WO2007024227A1 - Polymeres inorganiques et leur utilisation pour detecter des composes nitroaromatiques - Google Patents

Polymeres inorganiques et leur utilisation pour detecter des composes nitroaromatiques Download PDF

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WO2007024227A1
WO2007024227A1 PCT/US2005/030381 US2005030381W WO2007024227A1 WO 2007024227 A1 WO2007024227 A1 WO 2007024227A1 US 2005030381 W US2005030381 W US 2005030381W WO 2007024227 A1 WO2007024227 A1 WO 2007024227A1
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polymer
copolymer
metallole
quenching
analyte
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PCT/US2005/030381
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English (en)
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William C. Trogler
Sarah Urbas
Sarah J. Toal
Jason Sanchez
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The Regents Of The University Of California
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Priority to CA002620238A priority Critical patent/CA2620238A1/fr
Priority to EP05791438A priority patent/EP1931971A4/fr
Priority to US11/990,832 priority patent/US7927881B2/en
Priority to PCT/US2005/030381 priority patent/WO2007024227A1/fr
Publication of WO2007024227A1 publication Critical patent/WO2007024227A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/30—Germanium compounds
    • 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
    • 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
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6432—Quenching
    • 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
    • G01N2021/7769—Measurement method of reaction-produced change in sensor
    • G01N2021/7786—Fluorescence

Definitions

  • a field of the invention is analyte detection.
  • the instant invention is directed to inorganic polymers and use of inorganic polymers, namely photorecinescent metallole-containing polymers and copolymers, for detection of nitroaromatic compounds based on photoluminescence quenching.
  • Chemical sensors are preferable to other detection devices, such as metal detectors, because metal detectors frequently fail to detect explosives, such as in the case of the plastic casing of modern land mines. Similarly, trained dogs are both expensive and difficult to maintain.
  • Other detection methods such as gas chromatography coupled with a mass spectrometer, surface-enhanced Raman, nuclear quadrupole resonance, energy-dispersive X- ray diffraction, neutron activation analysis and electron capture detection are highly selective, but are expensive and not easily adapted to a small, low-power package.
  • vapor phase detection which is disadvantageous given the low volatility of many explosives.
  • the vapor pressure of TNT which is approximately 5 ppb at room temperature, may be up to six times lower when enclosed in a bomb or mine casing, or when present in a mixture with other explosives.
  • An embodiment of the present invention is a directed device and method for detecting solid-state, vapor phase and solution phase nitroaromatic compounds using an inorganic polymer sensor, namely photoluminescent metallole-containing polymers and copolymers.
  • the invention also includes a method for synthesizing an inorganic polymer sensor, namely photoluminescent metallole-containing copolymers.
  • FIGURE 1 is a model of a polysilole molecule;
  • FIG. 2 illustrates a pair of equations for the synthesis of polygermole and polysilole according to an embodiment of the invention;
  • FIG. 3 illustrates a pair of equations for the synthesis of a silole- germole copolymer according to an embodiment of the invention;
  • FIG. 4 illustrates a pair of equations for the synthesis of silole- silane alternating copolymers according to an embodiment of the invention
  • FIG. 5 is a table of the absorption and fluorescence spectra observed in one embodiment of the instant invention and taken at the concentrations of 2 mg/L in THF and 10 mg/L in toluene, respectively;
  • FIG. 6 is a schematic energy level diagram illustrating energy- levels for polymetalloles and metallole-silane copolymers
  • FIG. 7 is a graphical representation of UV- vis absorption spectra " in THF (solid line) and fluorescence spectra in toluene (dotted line) for (A) poly(tetraphenyl) germole 2. (B) silole-silane copolymer 4, and (C) germole- "silane copolymer 9;
  • FIGs. 8A and 8B illustrate a HOMO (A) and LUMO (B) of 2.5- diphenylsilole, Ph 2 C 4 SiH 2 from the ab initio calculations at the HF/6-31G* level;
  • FIG. 9 is a graphical representation of the fluorescence spectra of polysilole 1 in toluene solution (solid line) and in thin solid film (dotted line);
  • FIG. 10 is a graphical representation of the quenching of photoluminescence spectra of silole-silane copolymer 5 with (A) nitrobenzene, from top 2.0 x 10-5 M, ; 3.9 x 10 '5 M, 7.8 x 10 "5 M, and 11.5 x 10 "5 M, (B) DNT, from top 1.4 x 10 "5 M 5 3.9 x 10 '5 M, 7.8 x 10 "5 M, and 12.4 x 10 "5 M, (C) TNT, from top 2.1 x 10 "5 M 5 4.2 x 10 "5 M 5 8.1 x 10 "5 M 5 and 12.6 x 10 "5 M 5 (D) picric acid, from top 2.1 x 10 '5 M, 4.2 x 10 "5 M 5 8.0 x 10 '5 M, and 12.6 x 10 "5 M; FIGs.
