Overoxidized poly(3,4-ethylenedioxythiophene)-gold nanoparticles-graphene-modified electrode for the simultaneous detection of dopamine and uric acid in the presence of ascorbic acid

An innovative,ternary nanocomposite composed of overoxidized poly(3,4-ethylenedioxythiophene)(OPEDOT),gold nanoparticles(Au NPs),and electrochemically reduced graphene oxide(ERGO)was prepared on a glassy carbon electrode(GCE)(OPEDOT-Au NPs-ERGO/GCE)through homogeneous chemical reactions and heterogeneous electrochemical methods.The morphology,composition,and structure of this nanocomposite were characterized by transmission electron microscopy,scanning electron microscopy,X-ray diffraction,and X-ray photoelectron spectroscopy.The electrochemical properties of the OPEDOT-Au NPs-ERGO/GCE were investigated by cyclic voltammetry using potassium ferricyanide and hexaammineruthenium(III)chloride redox probe systems.This modified electrode shows excellent electro-catalytic activity for dopamine(DA)and uric acid(UA)under physiological p H conditions,but inhibits the oxidation of ascorbic acid(AA).Linear voltammetric responses were obtained when DA concentrations of approximately 4.0-100μM and UA concentrations of approximately 20-100μM were used.The detection limits(S/N=3)for DA and UA were 1.0 and 5.0μM,respectively,under physiological conditions and in the presence of 1.0 m M of AA.This developed method was applied to the simultaneous detection of DA and UA in human urine,where satisfactory recoveries from 96.7%to 105.0%were observed.This work demonstrates that the developed OPEDOT-Au NPs-ERGO ternary nanocomposite,with its excellent ion-selectivity and electro-catalytic activity,is a promising candidate for the simultaneous detection of DA and UA in the presence of AA in physiological and pathological studies.

Synthesis and Bio-activities of Poly(3,4-ethylenedioxythiophene)(PEDOT)/Poly(styrene sulfonate)(PSS)/Gelatin Layer on Indium Tin Oxide(ITO)-coated Glass

Poly （3, 4-ethylenedioxythiophene） （PEDOT）, together with its dopes, such as poly （styrene sulfonate） （PSS）, has been acknowledged to have a wide range of biomedical applications as an important conducting polymer. In this study, gelatin can be polymerized into PEDOT/PSS polymers on indium tin oxide （ITO）-coated glass. PEDOT/PSS/gelatin layer on ITO-coated glass significantly decreases electrochemical impedance spectroscopy （EIS） and increases charge delivery capacity relative to the gelatin layer and bare ITO- coated glass, comparable to the PEDOT/PSS layer on ITO-coated glass. PEDOT/PSS/gelatin layer on ITO- coated glass enhances pheochromocytoma （PC 12） cell affinity, possesses a high biocompatibility and promotes PC 12 cell growth by delivery of electrical stimulation. These results suggest that gelatin can be incorporated into the PEDOT/PSS polymers through electrochemical polymerization and the PEDOT/PSS/gelatin layer on ITO-coated glass possesses high electrochemical and biological activities.

Utilizing 3,4-ethylenedioxythiophene(EDOT)-bridged non-fullerene acceptors for efficient organic solar cells

A rational design of efficient low-band-gap non-fullerene acceptors(NFAs)for high-performance organic solar cells(OSCs)remains challenging;the main constraint being the decrease in the energy level of the lowest unoccupied molecular orbitals(LUMOs)as the bandgap of A-D-A-type NFAs decrease.Therefore,the short current density(J_(sc))and open-circuit voltage(V_(oc))result in a trade-off relationship,making it difficult to obtain efficient OSCs.Herein,three NFAs(IFL-ED-4 F,IDT-ED-4 F,and IDTT-ED-2 F)were synthesized to address the above-mentioned issue by introducing 3,4-ethylenedioxythiophene(EDOT)as aπ-bridge.These NFAs exhibit relatively low bandgaps(1.67,1.42,and 1.49 eV,respectively)and upshifted LUMO levels(-3.88,-3.84,and-3.81 eV,respectively)compared with most reported low-band-gap NFAs.Consequently,the photovoltaic devices based on IDT-ED-4 F blended with a PBDB-T donor polymer showed the best power conversion efficiency(PCE)of 10.4%with a high J_(sc) of 22.1 mA cm^(-2) and Voc of 0.884 V among the examined NFAs.In contrast,IDTT-ED-4 F,which was designed with an asymmetric structure of the D-p-A type,showed the lowest efficiency of 1.5%owing to the poor morphology and charge transport properties of the binary blend.However,when this was introduced as the third component of the PM6:BTP-BO-4 Cl,complementary absorption and cascade energy-level alignment between the two substances could be achieved.Surprisingly,the IDTT-ED-4 F-based ternary blend device not only improved the Jscand Voc,but also achieved a PCE of 15.2%,which is approximately 5.3%higher than that of the reference device with a minimized energy loss of 0.488 eV.In addition,the universality of IDTT-ED-2 F as a third component was effectively demonstrated in other photoactive systems,specifically,PM6:BTPe C9 and PTB7-Th:IEICO-4 F.This work facilitates a better understanding of the structure–property relationship for utilizing efficient EDOT-bridged NFAs in high-performance OSC applications.

