Effect of film thickness, blending and undercoating on optical detection of nitroaromatics using fluorescent polymer films

In this work, using a fluorescent poly(phenylene ethynylene) containing the rigid pentiptycene and large cholesteryl ester pendent groups, the fluorescence quenching properties of the polymer thin films in response to vapor of 2,4-dinitrotulene (DNT) have been investigated by varying the film thickness, applying an undercoating and blending with another polar polymer. A significant change in fluorescence intensity (51% in 60 s) in response to DNT vapor exposure at ambient temperature was achieved when the polymer film coated on glass plate was about 2 nm in thickness. In comparison with the film of polymer alone, the film undercoated with (3-aminopropyl)triethoxysilane and the film of polymer blend containing a non-fluorescent polymer showed additional 18.5% (in 20-s exposure) and 18.7% (in 5-min exposure) decrease in fluorescence intensity, respectively. The use of polymer or polymer blend coated on optic-fiber tip for detection of DNT vapor has also been demonstrated.     

Synthesis,characterization and fluorescence quenching of conjugated polymer containing triphenylamine group

Poly(triphenylamine-p-phenylenevinylene)s with two different end-groups were obtained through a Wittig polycondensation. The structures of two copolymers were characterized. Ultraviolet and visible spectroscopy (UV-Vis) and photoluminescence (PL) spectra show the end-capped polymer emits intensive green light in both solution and film state. Their applications in the detection of nitro compounds were investigated, and the results show high fluorescence quenching sensitivity of the end-capped polymer towards o-nitrotoluene (o-NT). When the concentration of o-NT was 21.5 × 10^-3 mol/L, the fluorescence quenching reached 96%. Additionally, after the exposure of polymer film in three different quenchers such as dinitrotoluene (DNT), p-nitrobenzoquinone (p-BQ) and p-nitrotoluene (p-NT) for 600 s, its fluorescence quenching reached 93.6%, 11.5% and 77.9%, respectively. This kind of polymer has great advantages in preparation and may find applications in the detection of nitro explosives.     

Insoluble porous conjugated polymer films via phase separation and photo‐crosslinking for the trace detection of 2,4‐dinitrotoluene

A novel conjugated polymer film with microscale/submicroscale porous morphology fabricated from crosslinked poly(fluorene‐co‐carbazole) (PFC1) was developed for the detection of 2,4‐dinitrotoluene (DNT). The fluorescent conjugated polymer PFC1 with pendant photo‐crosslinkable coumarin groups was synthesized by Suzuki coupling polymerization. Taking advantage of the phase separation of PFC1/polystyrene (PS) blends in the film and the solvent‐resistant network, porous structured films were prepared by removal of PS. Films with porous morphologies exhibited marked responsive sensitivity to trace DNT vapor due to the unique porous structure favoring the diffusion of and association with DNT molecules. The formation of a crosslinked network by dimerization of the coumarin moieties may be beneficial for isolating the polymeric backbones, thus to some extent preventing chain aggregation. This facile fabrication method enabled the crosslinked porous films to be efficient fluorescence chemosensors towards the detection of trace amounts of DNT vapor.© 2012 Society of Chemical Industry     

硝基芳烃爆炸物检测用荧光传感聚合物研究进展

使用荧光传感方法对硝基芳烃类爆炸物进行检测是当前研究的热点。在近年来用于检测的荧光聚合物中,侧链羟基型芴类聚合物对TNT的荧光淬灭效率最高,达到50%(20s);蝶烯基聚对苯乙炔撑型聚合物对DNT的荧光淬灭效率最高,达到75%(10s)。在国内外科研现状分析的基础上,提出了我国产业化道路发展方向的建议,对有前景的聚合物结构特点进行了点评。引用文献16篇。     

Synthesis, characterization and fluorescence quenching of conjugated polymer containing triphenylamine group

Poly(triphenylamine-p-phenylenevinylene)s with two different end-groups were obtained through a Wittig polycondensation. The structures of two copolymers were characterized. Ultraviolet and visible spectroscopy (UV-Vis) and photoluminescence (PL) spectra show the end-capped polymer emits intensive green light in both solution and film state. Their applications in the detection of nitro compounds were investigated, and the results show high fluorescence quenching sensitivity of the end-capped polymer towards o-nitrotoluene (o-NT). When the concentration of o-NT was 21.5 × 10⁻³ mol/L, the fluorescence quenching reached 96%. Additionally, after the exposure of polymer film in three different quenchers such as dinitrotoluene (DNT), p-nitrobenzoquinone (p-BQ) and p-nitrotoluene (p-NT) for 600 s, its fluorescence quenching reached 93.6%, 11.5% and 77.9%, respectively. This kind of polymer has great advantages in preparation and may find applications in the detection of nitro explosives. __________ Translated from Journal of Functional Polymers, 2008, 21(1): 11–16 [译自: 功能高分子学报]     

