US20030129085A1 - Siloxy porpyhrins and metal complexes thereof - Google Patents

Siloxy porpyhrins and metal complexes thereof Download PDF

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US20030129085A1
US20030129085A1 US10/278,421 US27842102A US2003129085A1 US 20030129085 A1 US20030129085 A1 US 20030129085A1 US 27842102 A US27842102 A US 27842102A US 2003129085 A1 US2003129085 A1 US 2003129085A1
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porphyrin
array
porphyrinatozinc
selective
analyte
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Kenneth Suslick
Neal Rakow
Avijit Sen
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University of Illinois System
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/27—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands using photo-electric detection ; circuits for computing concentration
    • G01N21/272—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands using photo-electric detection ; circuits for computing concentration for following a reaction, e.g. for determining photometrically a reaction rate (photometric cinetic analysis)
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour

Definitions

  • the present invention relates to methods and apparatus for artificial olfaction, e.g., artificial noses, for the detection of odorants by a visual display.
  • artificial olfaction e.g., artificial noses
  • artificial noses olfactory or vapor-selective detectors
  • Artificial noses that can detect many different chemicals are desirable for personal dosimeters in order to detect the type and amount of odorants exposed to a human, the presence of chemical poisons or toxins, the spoilage in foods, the presence of flavorings, or the presence of vapor emitting items, such as plant materials, fruits and vegetables, e.g., at customs portals.
  • Vapor-selective detectors or “artificial noses” are typically based upon the production of an interpretable signal or display upon exposure to a vapor emitting substance or odorant (hereinafter sometimes referred to as an “analyte”). More specifically, typical artificial noses are based upon selective chemical binding or an interface between a detecting compound of the artificial nose and an analyte or odorant, and then transforming that chemical binding into a signal or display, i.e., signal transduction.
  • Polymer arrays having a single dye have been used for artificial noses. That is, a series of chemically-diverse polymers or polymer blends are chosen so that their composite response distinguishes a given odorant or analyte from others.
  • Examples of polymer array vapor detectors including conductive polymer and conductive polymer/carbon black composites, are discussed in: M. S. Freund, N. S. Lewis, Proc. Natl. Acad. Sci. USA 92,2652-2656 (1995); B. J. Doleman, R. D. Sanner, E. J. Severin, R. H. Grubbs, N. S. Lewis, Anal. Chem. 70, 2560-2564 (1998); T. A.
  • interface materials include functionalized self-assembled monolayers (SAM), metal oxides, and dendrimers.
  • SAM functionalized self-assembled monolayers
  • SAW surface acoustic wave
  • Optical transducers (based on absorbance or luminescence) have also been examined. Examples of metal oxide, SAM, and dendrimer-based detectors are discussed in J. W. Gardner, H. V. Shurmer, P. Corcoran, Sensors and Actuators B 4, 117-121 (1991); J. W. Gardner, H. V. Shurmer, T. T. Tan, Sensors and Actuators B 6, 71-75 (1992); and R. M. Crooks, A. J. Ricco, Acc. Chem. Res. 31, 219-227 (1998). These devices also use a single dye.
  • the present invention comprises an array of dyes including at least a first dye and a second dye which in combination provide a spectral response distinct to an analyte or odorant.
  • the dyes of the present invention produce a response in the spectrum range of about 200 nanometers to 2,000 nanometers, which includes the visible spectrum of light. It has now been discovered that an array of two or more dyes responds to a given ligating species with a unique color pattern spectrally and in a time dependent manner. Thus, dyes in the array of the present invention are capable of changing color in a distinct manner when exposed to any one analyte or odorant.
  • the pattern of colors manifested by the multiple dyes is indicative of a specific or given analyte. In other words, the pattern of dye colors observed is indicative of a particular vapor or liquid species.
  • the dyes of the array are porphyrins
  • the porphyrin dyes are metalloporphyrins.
  • the array will comprise ten to fifty distinct metalloporphyrins in combination.
  • Metalloporphyrins are preferable dyes in the present invention because they can coordinate metal-ligating vapors through open axial coordination sites, and they produce large spectral shifts upon binding of or interaction with metal-ligating vapors.