Chemical Oxidative Synthesis and Conductivity of Poly(3,4-ethylenedioxythiophene)

[Objective] This paper was to introduce the chemical oxidative synthesis process, properties and test methods of 3,4-ethylenedioxythiophene(EDOT). [Method] The poor water solubility of EDOT was solved by using polyethylene glycol 20000(PEG) as the surfactant. The monomer was polymerized by chemical oxidative synthesis. The product was analyzed and verified by infrared spectrum, X-ray diffraction, ultraviolet-visible absorption spectra.[Result] The conductivity of the product was the best when the mass ratio of PEG and EDOT was 1∶1. The effects of oxidant dose and reaction time on the conductivity and yield of the product showed certain regularity. [Conclusion] EDOT could be polymerized by PEG and FeCl3, and the polymerization product was PEDOT.

A Study on Preparation and Use of Nano Poly Pyrrole and Nano Poly (3,4-Ethylenedioxythiophene) Coated Glassy Carbon Electrode For The Determination of Antihistamine in Pharmaceutical and Urine Sample

Pheniramine maleate (PA), an antihistamine, was determined by Differential Pulse Stripping voltammetry using nano polypyrrole (Ppy) and nano poly(3,4-ethylenedioxythiophene) (PEDOT) modified glassy carbon electrodes. The cyclic voltammetric behavior of pheniramine was studied in aqueous acidic, neutral and alkaline conditions. One well-defined oxidation peak was observed in the cyclic voltammograms at all pHs. The influence of pH, scan rate and concentration revealed irreversible electron transfer and the oxidation was diffusion controlled adsorption. The SEM analysis confirmed good accumulation of PA on the electrode surface. A systematic study of influence of various experimental parameters that affect the stripping voltammetric response was carried out and the maximum peak current conditions were arrived at. Calibration was made under maximum peak current conditions. The range of study was 0.05 to 0.4 μg/mL on Ppy/GCE and 0.025 to 0.4μg/mL on PEDOT/GCE and the lower limit of determination were 0.035μg/mL on Ppy/GCE and 0.016μg/mL on PEDOT/GCE. The suitability of the method for the determination of PA in pharmaceutical preparations and urine samples was also ascertained.

Preparation and Characterization of Clay (Maghnite-H)/Poly(3,4-Ethylenedioxythiophene) Composites

Composites of Maghnite-H, a Montmorillonite sheet silicate clay, exchanged with protons, and Poly(3,4-ethylenedioxythiophene) (PEDOT) were prepared by in situ chemical polymerization of the 3,4-ethylenedioxythiophene, without the use of solvent or oxidant. The effect of changing monomer/clay ratio was studied and the resultant composite structures were characterized by Inferred spectroscopy, 27Al and 13CSolid-State NMR spectroscopy, scanning electron microscopy and powder X-ray diffraction. All analyses are consistent with a structure were the polymer is (partially) intercalated into the clay structure, which in favourable cases lead to exfoliation. The presence of the clay in the polymer leads to a desired increase in thermal stability as witnessed by thermogravimetry.