Conformation of single PMMA chain in uniaxially stretched film studied by scanning near-field optical microscopy

The conformation of the single polymer chain in uniaxially stretched poly(methyl methacrylate) (PMMA) films was studied by scanning near-field optical microscopy (SNOM), which enabled us to observe the elongated conformation of each polymer chain embedded in the film. The conformation of the individual PMMA chains was quantitatively evaluated from the fluorescence intensity distribution. Observation of films with different strains showed that the microscopic strain of the single chain was smaller than the macroscopic strain (?) of the film. Especially at the later stage of the deformation (? > 1.5), the PMMA chain was not stretched with the increase in the macroscopic elongation of the film, suggesting the presence of slipping of polymer chain on the course of stretching.     

Synthesis and photophysical properties of a charm-bracelet type C60-grafted PPV derivative

Synthesis and photophysical properties of a new soluble C₆₀-grafted PPV polymer have been described. Fluorescence quenching of the PPV moiety in C₆₀-grafted PPV polymer was observed, suggesting the energy- and/or electron transfer within the polymer. The fluorescence decay profiles at around 500 nm of this polymer both in chloroform and benzonitrile display a single exponential decay giving the fluorescence lifetimes of 1.10-1.27 ns, which are slightly shorter than that of PPV (about 1.50 ns). The nanosecond transient absorption band of C₆₀-grafted PPV polymer was observed at 740 nm corresponded to the excited triplet state of C₆₀, which decreased in benzonitrile, indicating the existence of the extra decay path of the singlet excited state of the C₆₀ other than intersystem crossing. Upon heating this polymer exhibits typical semilunar liquid crystalline texture, being closely associated with its polymeric structure with long solubilizing alkoxy side chains.     

Synthesis of terpyridine-functionalized poly(phenylenevinylene)s: The role of meta-phenylene linkage on the Cu and Zn chemosensors

A meta-phenylene-containing poly(phenylenevinylene) (PPV) with pendant terdentate terpyridine ligand 2b was synthesized and its fluorescence properties were compared with its isomeric PPV. The meta-phenylene bridge interrupts the resonance connection between the PPV backbone and the metal-chelation sites, while jointing the structurally defined chromophores together. The fluorescence of the polymer, with emission λ_em = 460 nm and ?_fl ≈ 0.45, is found to be selectively quenched by Cu²⁺ ion with interference from Co²⁺ and Ni²⁺ ions. The nature of the quenching process in 2b is probed by using Stern-Volmer analysis, revealing that the quenching results from both dynamic collision and metal chelation. Addition of Zn²⁺ and Cd²⁺ ions only induces partial fluorescence quenching, accompanied with a broad new emission band occurring at ∼560 nm. With the aid of a model compound study, the new emission band at 560 nm is attributed to the complex formation with terpyridine to Zn ratio of 1:1. The study finds that the polymer has the potential for Cu²⁺ and Zn²⁺ sensors.     

Synthesis and electroluminescence properties of a novel tetraphenylsilane-oxadiazole-diphenyl(para-tolyl)amine polymer

A novel triarylaminooxadiazole-containing tetraphenylsilane light-emitting polymer (PTOA) has been synthesized. Excellent thermal stability was observed due to the presence of a rigid tetraphenylsilane-based polymer backbone (T_g = 218 °C, T_d = 373 °C). In solution, PTOA shows photoluminescence (PL) with an emission maximum at 426 nm, which is attributed to the light-emitting unit of the triarylaminooxadiazole group. In solid film, the emission maximum of PL is observed at 458 nm, a 32 nm red-shift from the PL in solution. The solvatochromic effect and excimer formed in the solid film are responsible for the red-shifting and broadening of the PL emission band. The PL stability and morphology of the PTOA solid film were further investigated by thermal annealing at elevated temperatures. No significant difference in the PL spectra or morphology was observed between a pristine sample and a repeatedly thermally annealed film (at 200 °C). PTOA-based PLED shows EL with a main peak at 458 nm accompanied by a shoulder at around 530 nm. The light emission from electromer or electroplex leads to a broadening of the EL spectra (400-650 nm), which corresponds to the interaction between the oxadiazole and diphenyl(4-tolyl)amine groups in different polymer segments or chains. A sky blue emission (Commission Internationale de L'Eclairage (CIE_x,y) coordinates (0.20,0.23)) was obtained for PTOA-based PLED. The brightness and efficiency of the PLED can be as high as 248 cd/m² and 0.54 cd/A, respectively. The EL of PTOA-based PLED has been further improved by blending the PTOA with poly(n-vinylcarbazole) (PVK) in different concentrations. The effects of concentration on the PL and EL were studied for the PTOA-PVK composite film-based PLEDs.     