  • porphyrins, metalloporphyrins, and many dyes show significant color changes upon changes in the polarity of their environment; this so-called solvatochromic effect will give net color changes even in the absence of direct bonding between the vapor molecules and the metal ions.
  • metalloporphyrins produce intense and distinctive changes in coloration upon ligand binding with metal ligating vapors.
  • the present invention provides a means for the detection or differentiation and quantitative measurement of a wide range of ligand vapors, such as amines, alcohols, and thiols. Further, the color data obtained using the arrays of the present innovation may be used to give a qualitative fingerprint of an analyte, or may be quantitatively analyzed to allow for automated pattern recognition and/or determination of analyte concentration. Because porphyrins also exhibit wavelength and intensity changes in their absorption bands with varying solvent polarity, weakly ligating vapors (e.g., arenes, halocarbons, or ketones) are also differentiable.
  • weakly ligating vapors e.g., arenes, halocarbons, or ketones
  • the parent porphyrin is also referred to as a free base (“FB”) porphyrin, which has two central nitrogen atoms protonated (i.e., hydrogen cations bonded to two of the central pyrrole nitrogen atoms).
  • FB free base
  • a preferred parent porphyrin is depicted in FIG. 2A, with the substitution of a two hydrogen ion for the metal ion (depicted as “M”) in the center of the porphyrin.
  • TTP stands for 5,10,15,20-tetraphenylporphyrinate(-2).
  • colorimetric difference maps can be generated by subtracting unexposed and exposed metalloporphyrin array images (obtained, for example, with a common flatbed scanner or inexpensive video or charge coupled device (“CCD”) detector) with image analysis software.
  • CCD charge coupled device
  • the present invention provides unique color change signatures for the analytes, for both qualitative recognition and quantitative analysis.
  • Sensor plates which incorporate vapor sensitive combinations of dyes comprise an embodiment of the present invention which is economical, disposable, and can be utilized to provide qualitative and/or quantitative identification of an analyte.
  • a catalog of arrays and the resultant visual pattern for each analyte can be coded and placed in a look-up table or book for future reference.
  • the present invention includes a method of detecting an analyte comprising the steps of forming an array of at least a first dye and a second dye, subjecting the array to an analyte, inspecting the first and second dyes for a spectral response, and comparing the spectral response with a catalog of analyte spectral responses to identify the analyte.
  • sensing is based upon either covalent interaction (i.e., ligation) or non-covalent solvation interactions between the analyte and the porphyrin array, a broad spectrum of chemical species is differentiable. While long response times (e.g., about 45 minutes) are observed at low analyte concentrations of about 1 ppm with large reverse phase silica gel plates, use of impermeable solid supports (such as polymer- or glass-based micro-array plates) or of small (e.g., about 1 square cm.) substantially increases the low-level response to about 5 minutes.
  • an object of the present invention to provide methods and devices for artificial olfaction, vapor-selective detectors or artificial noses for a wide variety of applications. It is another object of the present invention to provide methods of detection and artificial noses that can detect low levels of odorants and/or where odorants may be harmful to living human, animal or plant cells. It is also an object of the present invention to provide methods of olfactory detection and artificial noses that can detect and quantify many different chemicals for dosimeters that can detect chemical poisons or toxins, that can detect spoilage in foods, that can detect flavorings and additives, and that can detect plant materials, e.g., fruits and vegetables.
  • Another object of the present invention is to provide for the detection of analytes using data analysis/pattern recognition techniques, including automated techniques.
  • FIG. 1 illustrates an embodiment of the optical sensing plate of the present invention using a first elution in the y axis and a second elution in the x axis of the plate.
  • the first elution R—OH/hexane and the second elution is R—SH/hexane.
  • FIG. 2A illustrates an embodiment of the invention using metalloporphyrins as the sensing dyes.
  • FIG. 2B illustrates an embodiment of the invention using metalloporphyrins as the sensing dyes.
  • FIG. 3A illustrates a vapor exposure apparatus for demonstration of the present invention.
  • FIG. 3B illustrates a vapor exposure apparatus for demonstration of the present invention.
