Electrochemical polymerization of 3-fluoroalkoxy and 3-fluoroether thiophenes gives polymers with relatively high molecular weights and good processibility. Investigation of these polymers by means of GPC indicates th...Electrochemical polymerization of 3-fluoroalkoxy and 3-fluoroether thiophenes gives polymers with relatively high molecular weights and good processibility. Investigation of these polymers by means of GPC indicates that an increase in the number of fluorine atoms in the fluorinated group results in a decrease in degree of polymerization of the polymers in the same polythiophene series. As shown by NMR and FTIR, the polyfluorinated group substituted polythiophenes have regular 2, 5-coupling in their main chains. The SEM micrographs of the polymer films exhibit that polymer (1)-poly [3-2, 2, 3, 3-tetrafluoro-propoxy) thiophene] possesses more regular structure than the other polymers do. Substitution of polythiophenes by fluorinated groups leads to the polymers with high electric, electrochemical and thermal stability.展开更多
4,4＇-dibromo-2-nitro-biphenyl and 4,4＇-dibromo-2,3＇-dinitro-biphenyl have been synthesized via nitration reaction with 4,4＇-dibromobiphenyl as the raw material. Three novel thiophene derivatives, 4, 4＇-di（4-hexy...4,4＇-dibromo-2-nitro-biphenyl and 4,4＇-dibromo-2,3＇-dinitro-biphenyl have been synthesized via nitration reaction with 4,4＇-dibromobiphenyl as the raw material. Three novel thiophene derivatives, 4, 4＇-di（4-hexyl-thiophen-2-yl）biphenyl, 4,4＇-di（4-hexyl-thiophen-2-yl）-2- nitro-biphenyl and 4,4＇-di（4- hexyl-thiophen-2-yl）-2,3＇-dinitrobiphenyl were synthesized through Stille coupling reaction, followed by polymerization in the presence of FeC13, respectively. UV-vis absorption spectra, fluorescence spectra, photoluminescence spectra and electrochemical properties of the polymers were investigated. And the band-gap （Eg）, HOMO orbital energy （EHCMO）, and LUMO orbital energy （EUJMO） of the polymers were calculated. Among the polymers, polymer PBTN and PBTD show lower band-gap （2.67 and 2.63 eV）, lower HOMO energy level （-5.38 and -5.4 eV） and broader wavelength （432 and 438 nm） than that of polymer PBTB （2.69 eV, -5.36 eV and 424 nm） with incorporation of one nitro group or two nitro groups in the main chain, respectively.展开更多
Three series of polythiophenes containing fluoroalkoxy and fluoroether substituents were prepared by electrochemical polymerization. The effect of substituents with fluoroalkoxy or ether functional groups on the elect...Three series of polythiophenes containing fluoroalkoxy and fluoroether substituents were prepared by electrochemical polymerization. The effect of substituents with fluoroalkoxy or ether functional groups on the electrochemical polymerization of thiophene monomers and properties of the obtained polymers were analyzed. The introduction of a fluoroether functional group at the 3-position of the thiophene ring leads to an increase of the oxidation potential of the monomer and to a decrease of the conductivity of the resulting polymers, even with the use of a CH2 group as spacer. Conversely, the presence of an oxygen atom directly at the 3-position of the thiophene ring, which offsets the negative withdrawing effect of fluoroalkyl groups, facilitates the synthesis of highly conducting polythiophenes.展开更多
Four kinds of polythiophenes have been doped with CH3SO3H in CHCl3 under air,oxygen,and nitrogen. In the doping of two types of poly(3-hexylthiophene)s,P3HexTh(Zn/Ni)and P3HexTh(Fe)with different contents of a head-to...Four kinds of polythiophenes have been doped with CH3SO3H in CHCl3 under air,oxygen,and nitrogen. In the doping of two types of poly(3-hexylthiophene)s,P3HexTh(Zn/Ni)and P3HexTh(Fe)with different contents of a head-to-tail unit,the p-doping occurs at a similar rate.The reaction between poly(3-dodecylthiophene),P3DodTh,and the acid takes place more rapidly.P3OBuTh with a butoxy substituent undergoes more facile p-doping and receives photochemical reaction with CHCl3,and this reaction obeys a pseudo-first-order rate law with a rate constant kobs of 1.42×10-5s-1at room tempera- ture.展开更多
Chemosensor arrays have a great potential for on-site applications in real-world scenarios.However,to fabricate on chemosensor array a number of chemosensors are required to obtain various optical patterns for multian...Chemosensor arrays have a great potential for on-site applications in real-world scenarios.However,to fabricate on chemosensor array a number of chemosensors are required to obtain various optical patterns for multianalyte detection.Herein,we propose a minimized chemosensor array composed of only two types of carboxylate-functionalized polythiophene derivatives for the detection of eight types of metal ions.Upon recognition of the metal ions,the polythiophenes exhibited changes in their fluorescence intensity and various spectral shifts.Although both chemosensors have the same polymer backbone and recognition moiety,only the difference in the number of methylene groups contributed to the difference in the fluorescence response patterns.Consequently,the metal ions in aqueous media were successfully discriminated qualitatively and quantitatively by the chemosensor microarray on the glass chip.This study offers an approach for achieving a minimized chemosensor array just by changing the alkyl chain lengths without the necessity for many receptors and reporters.展开更多