3,4-二氢-2(1H)喹啉酮衍生物的合成研究

对3,4-二氢-2(1H)喹啉酮衍生物1,2,3(R= NO2,NH2,OH;R= H,NO2,NH2)的合成进行了研究。以苯胺和3-氯丙酰氯为原料,制得N-苯基-3-氯丙酰胺,然后经环合得到3,4-二氢-2(1H)喹啉酮,再经由硝化、还原、重氮化水解合成了一系列3,4-二氢-2(1H)喹啉酮衍生物:6-硝基-3,4-二氢-2(1H)喹啉酮(1a),6,8-二硝基-3,4-二氢-2(1H)喹啉酮(1b),6-氨基-3,4-二氢-2(1H)喹啉酮(2a),6,8-二氨基-3,4-二氢-2(1H)喹啉酮(2b),6-氨基-8-硝基-3,4-二氢-2(1H)喹啉酮(2c),6-羟基-3,4-二氢-2(1H)喹啉酮(3a)和6-羟基-8-硝基-3,4-二氢-2(1H)喹啉酮(3b),其中化合物(2c)及(3b)为新化合物。单步产率均在86%以上,路线简单,操作简便,反应条件温和。采用MS,1HNMR对产品进行了定性及结构表征。

1-取代-3-碘-1H-吡唑并[3,4-d]嘧啶-4-胺的合成

本研究报道一类1-取代-3-碘-1H-吡唑并[3,4-d]嘧啶-4-胺(1a~1e)的合成方法。以3-碘-1H-吡唑并[3,4-d]嘧啶-4-胺(2)为原料,分别与碘乙烷(3a)、碘甲烷(3b)、2-碘丙烷(3c)、碘代环丁烷(3d)及碘代环戊烷(3e)发生N-烷基化反应,得到5种1-取代-3-碘-1H-吡唑并[3,4-d]嘧啶-4-胺(1a~1e),产物结构经^(1)H NMR和ESI-MS确证。然后考察并确定该N-烷基化反应的适宜反应条件为:物料比为n(3a)∶n(2)=4∶1,N,N-二甲基甲酰胺为反应溶剂,碱为Cs_(2)CO_(3),反应温度为110℃。

基于1H-吡唑并[3,4-b]吡啶母核PI3Kδ抑制剂的设计合成

恶性肿瘤严重危害人类健康与生命,磷脂酰肌醇-3激酶家族(PI3Ks)在细胞增殖、分化过程中起着重要作用,该激酶及其相关通路的其他激酶可被药物干预,是抗癌药物的热门靶点。在以往的PI3K抑制剂中,均有1H-吡唑并[3,4-b]吡啶母核,通过虚拟筛选以及合成路线设计,合成了一系列1H-吡唑并[3,4-b]吡啶类化合物,该类化合物可能对PI3Kδ具有潜在抑制作用。

3,4-二氯苯基硫脲的连续化合成

采用连续进料方式合成3,4-二氯苯基硫脲。考察物料投料物质的量比、体系酸值、反应温度、反应停留时间及分散剂等参数对反应的影响。较优工艺参数为:硫氰酸铵与3,4-二氯苯胺投料物质的量比1.36,酸值7%,反应温度96℃,反应时间15h,此时产品纯度可达98.5%,收率达95.93%。3,4-二氯苯基硫脲的连续化合成相比于传统间歇反应,产品纯度及收率更加稳定。

聚(3,4-乙烯二氧噻吩)/MXene复合材料的制备及电容性能研究

MXene材料具有组分灵活可调、电容量较高等优势在超级电容器储能领域备受关注。采用电化学法制得聚3, 4-乙烯二氧噻吩/Nb_(2)CT_(x) MXene (PEDOT/MXene)复合电极材料。结果表明,在扫描速率为30 mV·s^(-1)时,PEDOT/MXene的面积比电容可达250.21 mF·cm^(-2),当电流密度从0.1 mA·cm^(-2)增加到5 mA·cm^(-2)时,PEDOT/MXene的面积比电容保持率为83.5%,远优于PEDOT的64.1%,并且在100 mV·s^(-1)的扫描速率下循环测试1 000次后初始电容保持率可达84%,表现出良好的倍率性能和稳定性。工作为基于MXene基材料构筑高性能电化学储能界面提供了一定的借鉴。