Dependence of relaxation processes in a low-density polyethylene with different crosslink densities investigated by fluorescence spectroscopy

Relaxation processes of one type of low-density polyethylene with three different degrees of crosslinking were studied using the fluorescence of 1-pyrenyl groups attached covalently to polymer chains. The average molecular weights between crosslinks (M_c) of the polyethylenes were 125, 76.5, and 7 kg mol⁻¹. As assessed by changes of the integrated fluorescence intensity and the full width at half maximum of the 0-0 emission band with temperature, chain mobility decreases with increasing crosslinking density. Chain mobility in the polyethylene with the smallest M_c value appears to be strongly inhibited up to 220 K, while motions of small segments of the polymer chains were observed for samples with lower crosslinking degrees at temperatures similar to those of the pristine (non-crosslinked) polymer. These data are discussed in terms of local versus bulk properties of the films.     

Efficient and color pure blue light emitting random copolymer with fluorene and fluorenylstilbene

A blue electroluminescent polymer, random copolymer of fluorenylstilbene and fluorene, was prepared by the nickel catalyzed coupling reaction. The structure and properties of the copolymer were analyzed by various spectroscopic methods. The obtained polymer had good solubility and thermal stability with high T_g. The polymer in thin film emits strong blue luminance (max=468 nm) with narrow bandwidth upon photoexcitation. PL spectrum of the polymer in the film is almost consistent with that of solution one as well as the EL spectrum, indicating that the aggregation and the excimer fluorescence are suppressed by the introduction of fluorenylstilbene comonomer. Moreover, the introduction of fluorenylstilbene comonomer lowered the oxidation potential to lead feasible hole injection, when the compared with poly(fluorene) homopolymer. The ITO/PEDOT/polymer/LiF/Al device showed the maximum brightness of 3500 cd/m² with a turn on voltage of 4.4, the maximum efficiency of 0.878 lm/W and blue emission with CIE chromaticity coordinates of ((x,y)=(0.17, 0.25)).     

Chemical anchoring of silica nanoparticles onto polyaniline chains via electro-co-polymerization of aniline and N-substituted aniline grafted on surfaces of SiO2

Chemical anchoring of silica nanoparticles onto polyaniline (PANI) chains was conducted through electro-co-polymerization of aniline and N-substituted aniline grafted on surfaces of silica nanoparticles. The grafting of N-substituted aniline on surfaces of silica nanoparticles were realized through hydrolysis of triethoxysilylmethyl N-substituted aniline (ND42) and the following condensation reaction with silanol groups on surfaces of SiO₂. Organic-inorganic interactions between PANI and SiO₂ involved in electro-co-polymerization process pushed the polymer chains apart and so facilitated the 1D growth of the polymer. Hence, the obtained hybrid film PANI/ND42-SiO₂ displayed nano-fibrous morphologies (ca. 50 nm in diameter). Consequently, PANI/ND42-SiO₂ exhibited an average specific capacitance of 380 F g⁻¹, ca. 40% higher than that of PANI/SiO₂ (276 F g⁻¹). The hybrid film also showed improved cyclic stability.     

Reversible thickness control of polymer thin films containing photoreactive coumarin derivative units

The reversible control of the thickness of polymer thin films was investigated using (meth)acrylic polymers containing photoreactive coumarin derivative units in the side chain. Coumarin derivative units underwent dimerization and the reverse-dimerization by photoirradiation and were used as a reversible cross-linking point. The homopolymer of 7-methacryloyloxy-4-methylcoumarin (T_g = 194 °C) did not cause changes in film thickness after photoreactions. The homopolymer of 7-(2′-acryloyloxyethoxy)-4-methylcoumarin (AEMC) (T_g = 89 °C) decreased 19% of film thickness by photodimerization and 73% of the decreased thickness was recovered after the reverse-dimerization and the subsequent thermal annealing at 130 °C. The reverse-dimerization of the copolymer of AEMC and n-butyl acrylate (AEMC content = 19 mol%, T_g = 11 °C) resulted in 53% of recovery from the decreased film thickness without annealing. The mobility of polymer main-chain was revealed to be essential factor to change film thickness by photoreactions. Photodimerization of coumarin derivative units in low glass transition temperature (T_g) tended to proceed faster than in high T_g polymers and resulted in larger decrease in film thickness.     