A series of poly(fluoroalkoxy thiophenes) have been prepared by electrochemical and chemical polymerization respectively. The substitution of thiophene by polyfluorinated alkoxy chains affords more favorable structure...A series of poly(fluoroalkoxy thiophenes) have been prepared by electrochemical and chemical polymerization respectively. The substitution of thiophene by polyfluorinated alkoxy chains affords more favorable structures in electronic effect and higher stabilities of their polymers than conventional alkoxy chain substituted polymers.展开更多
Regioregular poly(3-hexylthio)thiopene(P3HTT) has emerged tremendous potential in organic electronic applications due to the strong noncovalent interactions from the sulfur atom linked to thiophene. However, P3HTT gen...Regioregular poly(3-hexylthio)thiopene(P3HTT) has emerged tremendous potential in organic electronic applications due to the strong noncovalent interactions from the sulfur atom linked to thiophene. However, P3HTT generally exhibits low charge mobility mostly due to poor solution processability attributed to dense arrangement of hexylthio side chain in polymer, which led to strong noncovalent interactions among sulfur atoms. To balance the nonvalent interaction and aggregation for P3HTT, herein, we systematically study the effect of hexylthio side chain content in polymer backbone on the structure and properties. A series of regioregular P3HTT-based homopolymers(P3HTT, P3HTT-50,P3HTT-33 and P3HTT-25) were prepared via Kumada catalyst transfer polycondensation method from a set of mono-, bi-, ter-and quarterthiophenes containing different contents of hexylthio side chain. The DFT calculation shows the planarity of polymers backbone could be improved through reducing the density of hexylthio side chain in polymer mainchain. And significant changes in their crystallinity, aggregation and optical properties were observed with the content of hexylthio side chain reducing. The P3HTT-33 displayed the highest field-effect transistor hole mobility of 2.83×10^(-2) cm^(2)·V^(-1)·s^(-1) resulting from a balance between the crystallinity and planarity. This study demonstrates modulating the content of hexylthio side chain in P3HTT is an effective strategy to optimize the opto-electronic properties of polymer obtaining excellent semiconductor device performance.展开更多
As a type of bi-functional device,electrochromic supercapacitors(EC-SCs)have attracted extensive attention in diverse applications such as flexible electronics.However,despite recent encouraging progress,rational desi...As a type of bi-functional device,electrochromic supercapacitors(EC-SCs)have attracted extensive attention in diverse applications such as flexible electronics.However,despite recent encouraging progress,rational design and development of high-performance EC-SC materials with desirable stability remain challenging for practical applications.Here,we propose a fluorination strategy to develop high-performance EC-SC materials with tough hydrogen bonding cross-linked intermolecular polymer network by one-step electrosynthesis of 3-fluorothiophene.The electrosynthesized free-standing poly(3-fluorothiophene)(PFT)films simultaneously achieve high electrochromic performance(optical contrast 42%at 560 nm with reversible color changes between purple and blue),and good capacitance property(290 F·g^(-1),1 A·g^(-1)),as well as outstanding cyclic stability(<2%reduction after 20000 cycles).We further demonstrate the fabrication of PFT-based flexible electrochromic supercapacitor devices(FESDs),and the resultant devices can be used to visually monitor the energy storage state in real-time and maintain outstanding stability under mechanical distortion like bending.Such a tough fluorination hydrogen bonding cross-linking strategy may provide a new design concept for high-performance EC-SC materials and reliable FESDs toward practical applications.展开更多
Sonodynamic therapy(SDT)is a novel cancer treatment type showing the advantages of high tissue penetration ability,non-invasion,low systemic toxicity,and high selectivity.However,SDT depends on ultrasound(US)irradiati...Sonodynamic therapy(SDT)is a novel cancer treatment type showing the advantages of high tissue penetration ability,non-invasion,low systemic toxicity,and high selectivity.However,SDT depends on ultrasound(US)irradiation;once US is turned off,the sonosensitizer will stop producing reactive oxygen species(ROS).Moreover,most sonosensitizers generate oxygen-dependent ROS,that is,singlet oxygen(^(1)O_(2)),significantly limiting the therapeutic effect of SDT in treating deep and hypoxic tumor.Therefore,combining SDT with other treatment modalities is essential.Here,we designed and synthesized a series of cisplatin-coordinated copolythiophenes(CPT-Pts),simultaneously generating^(1)O_(2),superoxide anion,and hydroxyl radicals for synergistic chemotherapy and SDT of tumor.The sonodynamic toxicity and cytotoxicity of CPT-Pts were accurately regulated by tuning the monomer ratio of the polythiophene.This copolymerization strategy avoids the side effects originating from the high-dose chemotherapy drug while making up for limiting SDT relying on ultrasonic activation,effectively inhibiting cancer cells and tumors.展开更多