  • HA, HB and 11C are Stern- Volmer plots; from top polysilole 1, polygermole 2, and silole-silane copolymer 8; ⁇ (picric acid), ⁇ (TNT), ⁇ (DNT), • (nitrobenzene); the plots of fluorescence lifetime ( ⁇ o / ⁇ ), shown as inset, are independent of added TNT; FIG. 12 illustrates fluorescence decays of polysilole 1 for different concentrations of TNT: 0 M, 4.24 x 10 "5 M, 9.09 x 10 ⁇ 5 M, 1.82 x 10 "4 M;
  • FIG. 13 illustrates Stern- Volmer plots of polymers ⁇ (polymer
  • FIG. 14 illustrates a structure of the pentiptycene-derived polymer
  • FIG. 15 illustrates, from left to right, highest and lowest photoluminescence quenching efficiency for picric acid (left-most two lines), TNT (two lines immediately to the right of picric acid), DNT (two lines immediately to the right of TNT), and nitrobenzene (right-most two lines) showing how the varying polymer response to analyte could be used to distinguish analytes from each other;
  • FIG. 16 illustrates a comparison of the photoluminescence quenching constants (from Stern- Volmer plots) of polymers 1-12 with different nitroaromatic analytes
  • FIG 17 illustrates a plot of log K vs reduction potential of analytes: ⁇ (polymer 1), ⁇ (polymer 2), ⁇ (polymer 3), • (polymer 4), O (polymer 5), and (polymer 10);
  • FIG. 18 illustrates a schematic diagram of electron-transfer mechanism for quenching the photoluminescence of polymetallole by analyte;
  • FIG. 19 illustrates an absence of quenching of photoluminescence by polysilole 1 with 4 parts per hundred of THF; and
  • FIG. 20 illustrates an equation for a catalytic dehyrdocoupling method for synthesizing metallole polymers according to one embodiment of the invention.
  • FIGs. 21a, 21b and 21c illustrate various copolymers as well as their syntheses, namely PDEBSi 3 PDEBGe, PDEBSF, PDEBGF, PSF and PGF;
  • FIG. 22 is a table summarizing the detection limits of TNT, DNT, and picric acid using the five metallole-containing polymers synthesized, PSi, PDEBSi, PGe, PDEBGe, and PDEBSF;
  • FIG. 23 are black and white images of the luminescence quenching of three polymers, PSi, PDEBSi, and PGe, by 200, 100, 50, and 10 ng TNT on porcelain plates as observed on a porcelain plate;
  • FIG. 24 are exemplary black and white images of the luminescence quenching of polysilole by each analyte at different surface concentrations.
  • Solid state sensing may be especially desirable for trace residue detection on surfaces believed to be contaminated, such as, for example, where filter paper is used to swab or wipe a surface of interest and the filter paper is subsequently subjected to analysis.
  • Conventional solid state detection kits such as that manufactured under the brand name ExPray® by Plexus Scientific Corporation of Alexandria, VA are able to detect various explosive through a color change, with sensitivity down to the tens of nanogram level.
  • the vapor pressure of TNT may be up to 6 times lower when enclosed in a bomb or mine casing or when present in mixtures with other explosives.
  • embodiments of the invention include the solid-state detection of trace residue of nitroaromatics, such as picric acid (PA, 2,4,6-trinitrophenol or C 6 H 2 (NO 2 ) 3 OH), nitrobenzene (NB or C 6 H 5 NO 2 ), 2,4-dinitrotoluene (DNT or C 7 H 6 N 2 O 4 ) and 2,4,6-trinitrotoluene (TNT or C 7 H 5 N 3 O 6 ), using thin films of luminescent metallole-containing polymers.
  • PA picric acid
  • NB nitrobenzene
  • DNT 2,4-dinitrotoluene
  • DNT 2,4,6-trinitrotoluene
  • TNT or C 7 H 5 N 3 O 6
  • one preferred embodiment includes a method for detecting an analyte that may be present in ambient air, bound to a surface or as part of complex aqueous media that includes a metallole-containing polymer or copolymer being exposed to a system suspected of containing the analyte, such as on a solid surface or in an aqueous medium. By subsequently measuring the photoluminescence of the metallole-containing polymer or copolymer, the presence, absence and approximate quantity may be determined with great sensitivity.
  • Another preferred embodiment includes a metallole-containing polymer sensor for sensing trace amounts of nitroaromatic compounds that includes a metallole-containing polymer cast, sprayed or otherwise deposited on a surface suspected of containing the nitroaromatic compounds. It is contemplated that the solid surface on which detection may occur may include a virtually boundless number of surfaces, such as glass, paper, plastic, wood, porcelain or metal, to name a few.
  • embodiments of the invention include the synthesis and use of inorganic polymers, namely photoluminescent metallole-containing polymers and copolymers, in solid state or solution for detection of nitroaromatic compounds based on photoluminescence quenching.