Polysulfones tethered with benzimidazole

Benzimidazole units have been grafted onto a polysulfone (PSU) backbone via long alkyl thio-ether chains using a two-step procedure. In the first step, lithiated PSU was reacted with 10-undecenoyl chloride to graft PSU with undecenoyl side chains. The second step involved a free-radical thiol-ene coupling reaction between the CC bonds of the pendant undecenoyl chains and 2-(2-benzimidazolyl)ethanethiol. In this reaction, all the CC bonds were converted into thio-ether linkages without any detectable structural degradation, as confirmed by ¹H NMR spectroscopy and size-exclusion chromatography. The procedure constitutes a convenient and general pathway to attach functional or mesogenic groups to PSU via long flexible spacers. Thermogravimetry showed that the benzimidazole-functionalized polymers were stable up to 250 °C under nitrogen atmosphere, and that the first degradation step was attributed to the cleavage of the thio-ether bond. While the grafting of the undecenoyl side chains was found to significantly decrease the glass transition temperature (T_g), the subsequent tethering of the benzimidazole only slightly increased the T_g of the grafted PSU backbone. The concentration of benzimidazole was probably too low for the formation of a percolating benzimidazole domain. This explains the quite modest proton conductivity measured under completely dry conditions, e.g. 34 nS/cm at 180 °C for a polymer functionalized with 1.7 benzimidazole units per repeating unit of PSU.     

Swelling behavior of amphiphilic gels based on hydrophobically modified dimethylaminoethyl methacrylate

The amphiphilic gels based on hydrophobically modified dimethylaminoethyl methacrylate with different 1-bromoalkanes (1-C_nH_2n+1Br, n = 2, 4, 6, 8, 12) were synthesized by radiation-induced polymerization and crosslinking. The length of alkyl side chains had significant influence on the swelling behavior of the resulting gels. The swelling degree of the gels decreased with the increase of side chain length, and the gel hardly swelled when n = 12. The effect of temperature and ionic strength on the swelling behavior of the resulting gels revealed that (1) the gels with longer side chains (n ≥ 8) had upper critical solution temperature, while other gels were not thermo-sensitive. (2) Antipolyelectrolyte effect was observed when immersing the gels (n ≥ 8) in NaCl solutions in certain concentration range. The dramatic difference in swelling behavior was attributed to the different gel structures. The gels with short side chains (n ≤ 6) had cellular structure of normal polyelectrolyte gels. The gels (n ≥ 8) had an aggregation gel structure caused by the hydrophobic interaction among alkyl groups and the formation of ion-cluster between tetra-alkyl ammonium cation and Br⁻, which had been analyzed with the aid of SEM, Br⁻-selective electrode and fluorescence molecular probe.     

High glass transition and thermal stability of new pyridine-containing polyimides: Effect of protonation on fluorescence

A new diamine monomer containing heterocyclic pyridine and triphenylamine groups, 4-(4,4′-diaminotriphenylamine)-2,6-bis(4-methylphenyl)pyridine (4), was synthesized by Chichibabin and nucleophilic fluoro-displacement reactions. The diamine was used to prepare a series of novel polyimides via polycondensation with various aromatic tetracarboxylic dianhydrides in N-methyl-2-pyrrolidinone. The polyimide 4a derived from the diamine 4 with 4,4′-hexafluoroisopropylidenediphthalic anhydride and having high T_g (313 °C), mechanical, and thermal properties was soluble in various organic solvents, such as N-methyl-2-pyrrolidinone, N,N-dimethylacetamide, N,N-dimethylformamide, pyridine, chloroform, tetrahydrofuran, at room temperature. The polyimide (4a) could be cast into a self-standing film from DMAc solution and was thermally converted into tough and flexible film. The film had high tensile modulus of 2.2 GPa and exhibited excellent thermal stability in both nitrogen and air (T_d¹⁰ > 550 °C). The pristine polymer exhibited the UV-vis absorption bands in the region 240-400 nm and protonated polymer exhibited absorption in the region 390-500 nm. The protonated polymer possessed strong orange fluorescence (around 600 nm) in THF solution after protonation with acids as excited at 438 nm. The fluorescent intensity was influenced by the acid concentrations and the chemical structure of conjugated bases. The fluorescent intensity at 600 nm increased as acid concentration from a lower to a moderate concentration and decreased at higher concentrations.     