Polythiophenes(PTs)with flexible backbones possess inherent polymer behaviors,including molecular wire effects and dynamic structural changes inπ-conjugated systems.The chemical sensing at the functionalized side cha...Polythiophenes(PTs)with flexible backbones possess inherent polymer behaviors,including molecular wire effects and dynamic structural changes inπ-conjugated systems.The chemical sensing at the functionalized side chains can manipulate such polymer characteristics,resulting in various optical patterns depending on the analyte structures and their concentrations.The unique optical patterns derived from polymer properties contribute to group categorization over a wide concentration range for pattern recognition.This review aims to provide a concise overview of the potential of PT chemosensor arrays using actual sensing examples in environmental monitoring,medical diagnostics,and food analysis.Furthermore,this review summarizes the methodologies that use polymer gels to realize practical chemosensor array chips for onsite analysis.展开更多
Polythiophene （PTP） was prepared by a chemical oxidative polymerization and nanosized WO3 was prepared by a colloidal chemical method. The organic-inorganic PTP/WO3 hybrids with different mass fractions of PTP were ...Polythiophene （PTP） was prepared by a chemical oxidative polymerization and nanosized WO3 was prepared by a colloidal chemical method. The organic-inorganic PTP/WO3 hybrids with different mass fractions of PTP were obtained by a simple mechanically mixing the prepared PTP and WO3. The as-prepared PTP/WO3 hybrids have a higher thermal stability than the pure PTP. The gas sensing measurements demonstrate that the PTP/WO3 hybrid sensors exhibit higher response for detecting NO2 at low temperature than the pure PTP and WO3 sensor. The sensing mechanism is suggested to be related to the existence of p-n heterojunctions in the PTP/WO3 hybrids. The response of the PTP/WO3 hybrids is markedly influenced by the PTP mass fraction. The 20% PTP/WO3 hybrid shows high response and good selectivity to NO2 at low temperature （〈90℃）. Therefore, the PTP/WO3 hybrids can be expected to be potentially used as gas sensor material for detecting NO2 at low temperature.展开更多
The copolymer poly（3-（4-fluorophenyl）thiophene-co-3-methylthiophene） was successfully prepared from mixtures of 3-（4-fluorophenyl）thiophene （FPT） and 3-methylthiophene （MET） via electrochemical oxidation in ...The copolymer poly（3-（4-fluorophenyl）thiophene-co-3-methylthiophene） was successfully prepared from mixtures of 3-（4-fluorophenyl）thiophene （FPT） and 3-methylthiophene （MET） via electrochemical oxidation in boron trifluoride diethyl etherate （BFEE） and its mixed electrolytes with acetonitrile （ACN）. The influence of monomer concentration ratios on the copolymerization was investigated by using linear sweep voltammetry and cyclic voltammetry. The structure and morphology of these copolymer films were elucidated by UV-Vis, infrared spectroscopy, elemental analysis, thermal analysis and scanning electron microscopy （SEM）, respectively. The results showed that the molar ratio of FPT and MeT units, when copolymer was electrodeposited from feed ratio of FPT：MeT = 1：2, was about 1.08：1. In addition, the introduction of ACN into BFEE has little effect on the properties of as-formed copolymers.展开更多
The copolymerization of dibenzofuran(DBF)and 3-methylthiophene(MET)was successfully achieved electrochemically by direct anodic oxidation of the monomer mixtures in boron trifluoride diethyl etherate.The effects of ap...The copolymerization of dibenzofuran(DBF)and 3-methylthiophene(MET)was successfully achieved electrochemically by direct anodic oxidation of the monomer mixtures in boron trifluoride diethyl etherate.The effects of applied polymerization potential and the monomer concentration ratios on the copolymerization were investigated by linear sweep voltammetry and cyclic voltammetry(CV).The structure of copolymer films were investigated by UV-Vis,infrared spectroscopy,thermal analysis.As-formed novel copolymers own...展开更多
Polythiophene (PTh) was prepared by the direct electrochemical synthesis in an ionic liquid ([BMIM]PF6) containing 0.1 mol/L thiophene by cyclic voltammetry, constant potential and constant current techniques. It is ...Polythiophene (PTh) was prepared by the direct electrochemical synthesis in an ionic liquid ([BMIM]PF6) containing 0.1 mol/L thiophene by cyclic voltammetry, constant potential and constant current techniques. It is found that smooth and bluegreen PTh films can be obtained at a potential of ca. +1.75 V ( vs. Ag/AgCl ) or a current of ca. 1.5 mA cm-2 in the ionic liquid.展开更多
The deformation measurement of electrosynthesized polythiophene(Pth) thin films is difficult because of the small thickness and highflexibility of the specimen. An electronic speckle patterninterferom- etry (ESPI) met...The deformation measurement of electrosynthesized polythiophene(Pth) thin films is difficult because of the small thickness and highflexibility of the specimen. An electronic speckle patterninterferom- etry (ESPI) method is used to measure the deformation ofPth films of thicknesses in the range of 4-65 μm . Theirstress-strain curves are obtained. It is found that the mechanicalproperties of Pth films are sensitive to the specimen thickness. Thetensile strength increases with decreasing thickness of thin filmfrom 10 μm. The influence of the electrochemical synthesisconditions on the mechanical properties of Pth films is also dis-Cussed.展开更多