6-氟-4-羟基-3-氧代-3,4-二氢喹喔啉-1(2 H)-羧酸叔丁酯的合成、晶体结构及抗肿瘤活性研究

喹喔啉类化合物由于具有显著的生物活性而被广泛应用于医药、化工领域,特别是抗癌药物研发领域。本文通过四步反应法首次合成了6-氟-4-羟基-3-氧代-3,4-二氢喹喔啉-1(2 H)-羧酸叔丁酯,经溶液结晶法获得其单晶体。晶体学分析表明,该化合物属单斜晶系,空间群C2/c,晶胞常数a=1.28663(10)nm,b=2.25249(17)nm,c=1.01564(7)nm,Z=8,ρ_(c)=1.359 g·cm^(-3),R=0.0538,R_(w)=0.1406。在B3LYP/6-311+G(2d,p)模式下使用密度泛函理论(DFT)计算了该化合物的最佳结构,与X射线单晶衍射确定的晶体结构基本一致。抗肿瘤活性研究表明其有良好的抗肿瘤作用。此外,通过DFT计算了分子的静电势和前沿分子轨道。

反胶束刻蚀法制备具有多孔结构的高导电聚(3,4-二氧乙烯噻吩)纳米薄膜

图案化导电薄膜在传感器领域有着非常广泛的应用。本文中在亲水处理的二氧化硅晶片基板上涂覆氯化铁/PEG-PPG-PEG嵌段共聚物/正丁醇的混合溶液,形成含有反胶束纳米球的氧化剂薄膜;以3,4-二氧乙烯噻吩单体分子为气相,通过气相沉积的方式得到具有纳米孔图案的多孔性聚(3,4-二氧乙烯噻吩)(PEDOT)薄膜。利用偏光显微镜、扫描电镜研究PEDOT薄膜纳米多孔结构的形成机制,并采用四点探针测试图案化薄膜的电性能。结果表明,PEG-PPG-PEG嵌段共聚物浓度和环境湿度的增加都有助于孔的生成。在PEG-PPG-PEG质量分数0.2%和处理基片的环境湿度为60%的条件下,制备的导电图案化薄膜的电导率可达到83.68S/cm,其平均孔径可达到248nm。通过反胶束刻蚀法对导电薄膜进行图案化处理,相对于其他图案化方法操作简单、成本较低,在生物传感器、气体传感器等领域有巨大的应用潜力。

6-异丙基-3,4-二氢嘧啶类化合物的高效催化合成

开发了一种新型、简便的合成方法,在无溶剂条件下,以4,5-甲基-L-脯氨酸为催化剂,催化比吉内利反应(Biginelli reaction)高效合成6-异丙基-3,4-二氢嘧啶类化合物。反应条件温和,催化剂环保,产率优异(高达99%),可以获得广泛的具有显著生物活性的目标产物。

Structural characteristics and the label-free detection of poly(3,4-ethylenedioxythiophene/cucurbit[7]uril)pseudorotaxane at single molecule level

A multi-technique approach to prove the preparation of poly(3,4-ethylenedioxythiophene/cucurbit[7]uril)pseudorotaxanes(PEDOT∙CB7-PPs)is reported.Molecular docking simulation and matrix-assisted laser desorption/ionization mass spectrometry(MALDI MS)validate the complexation ability of the CB7 molecule towards 3,4-ethylenedioxythiophene(EDOT),which leads to the EDOT∙CB7 inclusion complex.Oxidative polymerization of EDOT∙CB7 enabled the synthesis of PEDOT∙CB7-PPs.The water-soluble part of PEDOT∙CB7-PPs was selected,freeze-dried,and chemically characterized.Furthermore,dynamic light scattering(DLS)has been used to study the particle size and z-potential(ZP-ζ)of PEDOT∙CB7-PPs.The ZP-ζvalue(35 mV)evidenced that the PEDOT∙CB7-PPs formed stable water dispersion.By combining the emerging nanopore resistive pulse sensing technique(Np-RPS)and computational modeling,we identified strong interactions of PEDOT∙CB7-PPs with the aerolysin(Ael)nanopore.PEDOT∙CB7-PPs behave as positive charged species,and thus trans negative bias promotes its interactions with the Ael nanopore.The computational modeling results are fully consistent with the Np-RPS detection,which also reveals strong interactions between PEDOT∙CB7-PPs and the Ael nanopore.With this study,we hope to provide new insights and a better understanding of the interactions between supramolecular complexes based on CB7 and biological entities,which is instrumental for future applications in the field of nanobiotechnology.