  • FIG. 4 illustrates the color change profile in a metalloporphyrin array of FIG. 2 when used in the vapor exposure apparatus of FIG. 3A to detect n-butylamine. Metalloporphyrins were immobilized on reverse phase silica gel plates.
  • FIG. 5 illustrates a comparison of color changes at saturation for a wide range of analytes.
  • Each analyte was delivered to the array as a nitrogen stream saturated with the analyte vapor at 20° C.
  • DMF stands for dimethylformamide
  • THF stands for tetrahydrofuran.
  • FIG. 6 illustrates two component saturation responses of mixtures of 2-methylpyridine and trimethylphosphite. Vapor mixtures were obtained by mixing two analyte-saturated N 2 streams at variable flow ratios.
  • FIG. 7 illustrates a comparison of Zn(TPP) spectral shifts upon exposure to ethanol and pyridine (py) in methylene chloride solution (A) and on the reverse phase support (B).
  • FIG. 8 illustrates another embodiment of the present invention, and more particularly, an small array comprising microwells built into a wearable detector which also contains a portable light source and a light detector, such as a charge-coupled device (CCD) or photodiode array.
  • a wearable detector which also contains a portable light source and a light detector, such as a charge-coupled device (CCD) or photodiode array.
  • CCD charge-coupled device
  • FIG. 9 illustrates another embodiment of the present invention, and more particularly, a microwell porphyrin array wellplate constructed from polydimethylsiloxane (PDMS).
  • PDMS polydimethylsiloxane
  • FIG. 10 illustrates another embodiment of the present invention, and more particularly, a microplate containing machined teflon posts, upon which the porphyrin array is immobilized in a polymer matrix (polystyrene/dibutylphthalate).
  • a polymer matrix polystyrene/dibutylphthalate
  • FIG. 11 illustrates another embodiment of the present invention, showing a microplate of the type shown in FIG. 10, consisting of a minimized array of four metalloporphyrins, showing the color profile changes for n-octylamine, dodecanethiol, and tri-n-butylphosphine, each at 1.8 ppm.
  • FIG. 12 illustrates the immunity of the present invention to interference from water vapor.
  • FIG. 13 illustrates the synthesis of siloxyl-substituted bis-pocket porphyrins in accordance with the present invention.
  • FIGS. 14 a , 14 b , and 14 c illustrate differences in K eq for various porphyrins.
  • FIG. 15 illustrates molecular models of Zn(Si 6 PP) (left column) and Zn(Si 8 PP) (right column).
  • FIG. 1 A sensor plate 10 fabricated in accordance with the present invention is shown in FIG. 1.
  • Sensor plate 10 comprises a two-dimensionally spatially resolved array 12 of various sensing elements or dyes 14 capable of changing color upon interaction (e.g., binding, pi-pi complexation, or polarity induced shifts in color).
  • a library of such dyes 14 can be given spatial resolution by two-dimensional chromatography or by direct deposition, including, but not limited to, ink-jet printing, micropipette spotting, screen printing, or stamping.
  • metalloporphyrin mixture 6 is placed at origin 7 .
  • Sensor plate 10 can be made from any suitable material or materials, including but not limited to, chromatography plates, paper, filter papers, porous membranes, or properly machined polymers, glasses, or metals.
  • FIG. 1 also illustrates an embodiment of the optical sensing plate of the present invention using a first elution 8 in the y axis and a second elution 9 in the x axis of sensor plate 10 .
  • the first elution 8 is R—OH/hexane
  • the second elution 9 is R—SH/hexane.
  • the order of the first and second elutions can be reversed.
  • the first and second elutions are used to spatially resolve the metalloporphyrin mixture 6 in silica gel 5 . As shown in FIG.
  • the upper left hand quadrant 3 is characterized by metalloporphyrins that are “hard” selective, i.e., having a metal center having a high chemical hardness, i.e., a high charge density.
  • the lower right hand quadrant 2 is characterized by metalloporphyrins that are “soft” selective, i.e., having a metal center having a low chemical hardness, i.e., a low charge density.
  • the array can be a spatially resolved collection of dyes, and more particularly a spatially resolved combinatorial family of dyes.