Polythiophene/WO3（PTP/WO3）organic-inorganic hybrids were synthesized by an in situ chemical oxidative polymerization method,and char- acterized by X-ray diffraction（XRD）,transmission electron microscopy（TEM）and ...Polythiophene/WO3（PTP/WO3）organic-inorganic hybrids were synthesized by an in situ chemical oxidative polymerization method,and char- acterized by X-ray diffraction（XRD）,transmission electron microscopy（TEM）and thermo-gravimetric analysis（TGA）.The Polythiophene/ WO3 hybrids have higher thermal stability than pure polythiophene,which is beneficial to potential application as chemical sensors.Gas sensing measurements demonstrate that the gas sensor based on the Polythiophene/WO3 hybrids has high response and good selectivity for de- tecting NO2 of ppm level at low temperature.Both the operating temperature and PTP contents have an influence on the response of PTP/WO3 hybrids to NO2.The 10 wt%PTP/WO3 hybrid showed the highest response at low operating temperature of 70-C.It is expected that the PTP/WO3 hybrids can be potentially used as gas sensor material for detecting the low concentration of NO2 at low temperature.展开更多
The Complexation of thiophene with a Lewis acid with moderate acidity as a solvent, such as BF3-ethyl ether (BFEE) remarkedly lowered the electrochemical polymerization potential. The positively charged metal surface ...The Complexation of thiophene with a Lewis acid with moderate acidity as a solvent, such as BF3-ethyl ether (BFEE) remarkedly lowered the electrochemical polymerization potential. The positively charged metal surface of electrode in the process of electrochemical deposition enhanced the coordination interaction between pi-electrons of thiophene unit and the metal, which makes thiophene rings lie parallel to the surface of electrode, resulting in a highly ordered polymeric structure. Because of the large intra-chain transfer integrals, the transport of charge is believed to be principally along the conjugated chains, which is much greater than the inter-chain hopping. The specific electrical resistance across the polythiophene film thickness is more than 10(4) times than that along the surface plane of the film. In this paper we review the recent development of polymerization technique by low potential electrochemical method performed in our lab and several electrical devices in which the compact polythiophene films, such as anionic and cationic sieves, and laminate film junction of undoped polythiophene derivatives were used.展开更多
A colorimetric and fluorometric dual probe based on a water-soluble polythiophene derivative(PMTPBA)was designed and synthesized.It can be applied to determination of picric acid(PA) in 100% aqueous solution.The appro...A colorimetric and fluorometric dual probe based on a water-soluble polythiophene derivative(PMTPBA)was designed and synthesized.It can be applied to determination of picric acid(PA) in 100% aqueous solution.The approach relies on the formation of supramolecular polythiophene assemblies in the presence of PA through electrostatic,charge transfer and π-π stacking interactions.This probe could be utilized for the rapid and visual detection of PA both in aqueous solution and solid support with high specificity and sensitivity.The detection limit of this sensor is as low as 5.0 × 10^-8 mol/L.展开更多
Electrical and magnetic properties are two crucial factors for the designing of broadband electromagnetic wave absorption(EWA)materials.In this work,we synthesized various magnetic metal sulfides/carbon(M_(x)S_(y)/C)n...Electrical and magnetic properties are two crucial factors for the designing of broadband electromagnetic wave absorption(EWA)materials.In this work,we synthesized various magnetic metal sulfides/carbon(M_(x)S_(y)/C)nanocomposites from the precursor complex of metal in microporous polythiophene(MPT),and systematically investigated their EWA properties and mechanism.The characterization results indicate that M_(x)S_(y) were determined to be Fe_(7)S_(8)/C,Co_(9)S_(8)/C and Ni_(4)S_(3)/C,respectively.It is observed that M_(x)S_(y)/C nanocomposites exhibit remarkable EWA performances,where the maximal absorption gets to-51.3 dB,and efficient absorption can be realized in 10.32-18 GHz(7.68 GHz),which is superior to most reported magnetic carbonaceous EWA composites.Beside,the efficient absorption can be tuned to cover Ku band X band,demonstrating their great potential in practical applications.Improved conductance loss,obvious polarization relaxation,and apparent eddy current loss are deemed to make the predominant contributions to the high-performance EWA.This research opens up the exploration of novel nanocomposite coupling dielectric loss and magnetic loss using MPT-metal complex precursor for EWA applications.展开更多
One conjugated polymer consisting of carbazole and 3-hexylthiophene moiety, poly(N-Hexyl-2,7-di(2-(4-hexylthiophene)carbazole)(PNDC), has been synthesized by ferric chloride oxidative polymerization. The monomer N-Hex...One conjugated polymer consisting of carbazole and 3-hexylthiophene moiety, poly(N-Hexyl-2,7-di(2-(4-hexylthiophene)carbazole)(PNDC), has been synthesized by ferric chloride oxidative polymerization. The monomer N-Hexyl-2,7-di(2-(4-hexylthiophene)carbazole was synthesized and characterized by IR, 1H-NMR, 13C-NMR and MS. UV-vis absorption spectrum, fluorescence spectrum, photoluminescence spectrum and electrochemical properties of the polymer were investigated. Polymer PNDC shows maximum peak appearing at 394 nm in UV-vis absorption spectrum, strongest fluorescence-emission at 482 nm in fluorescence spectrum and maximum emission peak at 492 nm in photoluminescence spectrum. The band-gap(Eg), HOMO energy(EHOMO), and LUMO energy(ELUMO) of the polymer were obtained as 2.58,-5.32, and-2.74 e V, respectively.展开更多
基金This work was supported by the National Natural Science Foundation of China.