Overoxidized poly(3,4-ethylenedioxythiophene)-overoxidized polypyrrole composite films with enhanced electrocatalytic ability for rutin and luteolin determination

In this study, a simple and effective method was proposed to improve the electrocatalytic ability of overoxidized poly(3,4-ethylenedioxythiophene)-overoxidized polypyrrole composite films modified on glassy carbon electrode for rutin and luteolin determination. The composite electrode was prepared by cyclic voltammetry copolymerization with LiClO_(4)-water as the supporting electrolyte. The peak current of rutin and luteolin on the composite electrode gradually decreased or even disappeared with the increase in the positive potential limit. After incubation in NaOH–ethanol solution with a volume ratio of 1:1, the composite electrodes prepared at positive potential limit greater than 1.5 V exhibited enhanced differential pulse voltammetry peak currents, reduced charge transfer resistance, larger effective specific surface area and higher electron transfer rate constant. The composite electrode prepared in the potential range of 0–1.7 V showed optimal electrocatalytic performance. The X-ray photoelectron spectroscopy results indicated that the content of –SO_(2)/–SO and –C=N– groups in the composite film increased significantly after incubation. Further, the Raman spectra and Fourier transform infrared spectra revealed that the thiophene ring structure changed from benzene-type to quinone-type, and the quinone-type pyrrole ring was formed. The electrocatalytic mechanism of the composite film was proposed based on the experimental results and further verified by Density Functional Theory calculation.

3-取代和3,4-二取代噻吩的合成与表征

以噻吩、48 % (m/m)氢溴酸水溶液、3 5 % (m/m)过氧化氢水溶液、高纯氨、金属钠为原料合成了 3 溴噻吩和 3 ,4 二溴噻吩 ,3 溴噻吩和 3 ,4 二溴噻吩分别以 (dppp)NiCl2 为催化剂合成了 3 烷基噻吩和 3 ,4 二烷基噻吩 .3 溴噻吩以CuI ,NaHSO4为催化剂合成了 3 烷氧基噻吩 ,产率较高 .并用核磁共振谱。

3,4-二氢吡喃[3,2-b]-吲哚-2-酮的合成

目前合成3,4-二氢吡喃[3,2-b]-吲哚-2-酮的方法均以卡宾为催化剂。本文以碳酸铯为催化剂,乙腈为反应溶剂,吲哚-3-酮与α,β-不饱和N-酰基琥珀酰亚胺为原料,于25℃条件下发生迈克尔加成反应介导的环化反应,合成3,4-二氢吡喃[3,2-b]-吲哚-2-酮,收率74%~93%,所得化合物的结构经^(1)H NMR,^(13)C NMR和HR-MS表征。该合成方法具有较高的新颖性,对本类物质的合成具有重要的参考价值。

微波促进下3-(2-苯并呋喃基)-4-氨基-5-巯基-1,2,4-三唑及其衍生物的合成

微波辐射条件下,首先由2-苯并呋喃甲酰肼依次与二硫化碳和水合肼反应合成3-(2-苯并呋喃基)-4-氨基-5-巯基-1,2,4-三唑,进一步在微波辐射条件下由4-氨基-5-巯基-1,2,4-三唑分别与芳甲酸/芳氧基乙酸、α-溴代苯乙酮及芳醛反应以较高产率制得了相应的1,2,4-三唑并[3,4-b]-1,3,4-噻二唑、1,2,4-三唑并[3,4-b]-1,3,4-噻二嗪及4-芳亚甲基亚胺基-5-巯基-1,2,4-三唑.产物结构经IR,1HNMR,MS及元素分析进行了表征.

新型吡唑并[3,4-d]嘧啶-4-酮类衍生物的结构表征和镇痛活性

本文以2-氰基-3-乙氧基丙烯酸乙酯与3,4-二甲基苯肼为原料,通过多步反应合成了三种新型吡唑并[3,4-d]嘧啶-4-酮类衍生物(A~C),通过核磁共振(NMR,包括^(1)H NMR、^(13)C NMR)和液相色谱-质谱联用(LC-MS)技术表征确证了其结构,并完整归属了三种化合物的^(1)H NMR数据.对所合成的化合物1-(3,4-二甲基苯基)-6-甲基-5-[3-(哌啶-1-基)丙氧基]-1,5-二氢-4H-吡唑并[3,4-d]嘧啶-4-酮(A),通过小鼠脑部质谱成像和福尔马林实验进行了初步的体内镇痛活性评价,我们发现化合物A能透过血脑屏障,并产生显著且剂量依赖的镇痛活性.本研究为以吡唑并[3,4-d]嘧啶-4-酮为骨架的镇痛药物的研发提供了结构和体内活性的基础研究数据.