  • Inorganic- organic polymers may be prepared by catalytic hydrosilation or hydrogermylation with dihydrosilole or dihydrogermole compounds and organic diynes or dialkenes.
  • the invention includes an inexpensive and highly efficient inorganic or inorganic-organic polymer sensor that can detect the existence of an analyte, namely nitroaromatic compounds such as picric acid, nitrobenzene, DNT and TNT in air, water, on surfaces, organic solution, or other complex aqueous media.
  • analyte namely nitroaromatic compounds such as picric acid, nitrobenzene, DNT and TNT in air, water, on surfaces, organic solution, or other complex aqueous media.
  • Photoluminescent metallole polymers are stable in air, water, acids, common organic solvents, and even seawater containing bioorganisms. Therefore, the inorganic polymer sensor of the instant invention includes the metallole copolymers for detection of analytes in these media. Importantly, the inorganic polymer sensors of the instant invention are insensitive to organic solvents and common environmental interferents, allowing the use of the sensor in a wide variety of environments and applications.
  • Metalloles are silicon (Si) or germanium (Ge)-containing metallocyclopentadienes that include one-dimensional Si-Si, Ge-Ge, or Si-Ge wires encapsulated with highly conjugated organic ring systems as side chains.
  • Polymetalloles and metallole-silane copolymers are unique in having both a M-M backbone as well as an unsaturated five-membered ring system. These polymers are highly photoluminscent, and are accordingly useful as light emitting diodes (LEDs) or as chemical sensors. Characteristic features of polymetalloles and metallole-silane copolymers include a low reduction potential and a low-lying lowest unoccupied molecular orbital (LUMO) due ⁇ *- ⁇ * conjugation arising from the interaction between the ⁇ * orbital of silicon or germanium and the ⁇ * orbital of the butadiene moiety of the five membered ring.
  • LUMO lowest unoccupied molecular orbital
  • the M-M backbones exhibit ⁇ *- ⁇ * derealization, which further delocalizes the conjugated metallole ⁇ electrons along the backbone. Electron derealization in these polymers provides a means of amplification, because interaction between an analyte molecule and any position along the polymer chain is communicated throughout the delocalized chain.
  • Detection may be accomplished by measurement of the quenching of photoluminescence of metallole copolymers by the analyte.
  • Sensitivity of metallole copolymers to the analytes picric acid, TNT, DNT and NB is as follows: PA > TNT > DNT > NB.
  • a plot of log K versus the reduction potential of analytes (NB, DNT, and TNT) for each metallole copolymer yields a linear relationship, indicating that the mechanism of quenching is attributable to electron transfer from the excited metallole copolymers to the lowest unoccupied orbital of the analyte. Excitation may be achieved with electrical or optical stimulation.
  • FIG. 1 illustrates a space filling model structure of polysilole 1, which features a Si-Si backbone inside a conjugated ring system of side chains closely packed to yield a helical arrangement.
  • FIG. 2 illustrates polymers 1 and 2
  • FIG. 3 illustrates polymer 3
  • FIG. 4 illustrates copolymers 4-12.
  • 21a through 21c illustrate additional copolymers as well as their syntheses, PoIy(1, 4-diethynylbenzene)2,3,4,5-tetraphenylsilole (PDEBsilole), Poly(l,4-diethynylbenzene)2,3,4,5-tetraphenylgermole (PDEBgermole),
  • PDEBSF Poly(l,4-diethynylbenzene)silafluorene
  • PDEBGF PoIy(1, 4- diethynylbenzene)germafluorene
  • PSF Polysilafluorene
  • PPF Polygermafluorene
  • a conventional method for preparing polymetalloles and metallole copolymers is Wurtz-type polycondensation.
  • the syntheses of polygermole and polysiloles, and other copolymers are analogous to one another, as illustrated in equation 1 in FIG. 2, and employ the Wurtz-type polycondensation.
  • yields from this method of synthesis are low (ca. -30%).
  • Wurtz-type polycondensation is not well-suited to large-scale production.
  • Embodiments of the instant invention include alternative methods for synthesizing polymetalloles that use catalytic dehydrocoupling of dihydrosiloles with a catalyst as an attractive alternative to Wurtz-type polycondensation.
  • Bis(cyclopentadienyl) complexes of Group 4 have been extensively studied and shown to catalyze the dehydrocoupling of hydrosilanes to polysilanes for the formation of Si-Si bonds.
  • the primary organosilanes react to give polysilane.
  • Secondary and tertiary silanes give dimers or oligomers in low yield. It has been reported that the reactivity decreases dramatically with increasing substitution at the silicon atom, since reactions catalyzed by metallocenes are typically very sensitive to steric effects.
  • Mechanisms for dehydrogenative coupling of silanes have also been extensively investigated, which involves ⁇ -bond metathesis.
  • Embodiments of the instant invention include catalytic dehydrocoupling of dihydrosiloles and dihydrogermoles with a catalyst.