文摘Electrochemical polymerization of 3-fluoroalkoxy and 3-fluoroether thiophenes gives polymers with relatively high molecular weights and good processibility. Investigation of these polymers by means of GPC indicates that an increase in the number of fluorine atoms in the fluorinated group results in a decrease in degree of polymerization of the polymers in the same polythiophene series. As shown by NMR and FTIR, the polyfluorinated group substituted polythiophenes have regular 2, 5-coupling in their main chains. The SEM micrographs of the polymer films exhibit that polymer (1)-poly [3-2, 2, 3, 3-tetrafluoro-propoxy) thiophene] possesses more regular structure than the other polymers do. Substitution of polythiophenes by fluorinated groups leads to the polymers with high electric, electrochemical and thermal stability.
基金Supported by the National Natural Science Foundation of China(No.21176193)
文摘4,4＇-dibromo-2-nitro-biphenyl and 4,4＇-dibromo-2,3＇-dinitro-biphenyl have been synthesized via nitration reaction with 4,4＇-dibromobiphenyl as the raw material. Three novel thiophene derivatives, 4, 4＇-di（4-hexyl-thiophen-2-yl）biphenyl, 4,4＇-di（4-hexyl-thiophen-2-yl）-2- nitro-biphenyl and 4,4＇-di（4- hexyl-thiophen-2-yl）-2,3＇-dinitrobiphenyl were synthesized through Stille coupling reaction, followed by polymerization in the presence of FeC13, respectively. UV-vis absorption spectra, fluorescence spectra, photoluminescence spectra and electrochemical properties of the polymers were investigated. And the band-gap （Eg）, HOMO orbital energy （EHCMO）, and LUMO orbital energy （EUJMO） of the polymers were calculated. Among the polymers, polymer PBTN and PBTD show lower band-gap （2.67 and 2.63 eV）, lower HOMO energy level （-5.38 and -5.4 eV） and broader wavelength （432 and 438 nm） than that of polymer PBTB （2.69 eV, -5.36 eV and 424 nm） with incorporation of one nitro group or two nitro groups in the main chain, respectively.
基金This work was supported by the National Natural Science Foundation of China.
文摘Three series of polythiophenes containing fluoroalkoxy and fluoroether substituents were prepared by electrochemical polymerization. The effect of substituents with fluoroalkoxy or ether functional groups on the electrochemical polymerization of thiophene monomers and properties of the obtained polymers were analyzed. The introduction of a fluoroether functional group at the 3-position of the thiophene ring leads to an increase of the oxidation potential of the monomer and to a decrease of the conductivity of the resulting polymers, even with the use of a CH2 group as spacer. Conversely, the presence of an oxygen atom directly at the 3-position of the thiophene ring, which offsets the negative withdrawing effect of fluoroalkyl groups, facilitates the synthesis of highly conducting polythiophenes.
文摘Four kinds of polythiophenes have been doped with CH3SO3H in CHCl3 under air,oxygen,and nitrogen. In the doping of two types of poly(3-hexylthiophene)s,P3HexTh(Zn/Ni)and P3HexTh(Fe)with different contents of a head-to-tail unit,the p-doping occurs at a similar rate.The reaction between poly(3-dodecylthiophene),P3DodTh,and the acid takes place more rapidly.P3OBuTh with a butoxy substituent undergoes more facile p-doping and receives photochemical reaction with CHCl3,and this reaction obeys a pseudo-first-order rate law with a rate constant kobs of 1.42×10-5s-1at room tempera- ture.
文摘Chemosensor arrays have a great potential for on-site applications in real-world scenarios.However,to fabricate on chemosensor array a number of chemosensors are required to obtain various optical patterns for multianalyte detection.Herein,we propose a minimized chemosensor array composed of only two types of carboxylate-functionalized polythiophene derivatives for the detection of eight types of metal ions.Upon recognition of the metal ions,the polythiophenes exhibited changes in their fluorescence intensity and various spectral shifts.Although both chemosensors have the same polymer backbone and recognition moiety,only the difference in the number of methylene groups contributed to the difference in the fluorescence response patterns.Consequently,the metal ions in aqueous media were successfully discriminated qualitatively and quantitatively by the chemosensor microarray on the glass chip.This study offers an approach for achieving a minimized chemosensor array just by changing the alkyl chain lengths without the necessity for many receptors and reporters.
基金supported by the National Natural Science Foundation of China.