  • a porphyrin-metalloporphyrin sensor plate was prepared and then used to detect various odorants. More specifically, solutions of various metalated tetraphenylporphyrins in either methylene chloride or chlorobenzene were spotted in 1 ⁇ L aliquots onto two carbon (“C2”, i.e, ethyl-capped) reverse phase silica thin layer chromatography plates (Product No. 4809-800, by Whatman, Inc., Clifton, N.J.) to yield the sensor array 16 seen in FIG. 2B. As shown in FIG. 2B and summarized in Table 1 below, the dyes have the following colors (the exact colors depend, among other things, upon scanner settings).
  • FIG. 2A A metalloporphyrin 15 , sometimes referred to as M(TPP), of the present invention is depicted in FIG. 2A.
  • FIG. 2A also depicts various metals of the metalloporphyrins 15 of the present invention, and corresponding metal ion charge to radius ratio (i.e., Z/r Ratio) in reciprocal angstroms.
  • the Z/r Ratio should preferably span a wide range in order to target a wide range of metal ligating analytes.
  • These metalloporphyrins have excellent chemical stability on the solid support and most have well-studied solution ligation chemistry.
  • Reverse phase silica was chosen as a non-interacting dispersion medium for the metalloporphyrin array 16 depicted in FIG.
  • FIG. 3A illustrates a vapor exposure apparatus 19 of the present invention.
  • FIG. 3B illustrates top and side views of bottom piece 21 and a top view of top piece 21 ′ of a vapor exposure flow cell 20 of the present invention.
  • each sensor plate 18 was placed inside of a stainless steel flow cell 20 equipped with a quartz window 22 as shown in FIGS. 3A and 3B. Scanning of the sensor plate 18 was done on a commercially available flatbed scanner 24 (Hewlett Packard Scanjet 3c) at 200 dpi resolution, in full color mode. Following an initial scan, a control run with a first pure nitrogen flow stream 26 was performed.
  • Hewlett Packard Scanjet 3c Hewlett Packard Scanjet 3c
  • the array 16 of plate 18 was then exposed to a second nitrogen flow stream 28 saturated with a liquid analyte 30 of interest.
  • the nitrogen flow stream 28 saturated with liquid analyte 30 results in a saturated vapor 32 .
  • Saturated vapor 32 , containing the analyte 30 of interest were generated by flowing nitrogen flow stream 28 at 0.47 L/min. through the neat liquid analyte 30 in a water-jacketed, glass fritted bubbler 34 . Vapor pressures were controlled by regulating the bubbler 34 temperature.
  • vapor channels 23 permit vapor flow to sensor plate 18 .
  • RGB red, green and blue
  • the system has parallels the mammalian olfactory system.
  • the dyes have the following colors in scans 42, 44, and 46. TABLE 2 (Summarizing Colors of Dyes in FIG. 4, Scans 42, 44, and 46) Sn 4+ —No Change Co 3+ —Green Cr 3+ —Green Mn 3+ —No Change Fe 3+ —Red Co 2+ —Faint Green Cu 2+ —No Change Ru 2+ —No Change Zn 2+ —Light Green Ag 2+ —No Change 2H + (Free Base “FB”)—Light Blue
  • porphyrins have been shown to exhibit wavelength and intensity changes in their absorption bands with varying solvent polarity, it is contemplated that the methods and apparatus of the present invention can be used to colorimetrically distinguish among a series of weakly ligating solvent vapors (e.g., arenes, halocarbons, or ketones), as shown for example in FIG. 5.
  • weakly ligating solvent vapors e.g., arenes, halocarbons, or ketones
  • FIG. 5 A comparison of color changes at saturation for a wide range of analytes is shown in FIG. 5. Each analyte is identified under the colored array 16 that identifies each analyte.). DMF stands for the analyte dimethylformamide, and THF stands for the analyte tetrahydrofuran. As shown in FIG. 5 and summarized in Table 4 below, the colors of each dye in response to a particular analyte are as follows.
  • the degree of ligand softness increases from left to right, top to bottom as shown in FIG. 1.
  • Each analyte is easily distinguished from the others, and there are family resemblances among chemically similar species (e.g., pyridine and n-hexylamine). Analyte distinction originates both in the metal-specific ligation affinities and in their specific, unique color changes upon ligation.