  • the invention includes catalytic dehydrocoupling polycondensation of dihydro(tetraphenyl)silole or dihydro(tetraphenyl)germole with 1-5 mol % of Wilkinson's catalyst, Rh(PPh 3 ) 3 Cl, or Pd(PPh 3 ) 4 , as illustrated in FIG.
  • silole-germole alternating copolymer 3 in which every other silicon or germanium atom in the polymer chain is also part of a silole or germole ring, was synthesized from the coupling of dichloro(tetraphenyl)germole and dilithio(tetraphenyl)silole. The latter is obtained in 39% yield from dichlorotetraphenylsilole by reduction with lithium, as illustrated in the equation of FIG. 3.
  • silole-silane alternating copolymers 4, 5, 6, 7, 8, which were also prepared from coupling of the silole dianion (Ph 4 C 4 Si)Li 2 with the corresponding silanes.
  • Germole-silane alternation copolymers 9, 10, 11, 12 were also synthesized from the coupling of the germole dianion (Ph 4 C 4 Ge)Li 2 with the corresponding silanes, as illustrated in FIG. 4.
  • These reactions generally employ reflux conditions in tetrahydrofuran under an argon atmosphere for about 72 hours.
  • Some silole-silane copolymers have been synthesized previously and shown to be electroluminescent.
  • Metallole-silane copolymers were developed so that they could be easily functionalized along the backbone by hydrosilation.
  • the molecular weights and polydisperity indices (PDI) of polymers 1-12 (FIG. 4) determined by gel permeation chromatography (GPC) are illustrated in Table 1 of FIG. 5.
  • Inorganic-organic poly(l,4-diethynylbenzene)metallole (DEB) type polymers may be obtained by hydrosilation of an dialkyne, specifically DEB, with a dihydrometallole using a catalyst such as chloroplatinic acid.
  • FIGs. 21a-21c illustrate the reaction whereby the DEB type polymers are obtained according to embodiments of the invention.
  • a reasonable extension of this principle includes hydrosilation and hydrogermylation of any organic diyne.
  • a reasonable interpolation of this principle includes hydrosilation and hydrogermylation of organic dialkenes to obtain less conjugated polymers.
  • the UV-vis absorption and fluorescence spectral data for polymers 1-12 are also illustrated in Table 1 of FIG. 5.
  • the poly(tetraphenyl)metalloles 1-3 and tetraphenylmetallole-silane copolymers 4- 12 exhibit three absorption bands, which are ascribed to the ⁇ - ⁇ * transition in the metallole ring and the ⁇ -( ⁇ *+ ⁇ *) and ⁇ - ⁇ * transitions in the M-M backbone.
  • FIG. 6 illustrates a schematic energy-level diagram for polymetalloles and metallole-silane copolymers.
  • FIG. 8 shows the HOMO (A) and LUMO (B) of 2,5- diphenylsilole, Ph2C4SiH2, from the ab initio calculations at the HF/6-31G* level.
  • Phenyl substituents at the 2,5 metallole ring positions may ⁇ -conjugate with the metallole ring LUMO.
  • Second absorptions at wavelengths of 304 to 320 nm for the ⁇ oly(tetraphenylmetallole)s 2-3 and tetraphenylmetallole-silane copolymers 4-12 are assigned to the ⁇ - ( ⁇ 2 * + ⁇ *) transition, which parallels that of the poly(tetraphenyl)silole 1.
  • Polymetallole 1-2 and silole-silane copolymers 4-7 exhibit one emission band ( ⁇ max , 486 to 513 nm) when excited at 340 nm, whereas the others exhibit two emission bands with ⁇ max of 480-510 nm and 385-402 nm.
  • the ratios of the two emission intensities are not concentration dependent, which indicates that the transition does not derive from an excimer.
  • Emission peaks for germole-silane copolymers 9-12 are only 2 to 33 nm blue-shifted compared to the other polymers.
  • FIG. 9 shows fluorescence spectra of the poly(tetraphenyl)silole in toluene solution (solid line) and in the solid state (dotted line). The bandwidth of the emission spectrum in solution is slightly larger than in the solid state. There is no shift in the maximum of the emission wavelength. This suggests that the polysilole exhibits neither ⁇ -stacking of polymer chains nor excimer formation.
  • the angles of C-M-C of dihydro(tetraphenyl)silole and dihydro(tetraphenyl)germole are 93.11° on C-Si-C and 89.76° on C-Ge-C, respectively.
  • Polymerization might take place, since the tetraphenylmetalloles have small angles at C-M-C in the metallocyclopentadiene ring, which results in less steric hindrance at the metal center.
  • the bulky phenyl groups of silole might prevent the formation of cyclic hexamer, which is often problematic in polysilane syntheses. Cyclic polymetallole product formation was not observed.