文摘A series of poly(fluoroalkoxy thiophenes) have been prepared by electrochemical and chemical polymerization respectively. The substitution of thiophene by polyfluorinated alkoxy chains affords more favorable structures in electronic effect and higher stabilities of their polymers than conventional alkoxy chain substituted polymers.
基金financially supported by the Science and Technology Commission of Shanghai Municipality (No.20JC1414900)the National Natural Science Foundation of China (No.52203005)the Science and Technology Commission of Shanghai Municipality (No.21ZR1401400)。
文摘Regioregular poly(3-hexylthio)thiopene(P3HTT) has emerged tremendous potential in organic electronic applications due to the strong noncovalent interactions from the sulfur atom linked to thiophene. However, P3HTT generally exhibits low charge mobility mostly due to poor solution processability attributed to dense arrangement of hexylthio side chain in polymer, which led to strong noncovalent interactions among sulfur atoms. To balance the nonvalent interaction and aggregation for P3HTT, herein, we systematically study the effect of hexylthio side chain content in polymer backbone on the structure and properties. A series of regioregular P3HTT-based homopolymers(P3HTT, P3HTT-50,P3HTT-33 and P3HTT-25) were prepared via Kumada catalyst transfer polycondensation method from a set of mono-, bi-, ter-and quarterthiophenes containing different contents of hexylthio side chain. The DFT calculation shows the planarity of polymers backbone could be improved through reducing the density of hexylthio side chain in polymer mainchain. And significant changes in their crystallinity, aggregation and optical properties were observed with the content of hexylthio side chain reducing. The P3HTT-33 displayed the highest field-effect transistor hole mobility of 2.83×10^(-2) cm^(2)·V^(-1)·s^(-1) resulting from a balance between the crystallinity and planarity. This study demonstrates modulating the content of hexylthio side chain in P3HTT is an effective strategy to optimize the opto-electronic properties of polymer obtaining excellent semiconductor device performance.
基金financially supported by the National Natural Science Foundation of China(Nos.52103214,52364039 and 51973102)Natural Science Foundation of Jiangxi Provincial(Nos.GJJ2201301 and 20232BAB202044)+4 种基金Natural Science Foundation of Shandong Province(Nos.ZR2022MB042 and ZR2019MB067)Innovation Ability Improvement Project ofScience and Technology Small and Medium-Size Enterprise in Shandong Province(No.2022TSGC1121)Qinghai Provincial Basic Research Program(No.2021-ZJ-710)Scientific Fund of Jiangxi Science&Technology Normal University(No.2022QNBJRC004)Talent Fund of QUST(2020)。
文摘As a type of bi-functional device,electrochromic supercapacitors(EC-SCs)have attracted extensive attention in diverse applications such as flexible electronics.However,despite recent encouraging progress,rational design and development of high-performance EC-SC materials with desirable stability remain challenging for practical applications.Here,we propose a fluorination strategy to develop high-performance EC-SC materials with tough hydrogen bonding cross-linked intermolecular polymer network by one-step electrosynthesis of 3-fluorothiophene.The electrosynthesized free-standing poly(3-fluorothiophene)(PFT)films simultaneously achieve high electrochromic performance(optical contrast 42%at 560 nm with reversible color changes between purple and blue),and good capacitance property(290 F·g^(-1),1 A·g^(-1)),as well as outstanding cyclic stability(<2%reduction after 20000 cycles).We further demonstrate the fabrication of PFT-based flexible electrochromic supercapacitor devices(FESDs),and the resultant devices can be used to visually monitor the energy storage state in real-time and maintain outstanding stability under mechanical distortion like bending.Such a tough fluorination hydrogen bonding cross-linking strategy may provide a new design concept for high-performance EC-SC materials and reliable FESDs toward practical applications.
基金supported by the National Key Research and Development Program of China(No.2022YFA1207600)the National Natural Science Foundation of China(No.62375289,62175262)the Science and Technology Innovation Program of Hunan Province(No.2022RC1201).
文摘Sonodynamic therapy(SDT)is a novel cancer treatment type showing the advantages of high tissue penetration ability,non-invasion,low systemic toxicity,and high selectivity.However,SDT depends on ultrasound(US)irradiation;once US is turned off,the sonosensitizer will stop producing reactive oxygen species(ROS).Moreover,most sonosensitizers generate oxygen-dependent ROS,that is,singlet oxygen(^(1)O_(2)),significantly limiting the therapeutic effect of SDT in treating deep and hypoxic tumor.Therefore,combining SDT with other treatment modalities is essential.Here,we designed and synthesized a series of cisplatin-coordinated copolythiophenes(CPT-Pts),simultaneously generating^(1)O_(2),superoxide anion,and hydroxyl radicals for synergistic chemotherapy and SDT of tumor.The sonodynamic toxicity and cytotoxicity of CPT-Pts were accurately regulated by tuning the monomer ratio of the polythiophene.This copolymerization strategy avoids the side effects originating from the high-dose chemotherapy drug while making up for limiting SDT relying on ultrasonic activation,effectively inhibiting cancer cells and tumors.
