EP1931971A1 - Inorganic polymers and use of inorganic polymers for detecting nitroaromatic compounds - Google Patents
Inorganic polymers and use of inorganic polymers for detecting nitroaromatic compoundsInfo
- Publication number
- EP1931971A1 EP1931971A1 EP05791438A EP05791438A EP1931971A1 EP 1931971 A1 EP1931971 A1 EP 1931971A1 EP 05791438 A EP05791438 A EP 05791438A EP 05791438 A EP05791438 A EP 05791438A EP 1931971 A1 EP1931971 A1 EP 1931971A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymer
- copolymer
- metallole
- quenching
- analyte
- 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.)
- Withdrawn
Links
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- 238000010791 quenching Methods 0.000 claims abstract description 69
- 230000000171 quenching effect Effects 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 43
- 238000005424 photoluminescence Methods 0.000 claims abstract description 29
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- 239000000758 substrate Substances 0.000 claims abstract description 13
- 229920000620 organic polymer Polymers 0.000 claims abstract description 8
- 239000012736 aqueous medium Substances 0.000 claims abstract description 6
- 239000012080 ambient air Substances 0.000 claims abstract description 3
- 239000012491 analyte Substances 0.000 claims description 41
- PWYVVBKROXXHEB-UHFFFAOYSA-M trimethyl-[3-(1-methyl-2,3,4,5-tetraphenylsilol-1-yl)propyl]azanium;iodide Chemical compound [I-].C[N+](C)(C)CCC[Si]1(C)C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 PWYVVBKROXXHEB-UHFFFAOYSA-M 0.000 claims description 24
- 239000002360 explosive Substances 0.000 claims description 22
- GMRJIOFCAMKRNJ-UHFFFAOYSA-N 1$l^{2}-germole Chemical compound [Ge]1C=CC=C1 GMRJIOFCAMKRNJ-UHFFFAOYSA-N 0.000 claims description 17
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 9
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
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- 238000005263 ab initio calculation Methods 0.000 description 2
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- 125000003456 2,6-dinitrophenyl group Chemical group [H]C1=C([H])C(=C(*)C(=C1[H])[N+]([O-])=O)[N+]([O-])=O 0.000 description 1
- YWSPWKXREVSQCA-UHFFFAOYSA-N 4,5-dimethoxy-2-nitrobenzaldehyde Chemical compound COC1=CC(C=O)=C([N+]([O-])=O)C=C1OC YWSPWKXREVSQCA-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- IDWXCSWWFNBRDD-UHFFFAOYSA-N CC1=C(C)C(C)=C(C)[SiH2]1 Chemical compound CC1=C(C)C(C)=C(C)[SiH2]1 IDWXCSWWFNBRDD-UHFFFAOYSA-N 0.000 description 1
- 241000282472 Canis lupus familiaris Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YQUNADBGHGGNFD-UHFFFAOYSA-N ClC=1C(=C(C=CC=1)C=1[SiH2]C(=C(C=1C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1)Cl Chemical compound ClC=1C(=C(C=CC=1)C=1[SiH2]C(=C(C=1C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1)Cl YQUNADBGHGGNFD-UHFFFAOYSA-N 0.000 description 1
- 229910005742 Ge—C Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- 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.
- PDEBSF Poly(l,4-diethynylbenzene)silafluorene
- PDEBGF PoIy(1, 4- diethynylbenzene)germafluorene
- PSF Polysilafluorene
- PPF Polygermafluorene
- 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.
- Metallole-silane copolymers were developed so that they could be easily functionalized along the backbone by hydrosilation.
- 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.
- 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.
- 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).
- 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.
- 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.
- 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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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 |
WO2013091432A1 (en) * | 2011-12-19 | 2013-06-27 | 中国科学院大连化学物理研究所 | Conjugated microporous macromolecule catalyst complexed with cobalt, chromium, zinc, copper or aluminium, preparation and use thereof |
CN103157513B (en) * | 2011-12-19 | 2015-02-11 | 中国科学院大连化学物理研究所 | Aluminum complexing conjugated micropore polymer catalyst, preparation thereof and application |
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