  • the method of detection of the instant invention includes using a chemical sensor, namely a variety of photoluminscent copolymers having a metalloid-metalloid backbone such as Si-Si, Si-Ge, or Ge-Ge, or altelrnatively an inorganic-organic metallole-containing copolymer.
  • a chemical sensor namely a variety of photoluminscent copolymers having a metalloid-metalloid backbone such as Si-Si, Si-Ge, or Ge-Ge, or altelrnatively an inorganic-organic metallole-containing copolymer.
  • polymetalloles in various forms may be used to detect analytes
  • one embodiment includes casting a thin film of the copolymers is employed in detecting, the analyte, e.g., picric acid, DNT, TNT and nitrobenzene. Detection is achieved by measuring the quenching of the photoluminescence of the copolymer
  • the instant invention contemplates use of the polymetallole polymers and copolymers in any form susceptible to measurement of photoluminescence quenching.
  • other embodiments of the instant method of detection may optionally include a polymetallole in solution phase, where powdered bulk polymer is dissolved in solution.
  • Yet another embodiment includes producing a colloid of the polymer, which is a liquid solution with the polymer precipitated and suspended as nanoparticles.
  • the detection method involves measurement of the quenching of photoluminescence of the polymetalloles 1-3 and metallole-silane copolymers 4-12 by the analyte, such as a toluene solution (using a Perkin-Elmer LS 5OB fluorescence spectrometer, 340 nm excitation wavelength).
  • a toluene solution using a Perkin-Elmer LS 5OB fluorescence spectrometer, 340 nm excitation wavelength.
  • fluorescence spectra of a toluene solution of the metallole copolymers were obtained upon successive addition of aliquots of TNT.
  • Photoluminescence quenching of the polymers 1- 12 in toluene solutions were also measured with nitrobenzene, DNT, TNT and nitrobenzene.
  • the relative efficiency of photoluminescence quenching of metallole copolymers is unique for TNT, DNT, and nitrobenzene, respectively, as indicated in FIG. 10 by the values of K determined from the slopes of the steady-state Stern- Volmer plots.
  • FIG. 10 demonstrates that each copolymer has a unique ratio of quenching efficiency to the corresponding analyte.
  • the purity of the TNT sample was found to be important to obtain reproducible results. It was synthesized by nitration of dinitrotoluene and recrystallized twice from methanol. A third recrystallization produces the same results as the twice-recrystallized material. When the quenching experiment was undertaken without recrystallization of TNT, higher (ca. 10 x) quenching percentages are obtained. Presumably, impurities with higher quenching efficiencies are present in crude TNT.
  • FIG. 11 shows the Stern- Volmer plots of polysilole 1, polygermole 2, and silole-silane copolymer 8 for each analyte.
  • a linear Stern- Volmer relationship was observed in all cases, but the Stern- Volmer plot for picric acid exhibits an exponential dependence when its concentration is higher than 1.0 x 10 "4 M.
  • a linear Stern- Volmer relationship may be observed if either static or dynamic quenching process is dominant.
  • the two processes may be competitive, which results in a nonlinear Stern- Volmer relationship. This could also arise from aggregation of analyte with chromophore.
  • Photoluminescence may arise from either a static process, by the quenching of a bound complex, or a dynamic process, by collisionally quenching the excited state.
  • K sv is an association constant due to the analyte-preassociated receptor sites.
  • the collision rate of the analyte is not involved in static quenching and the fluorescence lifetime is invariant with the concentration of analyte.
  • the fluorescence lifetime should diminish as quencher is added.
  • a single “mean" characteristic lifetime ( ⁇ ) for polymetalloles and metallole-silane copolymers 1-12 has been measured and summarized in Table 1 of FIG. 5. Luminescence decays were not single-exponential in all cases.
  • the mean lifetime parameter reported is an average of the three lifetimes determined by the fitting procedure, weighted by their relative amplitudes. This is the appropriate average for comparison with the "amount" of light emitted by different samples under different quenching conditions, as has been treated in the literature. Given this heterogeneity, possible long-lived luminescence that might be particularly vulnerable to quenching has been a concern. However, measurements with a separate nanosecond laser system confirmed that there were no longer-lived processes other than those captured by the time-correlated photon counting measurement and incorporated into Table 1 of FIG. 5.
  • polysilole 1 and silole-silane copolymers 4-8 have about 3 to 11 times longer fluorescence lifetimes than polygermole 2 and germole-silane copolymers 9-12. Fluorescence lifetimes in the thin films (solid state) for polysilole 1 and polygermole 2 are 2.5 and 4.2 times longer than in toluene solution, respectively. The fluorescence lifetimes as a function of TNT concentration were also measured and are shown in the inset of Figure 11 for polymers 1, 2, and 8. No change of mean lifetime was observed by adding TNT, indicating that the static quenching process is dominant for polymetalloles and metallole-silane copolymers 1-12 (FIG. 12). Some issues with such analyses have been discussed in the literature. This result suggests that the polymetallole might act as a receptor and a TNT molecule would intercalate between phenyl substituents of the metallole moieties (FIG. 1).