基金support from the Japan Society for the Promotion of Science(JSPS)KAKENHI(Grant Nos.JP23H03864 and JP24K01315)JST CREST(Grant No.JPMJCR2011)+1 种基金Y.Sasaki thanks JSPS KAKENHI(Grant No.JP24K17667)JST PRESTO(JPMJPR23H2).
文摘Polythiophenes(PTs)with flexible backbones possess inherent polymer behaviors,including molecular wire effects and dynamic structural changes inπ-conjugated systems.The chemical sensing at the functionalized side chains can manipulate such polymer characteristics,resulting in various optical patterns depending on the analyte structures and their concentrations.The unique optical patterns derived from polymer properties contribute to group categorization over a wide concentration range for pattern recognition.This review aims to provide a concise overview of the potential of PT chemosensor arrays using actual sensing examples in environmental monitoring,medical diagnostics,and food analysis.Furthermore,this review summarizes the methodologies that use polymer gels to realize practical chemosensor array chips for onsite analysis.
基金Foundation item: Project (21171099) supported by the National Natural Science Foundation of ChinaProjects (09JCYBJC03600,10JCYBJC03900) supported by Technology Commission Foundation of Tianjin,China
文摘Polythiophene （PTP） was prepared by a chemical oxidative polymerization and nanosized WO3 was prepared by a colloidal chemical method. The organic-inorganic PTP/WO3 hybrids with different mass fractions of PTP were obtained by a simple mechanically mixing the prepared PTP and WO3. The as-prepared PTP/WO3 hybrids have a higher thermal stability than the pure PTP. The gas sensing measurements demonstrate that the PTP/WO3 hybrid sensors exhibit higher response for detecting NO2 at low temperature than the pure PTP and WO3 sensor. The sensing mechanism is suggested to be related to the existence of p-n heterojunctions in the PTP/WO3 hybrids. The response of the PTP/WO3 hybrids is markedly influenced by the PTP mass fraction. The 20% PTP/WO3 hybrid shows high response and good selectivity to NO2 at low temperature （〈90℃）. Therefore, the PTP/WO3 hybrids can be expected to be potentially used as gas sensor material for detecting NO2 at low temperature.
基金This work was financially supported by the National Natural Science Foundation of China (No. 20564001)the Natural Science Foundation of Jiangxi Province (No. 050017)
文摘The copolymer poly（3-（4-fluorophenyl）thiophene-co-3-methylthiophene） was successfully prepared from mixtures of 3-（4-fluorophenyl）thiophene （FPT） and 3-methylthiophene （MET） via electrochemical oxidation in boron trifluoride diethyl etherate （BFEE） and its mixed electrolytes with acetonitrile （ACN）. The influence of monomer concentration ratios on the copolymerization was investigated by using linear sweep voltammetry and cyclic voltammetry. The structure and morphology of these copolymer films were elucidated by UV-Vis, infrared spectroscopy, elemental analysis, thermal analysis and scanning electron microscopy （SEM）, respectively. The results showed that the molar ratio of FPT and MeT units, when copolymer was electrodeposited from feed ratio of FPT：MeT = 1：2, was about 1.08：1. In addition, the introduction of ACN into BFEE has little effect on the properties of as-formed copolymers.
基金This work was financially supported by the Natural Science Foundation of China(Nos.50663001,20564001)Ministry of Education(No.2007-207058).
文摘The copolymerization of dibenzofuran(DBF)and 3-methylthiophene(MET)was successfully achieved electrochemically by direct anodic oxidation of the monomer mixtures in boron trifluoride diethyl etherate.The effects of applied polymerization potential and the monomer concentration ratios on the copolymerization were investigated by linear sweep voltammetry and cyclic voltammetry(CV).The structure of copolymer films were investigated by UV-Vis,infrared spectroscopy,thermal analysis.As-formed novel copolymers own...
基金support from the National Natural Science Foundation of China(20004010)
文摘Polythiophene (PTh) was prepared by the direct electrochemical synthesis in an ionic liquid ([BMIM]PF6) containing 0.1 mol/L thiophene by cyclic voltammetry, constant potential and constant current techniques. It is found that smooth and bluegreen PTh films can be obtained at a potential of ca. +1.75 V ( vs. Ag/AgCl ) or a current of ca. 1.5 mA cm-2 in the ionic liquid.
基金the Basic-Research Foundation of Tsinghua University(JC2000057)the Visiting Scholar Foundation of Solid Mechanical Key Lab in Tongji University of the Ministry of Education of China
文摘The deformation measurement of electrosynthesized polythiophene(Pth) thin films is difficult because of the small thickness and highflexibility of the specimen. An electronic speckle patterninterferom- etry (ESPI) method is used to measure the deformation ofPth films of thicknesses in the range of 4-65 μm . Theirstress-strain curves are obtained. It is found that the mechanicalproperties of Pth films are sensitive to the specimen thickness. Thetensile strength increases with decreasing thickness of thin filmfrom 10 μm. The influence of the electrochemical synthesisconditions on the mechanical properties of Pth films is also dis-Cussed.