  • Each analyte was delivered to the array as a nitrogen stream saturated with the analyte vapor at 20° C. (to ensure complete saturation, 30 min. exposures to vapor were used. Although these fingerprints were obtained by exposure to saturated vapors (thousands of ppm), unique patterns can be identified at much lower concentrations.
  • the metalloporphyrin array 16 has been used to quantify single analytes and to identify vapor mixtures. Because the images' color channel data (i.e., RGB values) vary linearly with porphyrin concentration, we were able to quantify single porphyrin responses to different analytes. Color channel data were collected for individual spots and plotted, for example, as the quantity (R plt ⁇ R spt )/(R plt ), (where R plt was the red channel value for the initial silica surface and R spt the average value for the spot. For example, Fe(TFPP)(Cl) responded linearly to octylamine between 0 and 1.5 ppm. Other porphyrins showed linear response ranges that varied with ligand affinity (i.e., equilibrium constant).
  • the array of the present invention has demonstrated interpretable and reversible responses even to analyte mixtures of strong ligands, such as pyridines and phosphites, as is shown in FIG. 6. Color change patterns for the mixtures are distinct from either of the neat vapors. Good reversibility was demonstrated for this analyte pair as the vapor mixtures were cycled between the neat analyte extremes, as shown in FIG. 6, which shows the two component saturation responses to mixtures of 2-methylpyridine (“2MEPY”) and trimethylphosphite (“TMP”). Vapor mixtures were obtained by mixing the analyte-saturated N 2 streams at variable flow ratios.
  • strong ligands such as pyridines and phosphites
  • a single plate was first exposed to pure trimethylphosphite vapor in N 2 (Scan A), followed by increasing mole fractions of 2-methylpyridine up to pure 2-methylpyridine vapor (Scan C), followed by decreasing mole fractions of 2-methylpyridine back to pure trimethylphosphite vapor.
  • Response curves for the individual porphyrins allow for quantification of the mixture composition.
  • FIG. 7 shows a comparison of Zn(TPP) spectral shifts upon exposure to ethanol and pyridine (py) in methylene chloride solution (A) and on the reverse phase support (B).
  • the bands correspond, from left to right, to Zn(TPP), Zn(TPP)(C 2 H 5 OH), and Zn(TPP)(py), respectively.
  • Solution spectra (A) were collected using a Hitachi U-3300 spectrophotometer; Zn(TPP), C 2 H 5 OH, and py concentrations were approximately 2 ⁇ M, 170 mM, and 200 ⁇ M, respectively.
  • Diffuse reflectance spectra (B) were obtained with an integrating sphere attachment before exposure to analytes, after exposure to ethanol vapor in N 2 , and after exposure to pyridine vapor in N 2 for 30 min. each using the flow cell.
  • the present invention contemplates miniaturization of the array using small wells 60 ( ⁇ 1 mm), for example in glass, quartz, or polymers, to hold metalloporphyrin or other dyes as thin films, which are deposited as a solution, by liquid droplet dispersion (e.g., airbrush or inkjet), or deposited as a solution of polymer with metalloporphyrin.
  • small wells 60 ⁇ 1 mm
  • liquid droplet dispersion e.g., airbrush or inkjet
  • FIGS. 8, 9, and 10 These embodiments are depicted in FIGS. 8, 9, and 10 .
  • FIG. 8 illustrates the interfacing of a microplate 60 into an assembly consisting of a CCD 70 , a microplate 72 and a light source 74 .
  • FIG. 9 illustrates another embodiment of the present invention, and more particularly, a microwell porphyrin array wellplate 80 constructed from polydimethylsiloxane (PDMS).
  • PDMS polydimethylsiloxane
  • FIG. 10 demonstrates deposition of metalloporphyrin/polymer (polystyrene/dibutylphthalate) solutions upon a plate, which includes a series of micro-machined Teflon® posts 100 having the same basic position relative to each other as shown in FIG. 2A and FIG. 2B.
  • the colors for the dyes in the middle of FIG. 10 are summarized in Table 7 below.
  • FIG. 11 shows the color profile changes from a microplate of the type shown in FIG. 10.