  • FIG. 13 displays the Stern- Volmer plots of polymers 1, 2, 4, 5, and 6 for TNT, indicating that the range of photoluminescence quenching efficiency for TNT is between 2.05 x 10 3 and 4.34 x 10 3 M "1 .
  • Stern-Volmer constants usually reflects an enhanced charge-transfer interaction from metallole polymer to analyte.
  • the relative efficiency of photoluminescence quenching of polysilole 1 is about 9.2:3.6:2.0:1.0 for picric acid, TNT, DNT, and nitrobenzene, respectively.
  • polysilole 1 shows best photoluminescence quenching efficiency for picric acid and TNT
  • polymer 9 and 5 exhibit best quenching efficiency for DNT and nitrobenzene, respectively.
  • Polygermole 2 has the lowest quenching efficiency for all analytes.
  • Polysilole l (11.0 x 10 3 M “1 and 4.34 xlO 3 M “1 ) exhibits 164% and 212% better quenching efficiency than polygermole 2 (6.71 x 10 3 M “1 and 2.05 x 10 3 M “1 ) with picric acid and TNT, respectively.
  • Polymer 9 (2.57 x 10 3 M '1 ) has 253% better quenching efficiency than polymer 2 (1.01 x 10 3 M "1 ) with DNT.
  • Polymer 5 (1.23 x 10 3 M "1 ) has 385% better quenching efficiency than metallole polymer 2 (0.32 x 10 3 M '1 ) with nitrobenzene.
  • FIG. 16 illustrates how an analyte might be specified using an array of multi- sensors.
  • FIG. 17 shows a plot of log Ksv vs. reduction potential of analytes. All metallole polymers exhibit a linear relationship, even though they have different ratios of photoluminescence quenching efficiency to analytes. This result indicates that the mechanism of photoluminescence quenching is primarily attributable to electron transfer from the excited metallole polymers to the LUMO of the analyte.
  • TNT (-0.7 V vs NHE) is less negative than that of either DNT (-0.9 V vs NHE) or nitrobenzene (-1.15 V vs NHE), it is detected with highest sensitivity.
  • FIG. 18 A schematic diagram of the electron-transfer mechanism for the quenching of photoluminescence of the metallole polymers with analyte is shown in FIG. 18. Optical excitation produces an electron-hole pair, which is delocalized through the metallole copolymers. When an electron deficient molecule, such as TNT is present, electron-transfer quenching occurs from the excited metallole copolymer to the LUMO of the analyte.
  • metallole copolymers An important aspect of the metallole copolymers is their relative insensitivity to common interferents. Control experiments using both solutions and thin films of metallole copolymers (deposited on glass substrates) with air displayed no change in the photoluminescence spectrum. Similarly, exposure of metallole copolymers both as solutions and thin films to organic solvents such as toluene, THF, and methanol or the aqueous inorganic acids H 2 SO 4 and HF produced no significant decrease in photoluminescence intensity.
  • Figure 19 shows that the photoluminescence spectra of polysilole 1 in toluene solution display no quenching of fluorescence with 4 parts per hundred of THF.
  • the ratio of quenching efficiency of polysilole 1 with TNT vs benzoquinone is much greater than that of polymer 13.
  • NMR data were collected with Varian Unity 300, 400, or 500 MHz spectrometers (300.1 MHz for 1 H NMR, 75.5 MHz for 13 C NMR and 99.2 MHz for 29 Si NMR) and all NMR chemical shifts are reported in parts per million ( ⁇ ppm); downfield shifts are reported as positive values from tetramethylsilane (TMS) as standard at 0.00 ppm.
  • TMS tetramethylsilane
  • the 1 H and 13 C chemical shifts are reported relative to CHCl 3 ( ⁇ 77.0 ppm) as an internal standard, and the 29 Si chemical shifts are reported relative to an external TMS standard.
  • NMR spectra were recorded using samples dissolved in CDCl 3 , unless otherwise stated, on the following instrumentation.
  • the polymer was detected with a Waters Model 440 ultraviolet absorbance detector at a wavelength of 254 nm, and the data were manipulated using a Waters Model 745 data module. Molecular weight was determined relative to calibration from polystyrene standards. Fluorescence emission and excitation spectra were recorded on a Perkin-Elmer Luminescence Spectrometer LS 50B.
  • Monomers, l,l-dichloro-2,3,4,5- tetraphenylsilole, 1 , 1 -dichloro-2,3,4,5-tetraphenylgermole, 1 , 1 -dilithio- 2,3,4,5-tetraphenylsilole, and l,l-dilithio-2,3,4,5-tetraphenylgermole were synthesized by following the procedures described in the literature. All reactions were performed under Ar atmosphere.