A new conducting polymer bearing 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) subunit: Synthesis and characterization

A new monomer system based on thiophene, pyrrole and 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene dye (SNS-BODIPY) was synthesized and its corresponding polymer (PSNS-BODIPY) was obtained via repetitive cycling or constant potential electrolysis in 0.1 M tetrabutylammonium hexafluorophosphate dissolved in dichloromethane. The PSNS-BODIPY film has very stable and well-defined reversible redox couples during p-doping process. Multi-electrochromic polymer film has a band gap of 2.9 eV with two absorption bands in its neutral state at 351 and 525 nm, attributed to the polymer backbone and BODIPY subunits, respectively. The percentage transmittance changes between both states (neutral and oxidized) were found as 12.1% for 351 nm and 17.7% for 525 nm in the visible region as well as 46.2% for 1050 nm in the near-infrared region. Beyond the robustness, the PSNS-BODIPY film has high redox stability (retaining 53.3% of its electroactivity at 351 nm after 2000 switching) with a low response time of 1.0 s.     

Synthesis of a soluble conjugated copolymer based on dialkyl-substituted dithienothiophene and its application in photovoltaic cells

A soluble conjugated alternating 3,5-didecanyldithieno[3,2-b:2′,3′-d]thiophene-thiophene copolymer was synthesized by palladium(0)-catalyzed Stille coupling reaction. The thermal, absorption, emission, electrochemical, and photovoltaic properties of the polymer were examined. A weight-average molecular weight around 6.2 × 10⁴ and a polydispersity index of 1.8 was estimated for the polymer using gel permeation chromatography. The polymer exhibits good thermal stability with decomposition temperature of 340 °C and glass-transition temperature of 136 °C. The polymer shows strong absorption peaked at 505 nm in diluted solution and 518 nm in thin film with an optical band gap 2.0 eV. The polymer exhibits intense emission located at 550 nm in solution and 603 nm in film. The HOMO and LUMO energies of the polymer were estimated to be −5.4 and −3.4 eV, respectively, by cyclic voltammetry. Polymer solar cells were fabricated based on the blend of the polymer and methanofullerene [6,6]-phenyl C61-butyric acid methyl ester (PCBM). The power conversion efficiency of 0.7% was achieved under AM 1.5, 100 mW/cm² using polymer:PCBM (1:4, w/w) as active layer.     

Triphenylamine-based fluorescent conjugated glycopolymers: Synthesis, characterization and interactions with lectins

Two well-defined triphenylamine-based fluorescent conjugated glycopolymers were easily synthesized through Suzuki coupling polymerization of peracetylated galactopyranosyl-carrying monomer and consequent efficient deacetylation under Zemplén condition. Their structures were characterized using ¹H NMR, IR, and UV-vis spectroscopies. The preliminary insight into carbohydrate-lectin interactions was revealed by the titration of peanut agglutinin (PNA) to one of the final polymers, d-galactose-bearing poly(fluorene-alt-triphenylamine) copolymer (P-2), resulting in a significant fluorescence quenching of the polymer with a Stern-Volmer quenching constant of 1.56 × 10⁵ M⁻¹. Whereas no distinct change in the fluorescent properties of P-2 was observed when concanavalin A (Con A) was employed.     

All solid-state polymer electrolytes prepared from a hyper-branched graft polymer using atom transfer radical polymerization

We propose an all solid-state (liquid free) polymer electrolyte (SPE) prepared from a hyper-branched graft copolymer. The graft copolymer consisting of a poly(methyl methacrylate) main chain and poly(ethylene glycol) methyl ether methacrylate side chains was synthesized by atom transfer radical polymerization changing the average chain distance between side chains, side chain length and branched chain length of the proposed structure of the graft copolymer. The ionic conductivity of the SPEs increases with increasing the side chain length, branched chain length and/or average distance between the side chains. The ionic conductivity of the SPE prepared from POEM₉ whose POEM content = 51 wt% shows 2 × 10⁻⁵ S/cm at 30 °C. The tensile strength of the SPEs decreases with increases the side chain length, branched chain length and/or average distance between the side chains. These results indicate that a SPE prepared from the hyper-branched graft copolymer has potential to be applied to an all-solid polymer electrolyte.