  • the microplate consisting of a minimized array of four metalloporphyrins, i.e., Sn(TPP)(Cl 2 ), Co(TPP)(Cl), Zn(TPP), Fe(TFPP)(Cl), clockwise from the upper left (where TFPP stands for 5,10,15,20-tetrakis(pentafluorophenyl)porphyrinate).
  • TFPP stands for 5,10,15,20-tetrakis(pentafluorophenyl)porphyrinate.
  • FIG. 12 illustrates the immunity of the present invention to interference from water vapor.
  • the hydrophobicity of the reverse phase support greatly any possible effects from varying water vapor in the atmosphere to be tested.
  • a color fingerprint generated from exposure of the array to n-hexylamine (0.86% in N 2 ) was identical to that for n-hexylamine spiked heavily with water vapor (1.2% H 2 O, 0.48% hexylamine in N 2 ). See scans 120, 122 and 124.
  • the ability to easily detect species in the presence of a large water background represents a substantial advantage over mass-sensitive sensing techniques or methodologies that employ polar polymers as part of the sensor array.
  • analytes e.g., n-hexylamine vs. cyclohexylamine.
  • Functionalized metalloporphyrins that limit steric access to the metal ion are candidates for such differentiation. For instance, we have been able to control ligation of various nitrogenous ligands to dendrimer-metalloporphyrins and induce selectivities over a range of more than 10 4 .
  • TTMPP slightly-hindered tetrakis(2,4,6-trimethoxyphenyl)porphyrins
  • porphyrins include those whose periphery is decorated with dendrimer, siloxyl, phenyl, t-butyl and other bulky substituents, providing sterically constrained pockets on at least one face (and preferably both) of the porphyrin.
  • the sensor plates of the present invention can be used for the detection of analytes in liquids or solutions, or solids.
  • a device that detects an analyte in a liquid or solution or solid can be referred to as an artificial tongue.
  • the metal complexes and the solid support must preclude their dissolution into the solution to be analyzed. It is preferred that the surface support repel any carrier solvent to promote the detection of trace analytes in solution; for example, for analysis of aqueous solutions, reverse phase silica has advantages as a support since it will not be wetted directly by water.
  • Alternative sensors in accordance with the present invention may include any other dyes or metal complexes with intense absorbance in the ultraviolet, visible, or near infrared spectra that show a color change upon exposure to analytes.
  • These alternative sensors include, but are not limited to, a variety of macrocycles and non-macrocycles such as chlorins and chlorophylls, phthalocyanines and metallophthalocyanines, salen-type compounds and their metal complexes, or other metal-containing dyes.
  • the present invention can be used to detect a wide variety of analytes regardless of physical form of the analytes. That is, the present invention can be used to detect any vapor emitting substance, including liquid, solid, or gaseous forms, and even when mixed with other vapor emitting substances, such solution mixtures of substances.
  • the present invention can be used in combinatorial libraries of metalloporphyrins for shape selective detection of substrates where the substituents on the periphery of the macrocycle or the metal bound by the porphyrin are created and then physically dispersed in two dimensions by (partial) chromatographic or electrophoretic separation.
  • the present invention can be used with chiral substituents on the periphery of the macrocycle for identification of chiral substrates, including but not limited to drugs, natural products, blood or bodily fluid components.
  • the present invention can be used for analysis of biological entities based on the surface proteins, oligosacharides, antigens, etc., that interact with the metalloporphyrin array sensors of the present invention. Further, the sensors of the present invention can be used for specific recognition of individual species of bacteria or viruses.
  • the present invention can be used for analysis of nucleic acid sequences based on sequence specific the surface interactions with the metalloporphyrin array sensors.
  • the sensors of the present invention can be used for specific recognition of individual sequences of nucleic acids.
  • Substituents on the porphyrins that would be particularly useful in this regard are known DNA intercalating molecules and nucleic acid oligomers.
  • the present invention can be used with ordinary flat bed scanners, as well as portable miniaturized detectors, such as CCD detectors with microarrays of dyes such as metalloporphyrins.
  • the present invention can be used for improved sensitivity, automation of pattern recognition of liquids and solutions, and analysis of biological and biochemical samples.