  • metallole-silane and metallole-germane copolymers such as tetraalkylmetallole -silane copolymers and tetraarylmetallole-germane copolymers can be prepared by the above method described.
  • Reaction conditions for preparing the polygermole are the same as those for polysilole.
  • l,l-dihydro-2,3,4,5-tetraphenylsilole (1.0 g, 2.59 mmol) and 1-5 mol % of RhCl(PPh 3 ) 3 or Pd(PPh 3 ) 4 in toluene (10 mL) were placed under an Ar atmosphere and degassed through 3 freeze-pump-thaw cycles.
  • the reaction mixture was vigorously refluxed for 72 h.
  • the solution was passed rapidly through a Florisil column and evaporated to dryness under Ar atmosphere. 1 mL of THF was added to the reaction mixture and the resulting solution was then poured into 10 mL of methanol.
  • Poly(tetraphenyl)silole, 1, was obtained as a pale yellow powder after the third cycle of dissolving-precipitation followed by freeze-drying.
  • An alternative method for poly(tetraphenyl)silole preparation is as follows. l,l-dihydro-2,3,4,5-tetraphenylsilole (1.0 g, 2.59 mmol) and 0.1-0.5 mol % H 2 PtCl 6 -XH 2 O and 2-5 mol equivalents of allylamine in toluene (10 mL) were vigorously refluxed for 24 hours. The solution was passed through a sintered glass frit and evaporated to dryness under an Ar atmosphere.
  • 1,4-diethynylbenzene 34 mg, 0.26 mmol
  • 0.1-0.5 mol % H 2 PtCl 6 *xH 2 O were vigorously refluxed in toluene (10 mL), under argon for 12 hours.
  • the catalyst was removed by filtration, and the filtrate then evaporated to dryness.
  • the remaining solid was dissolved in THF (1 mL) and precipitated by subsequent addition of methanol (10 mL).
  • the polymer was collected by filtration and dried to afford the yellow powder (0.095 g, 73%).
  • 1,1 dihydrosilafluorene (0.25 g, 1.37 mmol), 1,4- diethynylbenzene (0.19 g, 1.51 mmol), and 0.1-0.5 mol % H 2 PtCl 6 -XH 2 O were vigorously refluxed in toluene (3 mL), under argon for 24 hours. The dark orange/red solution was filtered and evaporated to dryness. The remaining solid was dissolved in 4 ml of THF, precipitated with 40 ml of methanol. The white solid (0.17 g, 34%) was collected by filtration on a sintered glass frit. The molecular weight of the polymer was determined by GPC with polystyrene standards.
  • TNT trinitrotoluene
  • DNT dinitrotoluene
  • PA picric acid
  • DMNB 2,2'-dimethyl-2,2'-dinitrobutane
  • OMNT orthomononitrotoluene
  • PMNT paramononitrotoluene
  • 1,1 dihydrogermafluorene (0.15 g, 0.66 mmol), 1,4- diethynylbenzene (0.092 g, 0.73 mmol), and 0.1-0.5 mol % H 2 PtCl 6 « xH 2 O were vigorously refluxed in toluene (4 mL), under argon for 24 hours.
  • the dark orange-red solution was filtered and evaporated to dryness.
  • the remaining solid was dissolved in 4 ml of THF and precipitated with 40 ml of methanol.
  • the light orange solid (0.021 g, 15%) was collected by filtration on a sintered glass frit.
  • the molecular weight of the polymer was determined by GPC with polystyrene standards.
  • the method of explosives detection is through luminescence quenching of the metallole-containing polymers by the nitroaromatic analyte.
  • Three common explosives were tested, Trinitrotoluene (TNT), 2,4- dinitrotoluene (DNT), and picric acid (PA).
  • Stock solutions of the explosives were prepared in toluene. Aliquots (1-5 ⁇ L) of the stock (containing 5 to 100 ng analyte) were syringed onto either Whatman filter paper or a CoorsTek® porcelain spot plate and allowed to dry completely. The spots were between 3 and 10 mm in diameter, producing a surface concentration of not more than 64 ng/cm 2 and not less than 17 ng/cm 2 .
  • Solutions of the polymers were prepared in acetone (PSi, PGe), 1:1 toluene:acetone (PDEBGe), 2:1 toluene: acetone (PDEBSi), or toluene (PDEBSF).
  • a thin film of a polymer was applied to the substrate by spray coating a polymeric solution onto the substrate and air drying.
  • the coated substrates were placed under a black light to excite the polymer fluorescence. Dark spots in the film indicate luminescence quenching of the polymer by the analyte.
  • the process was carried out for each of the three explosive analytes with each of the six polymers on both substrates.
  • Nitroaromatic explosives may be visually detected in nanogram quantities by fluorescence quenching of photoluminescent metallole-containing polymers. Detection limits depend on the nitroaromatic analyte as well as on the polymer used.
