Of Trustees Of The Leland Stanford Junior University Superagrégats d'or binaires métabolisables et utilisations associées

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002048432A2 (fr) * 2000-12-15 2002-06-20 The Arizona Board Of Regents Procede permettant de realiser le moirage d'un metal a l'aide de precurseurs contenant des nanoparticules
WO2004003558A1 (fr) * 2002-06-27 2004-01-08 Georgia Tech Research Corporation Etiquettes optiques fluorescentes de dimensions nanometriques et utilisations
WO2017099313A1 (fr) * 2015-12-11 2017-06-15 재단법인 대구경북첨단의료산업진흥재단 Nanoparticules de diffusion raman exaltée de surface (sers), leur procédé de préparation et leurs applications

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002048432A2 (fr) * 2000-12-15 2002-06-20 The Arizona Board Of Regents Procede permettant de realiser le moirage d'un metal a l'aide de precurseurs contenant des nanoparticules
WO2004003558A1 (fr) * 2002-06-27 2004-01-08 Georgia Tech Research Corporation Etiquettes optiques fluorescentes de dimensions nanometriques et utilisations
WO2017099313A1 (fr) * 2015-12-11 2017-06-15 재단법인 대구경북첨단의료산업진흥재단 Nanoparticules de diffusion raman exaltée de surface (sers), leur procédé de préparation et leurs applications

Non-Patent Citations (4)

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Title
DALTON TRANS., vol. 46, no. 46, 2017, pages 16236 - 16243
DIVYA MADHURI U ET AL: "Gold nanoclusters with a wide range of fluorescence characteristics generated in situ in polymer thin films: potential gas sensing application.", DALTON TRANSACTIONS (CAMBRIDGE, ENGLAND : 2003) 28 NOV 2017, vol. 46, no. 46, 28 November 2017 (2017-11-28), pages 16236 - 16243, XP002800086, ISSN: 1477-9234 *
LANGMUIR, vol. 25, no. 24, 2009, pages 13888 - 13893
SAKAMOTO MASANORI ET AL: "Photochemical reactivity of gold clusters: dependence on size and spin multiplicity.", LANGMUIR : THE ACS JOURNAL OF SURFACES AND COLLOIDS 15 DEC 2009, vol. 25, no. 24, 15 December 2009 (2009-12-15), pages 13888 - 13893, XP002800085, ISSN: 1520-5827 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115429902A (zh) * 2021-06-04 2022-12-06 中南大学 磁性氧化铁细胞标记材料及其制备和应用
CN115429902B (zh) * 2021-06-04 2023-08-18 中南大学 磁性氧化铁细胞标记材料及其制备和应用
CN113466199A (zh) * 2021-07-06 2021-10-01 长春工业大学 一种铜纳米簇与硅藻土复合荧光传感器的制备用于六价铬离子的检测
CN114855366A (zh) * 2022-05-20 2022-08-05 齐齐哈尔大学 一种聚乙烯醇/金纳米簇光致发光薄膜的制备方法
CN117025209A (zh) * 2023-08-09 2023-11-10 湖北大学 一种检测四环素类抗生素的橙色银荧光探针及其制备方法
CN117025209B (zh) * 2023-08-09 2024-02-09 湖北大学 一种检测四环素类抗生素的橙色银荧光探针及其制备方法
WO2026085291A1 (fr) * 2024-10-16 2026-04-23 The Board Of Trustees Of The Leland Stanford Junior University Superagrégats d'or binaires métabolisables et utilisations associées

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