  • the present invention includes modified porphyrins that have a superstructure bonded to the periphery of the porphyrin.
  • a superstructure bonded to the periphery of the porphyrin in accordance with the present invention includes any additional structural element or chemical structure built at the edge of the porphyrin and bonded thereto.
  • the superstructures can include any structural element or chemical structure characterized in having a certain selectivity.
  • the superstructures of the present invention include structures that are shape selective, polarity selective, inantio selective, regio selective, hydrogen bonding selective, and acid-base selective. These structures can include siloxyl-substituted substituents, nonsiloxyl-substituted substituents and nonsiloxyl-substituted substituents, including but not limited to aryl substituents, alkyl substituents, and organic, organometallic, and inorganic functional group substituents.
  • a number of modified porphyrins have been synthesized to mimic various aspects of the enzymatic functions of heme proteins, especially oxygen binding (myoglobin and hemoglobin) and substrate oxidation (cytochrome P-450). See Suslick, K. S.; Reinert, T. J. J. Chem. Ed. 1985, 62, 974; Collman, J. P.; Zhang, X.; Lee, V. J.; Uffelman, E. S.; Brauman, J. I. Science 1993,261, 1404; Collman, J. P.; Zhang, X. in Comprehensive Supramolecular Chemistry; Atwood, J. L.; Davies, J. E. D.; MacNicol, D.
  • the present invention includes the synthesis, characterization and remarkable shape-selective ligation of silylether-metalloporphyrin scaffolds derived from the reaction of 5,10,15,20-tetrakis(2′,6′-dihydroxyphenyl)porphyrinatozinc(II) with t-butyldimethylsilyl chloride, whereby the two faces of the Zn(II) porphyrin were protected with six, seven, or eight siloxyl groups.
  • Ligation to Zn by classes of different sized ligands reveal shape selectivities as large as 10 7 .
  • a family of siloxyl-substituted bis-pocket porphyrins were prepared according to the scheme of FIG. 13.
  • the abbreviations of the porphyrins that can be made in accordance with the scheme shown in FIG. 13 are as follows:
  • the synthesis of Zn[(OH) 6 PP], Zn(Si 6 PP), and Zn(Si 8 PP) is detailed below.
  • Zn[(OH) 6 PP] and Zn[(OH) 8 PP] were obtained (see Bhyrappa, P.; Vaijarnahimala, G.; Suslick, K. S. J. Am. Chem. Soc.
  • t-butyldimethylsilyl groups were incorporated into the metalloporphyrin by stirring a DMF solution of hydroxyporphyrin complex with TBDMSiCl (i.e., t-butyldimethylsilyl chloride) in presence of imidazole. See Corey, E. J; Venkateswarlu, A. J. Am. Chem. Soc. 1972, 94, 6190.
  • the octa (Zn(Si 8 PP)), hepta (Zn(Si 7 OHPP)), and hexa (Zn(Si 6 PP)) silylether porphyrins were obtained from Zn[(OH) 8 PP] and Zn[(OH) 6 PP], respectively.
  • the compounds were purified by silica gel column chromatography and fully characterized by UV-Visible, 1 H-NMR, HPLC, and MALDI-TOF MS.
  • the binding constants of silylether porphyrins are remarkably sensitive to the shape and size of the substrates relative to Zn(TPP). See FIGS. 14 a , 14 b , and 14 c .
  • the binding constants of different amines could be controlled over a range of 10 1 to 10 7 relative to Zn(TPP). It is believed that these selectivities originate from strong steric repulsions created by the methyl groups of the t-butyldimethylsiloxyl substituents. The steric congestion caused by these bulky silylether groups is pronounced even for linear amines and small cyclic amines (e.g., azetidine and pyrrolidine).
  • silylether porphyrins showed remarkable selectivities for normal, linear amines over their cyclic analogues.
  • K eq were very similar for each of the silylether porphyrins.
  • the relative K eq for linear versus cyclic primary amines FIG. 14 a , n-butylamine vs.
  • K eq linear /K eq cyclic ranges from 1 to 23 to 115 to >200 for Zn(TPP), Zn(Si 6 PP), Zn(Si 7 OHPP), and Zn(Si 8 PP), respectively.