  • FIG. 22 summarizes the detection limits of TNT 3 DNT, and picric acid using the five metallole-containing polymers synthesized, PSi, PDEBSi, PGe, PDEBGe, PSF and PDEBSF.
  • the detection limit of the explosives was as low or lower on the porcelain than on paper, likely because the solvated analyte may be carried deep into the fibers of the paper during deposition, thus lowering the surface contamination after solvent evaporation. Less explosive would be present to visibly quench the thin film of polymer on the surface. This situation is less pronounced in actuality when explosives are not deposited via drop-casting from an organic solution, but handled as the solid. Illumination with a black light ( ⁇ ex - 360 nm) excites the polymer fluorescence near 490 - 510 nm for the siloles, 470 - 500 for germoles.
  • FIG. 23 shows a sample black and white images of the luminescence quenching of three polymers, PSi, PDEBSi, and PGe, by 200, 100, 50, and 10 ng TNT on porcelain plates as observed on a porcelain plate.
  • FIG. 24 shows sample black and white images of the luminescence quenching of polysilole by each analyte at different surface concentrations. The method of detection is through electron-transfer luminescence quenching of the polymer luminescence by the nitroaromatic analytes.
  • the ability of the polymers to detect the explosives depends on the oxidizing power of the analytes.
  • the oxidation potentials of the analytes follow the order TNT > PA > DNT.
  • Both TNT and PA have three nitro substituents on the aromatic ring which account for their higher oxidizing potential relative to DNT, which has only two nitroaromatic substituents.
  • PA has a lower oxidation potential than TNT due to the electron donating power of the hydroxy substituent.
  • the molecular structure accounts for the lowest detection limit for TNT, followed by PA and DNT. Luminescence quenching is observed immediately upon illumination.
  • the polymers are photodegradable, however, and luminescence begins to fade after a few minutes of continual UV exposure. Nevertheless, these polymers present an inexpensive and simple means to detect low nanogram level of nitroaromatic explosives.

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Abstract

L'invention concerne un procédé permettant de détecter un analyte qui peut être présent dans l'air ambiant air, lié à une surface ou faisant partie d'un milieu aqueux complexe. Ledit procédé consiste: à fournir un polymère ou un copolymère de métallole, à exposer ce polymère ou ce copolymère à une analyse ou à un système suspecté de comprendre l'analyte, et à mesurer la désactivation de la photoluminescence du polymère ou du copolymère de métallole exposé audit système. L'invention concerne également un capteur polymère organique-inorganique à semi-conducteur permettant de détecter des composés nitroaromatiques qui comprend un substrat et un film mince de polymère ou de copolymère de métallole déposé sur ledit substrat.
PCT/US2005/030381 2002-10-05 2005-08-25 Polymeres inorganiques et leur utilisation pour detecter des composes nitroaromatiques WO2007024227A1 (fr)

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CA002620238A CA2620238A1 (fr) 2005-08-25 2005-08-25 Polymeres inorganiques et leur utilisation pour detecter des composes nitroaromatiques
EP05791438A EP1931971A4 (fr) 2005-08-25 2005-08-25 Polymeres inorganiques et leur utilisation pour detecter des composes nitroaromatiques
US11/990,832 US7927881B2 (en) 2002-10-05 2005-08-25 Inorganic polymers and use of inorganic polymers for detecting nitroaromatic compounds
PCT/US2005/030381 WO2007024227A1 (fr) 2005-08-25 2005-08-25 Polymeres inorganiques et leur utilisation pour detecter des composes nitroaromatiques

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WO2013091432A1 (fr) * 2011-12-19 2013-06-27 中国科学院大连化学物理研究所 Catalyseur macromoléculaire microporeux conjugué complexé avec du cobalt, du chrome, du zinc, du cuivre ou de l'aluminium, préparation et utilisation de celui-ci
US8557596B2 (en) 2007-07-18 2013-10-15 The Regents Of The University Of California Fluorescence detection of nitrogen-containing explosives and blue organic LED
US9134239B2 (en) 2011-03-21 2015-09-15 The Regents Of The University Of California Thin layer high explosive fluorescent polymer sensing methods, sensors and kits

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8557596B2 (en) 2007-07-18 2013-10-15 The Regents Of The University Of California Fluorescence detection of nitrogen-containing explosives and blue organic LED
US9134239B2 (en) 2011-03-21 2015-09-15 The Regents Of The University Of California Thin layer high explosive fluorescent polymer sensing methods, sensors and kits
CN103157513A (zh) * 2011-12-19 2013-06-19 中国科学院大连化学物理研究所 一种铝络合共轭微孔高分子催化剂及其制备和应用
WO2013091432A1 (fr) * 2011-12-19 2013-06-27 中国科学院大连化学物理研究所 Catalyseur macromoléculaire microporeux conjugué complexé avec du cobalt, du chrome, du zinc, du cuivre ou de l'aluminium, préparation et utilisation de celui-ci

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