基金financially supported by the National Natural Science Foundation of China(No.20871071)the Science and Technology Commission Foundation of Tianjin(No.09JCYBJC03600 and 10JCYBJC03900)
文摘Polythiophene/WO3（PTP/WO3）organic-inorganic hybrids were synthesized by an in situ chemical oxidative polymerization method,and char- acterized by X-ray diffraction（XRD）,transmission electron microscopy（TEM）and thermo-gravimetric analysis（TGA）.The Polythiophene/ WO3 hybrids have higher thermal stability than pure polythiophene,which is beneficial to potential application as chemical sensors.Gas sensing measurements demonstrate that the gas sensor based on the Polythiophene/WO3 hybrids has high response and good selectivity for de- tecting NO2 of ppm level at low temperature.Both the operating temperature and PTP contents have an influence on the response of PTP/WO3 hybrids to NO2.The 10 wt%PTP/WO3 hybrid showed the highest response at low operating temperature of 70-C.It is expected that the PTP/WO3 hybrids can be potentially used as gas sensor material for detecting the low concentration of NO2 at low temperature.
文摘The Complexation of thiophene with a Lewis acid with moderate acidity as a solvent, such as BF3-ethyl ether (BFEE) remarkedly lowered the electrochemical polymerization potential. The positively charged metal surface of electrode in the process of electrochemical deposition enhanced the coordination interaction between pi-electrons of thiophene unit and the metal, which makes thiophene rings lie parallel to the surface of electrode, resulting in a highly ordered polymeric structure. Because of the large intra-chain transfer integrals, the transport of charge is believed to be principally along the conjugated chains, which is much greater than the inter-chain hopping. The specific electrical resistance across the polythiophene film thickness is more than 10(4) times than that along the surface plane of the film. In this paper we review the recent development of polymerization technique by low potential electrochemical method performed in our lab and several electrical devices in which the compact polythiophene films, such as anionic and cationic sieves, and laminate film junction of undoped polythiophene derivatives were used.
基金financially supported by the National Natural Science Foundation of China(No.31871877)Chinese Universities Scientific Fund(Nos.2018QC151,2019TC036)+1 种基金the"Talents Scheme"Program of Beijing(No.31050003)the Research Fund Program of Guangdong Provincial Key Laboratory of Radionuclides Pollution Control and Resources(No.2017B030314182)。
文摘A colorimetric and fluorometric dual probe based on a water-soluble polythiophene derivative(PMTPBA)was designed and synthesized.It can be applied to determination of picric acid(PA) in 100% aqueous solution.The approach relies on the formation of supramolecular polythiophene assemblies in the presence of PA through electrostatic,charge transfer and π-π stacking interactions.This probe could be utilized for the rapid and visual detection of PA both in aqueous solution and solid support with high specificity and sensitivity.The detection limit of this sensor is as low as 5.0 × 10^-8 mol/L.
基金financially supported by the Fundamental Research Funds for the Central Universities(No.30920021107)the National Natural Science Foundation of China(No.51702161)。
文摘Electrical and magnetic properties are two crucial factors for the designing of broadband electromagnetic wave absorption(EWA)materials.In this work,we synthesized various magnetic metal sulfides/carbon(M_(x)S_(y)/C)nanocomposites from the precursor complex of metal in microporous polythiophene(MPT),and systematically investigated their EWA properties and mechanism.The characterization results indicate that M_(x)S_(y) were determined to be Fe_(7)S_(8)/C,Co_(9)S_(8)/C and Ni_(4)S_(3)/C,respectively.It is observed that M_(x)S_(y)/C nanocomposites exhibit remarkable EWA performances,where the maximal absorption gets to-51.3 dB,and efficient absorption can be realized in 10.32-18 GHz(7.68 GHz),which is superior to most reported magnetic carbonaceous EWA composites.Beside,the efficient absorption can be tuned to cover Ku band X band,demonstrating their great potential in practical applications.Improved conductance loss,obvious polarization relaxation,and apparent eddy current loss are deemed to make the predominant contributions to the high-performance EWA.This research opens up the exploration of novel nanocomposite coupling dielectric loss and magnetic loss using MPT-metal complex precursor for EWA applications.
基金Supported by the National Nature Science Foundation of China(No.21176193)
文摘One conjugated polymer consisting of carbazole and 3-hexylthiophene moiety, poly(N-Hexyl-2,7-di(2-(4-hexylthiophene)carbazole)(PNDC), has been synthesized by ferric chloride oxidative polymerization. The monomer N-Hexyl-2,7-di(2-(4-hexylthiophene)carbazole was synthesized and characterized by IR, 1H-NMR, 13C-NMR and MS. UV-vis absorption spectrum, fluorescence spectrum, photoluminescence spectrum and electrochemical properties of the polymer were investigated. Polymer PNDC shows maximum peak appearing at 394 nm in UV-vis absorption spectrum, strongest fluorescence-emission at 482 nm in fluorescence spectrum and maximum emission peak at 492 nm in photoluminescence spectrum. The band-gap(Eg), HOMO energy(EHOMO), and LUMO energy(ELUMO) of the polymer were obtained as 2.58,-5.32, and-2.74 e V, respectively.