  • the ability to discriminate between linear and cyclic compounds is thus established.
  • FIG. 14 b A series of cyclic 2° amines (FIG. 14 b ) demonstrate the remarkable size and shape selectivities of this family of bis-pocket porphyrins. Whereas the binding constants to Zn(TPP) with those amines are virtually similar. In contrast, the K eq values for silylether porphyrins strongly depend on the ring size and its peripheral substituents. The effect of these shape-selective binding sites is clear, even for compact aromatic ligands with non-ortho methyl substituents (FIG. 14 c ).
  • FIG. 15 illustrates molecular models of Zn(Si 6 PP) (left column) and Zn(Si 8 PP) (right column).
  • the pairs of images from top to bottom are cylinder side-views, side-views, and top-views, respectively; space filling shown at 70% van der Waals radii; with the porphyrin carbon atoms shown in purple, oxygen atoms in red, silicon atoms in green, and Zn in dark red.
  • the x-ray single crystal structure of Zn(Si 8 PP) is shown; for Zn(Si 6 PP), an energy-minimized structure was obtained using Cerius 2 from MSI.
  • the Zn derivative was obtain by stirring methanol solution of H 2 [(OH) 6 PP] with excess Zn(O 2 CCH 3 ) 2 2H 2 O for 1 hour. Methanol was evaporated to dryness and the residue was dissolved in ethylacetate, washed with water, and the organic layer passed through anhyd. Na 2 SO 4 . The concentrated ethylacetate solution was passed through a silica gel column and the first band was collected as the desired product. The yield of the product was nearly quantitative.
  • the hexasilylether porphyrin was synthesized by stirring a DMF solution of 5-phenyl-10,15,20-tris(2 / ,6 / -dihydroxyphenyl)-porphyrinatozinc(II) (100 mg, 0.13 mmol) with t-butyldimethyl silylchloride (1.18 g, 7.8 mmol) in presence of imidazole (1.2 g, 17.9 mmol) at 60° C. for 24 h under nitrogen. After this period the reaction mixture was washed with water and extracted in CHCl 3 . The organic layer was dried over anhyd. Na 2 SO 4 .
  • the crude reaction mixture was loaded on a short silica gel column and eluted with mixture of CHCl 3 /petether (1:1, v/v) to get rid of unreacted starting material and lower silylated products.
  • the desired compound was further purified by running another silica gel column chromatography using mixture of CHCl 3 /petether (1:3, v/v) as eluant.
  • the yield of the product was 60% based on starting hydroxyporphyrin.
  • the hepta-and octa-silylether porphyrins were synthesized by stirring DMF solution of 5,10,15,20-tetrakis(2 / ,6 / -dihydroxyphenyl)porphyrinatozinc(II) (100 mg, 0.12 mmol) with t-butyldimethyl silylchloride (1.45 g, 9.6 mmol) in presence of imidazole (1.50 g, 22.1 mmol) at 60° C. for 24 h under nitrogen. After usual work-up the mixture of crude products were loaded on a silica gel column and eluted with mixture of CHCl 3 /pet.
  • ether (1:1, v/v) to remove unreacted starting material and lower silylated products.
  • the major product isolated from this column is a mixture of hepta- and octa-silylated porphyrins.
  • the mixture thus obtained was further purified by another silica gel column chromatography using mixture of CHCl 3 /pet. ether (1:3, v/v) as eluant.
  • the first two bands were isolated as octa- and hepta-silylether porphyrin at 45% and 30% yield, respectively. Both the compounds were characterized by UV-Visible, 1 H NMR and MALDI-TOF spectroscopic techniques. The homogeneity of the sample was verified by HPLC.

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EP1274983A1 (de) 2003-01-15
US20030143112A1 (en) 2003-07-31
BR0109432A (pt) 2004-06-22
WO2001071318A1 (en) 2001-09-27
AU2001247660A1 (en) 2001-10-03
US7261857B2 (en) 2007-08-28
US20030166298A1 (en) 2003-09-04
CN1430726A (zh) 2003-07-16
EP1274983B1 (de) 2012-02-01

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