Spectroscopic Studies of the Stability of Doped Polythiophenes Under Air

Abstract

The stability of the doped state of conductive polythiophenes under air was investigated by the use of Infrared (IR) and UV-visible (UV) spectroscopies. Poly(3-methyl thiophene) doped with BF₃-ethyl ether (BFEE). shows higher stability due to its stereoregularity-chain structure. While the doped polythiophene (PT) degrades easily under the moisture.     

Effect of graft polymer prepared by living radical polymerisation on electro-optical properties of polymer dispersed liquid crystal

In this study, a graft polymer matrix prepared by living radical polymerisation had been incorporated into polymer dispersed liquid crystals (PDLCs). The electro-optical properties of the PDLCs were investigated. The results showed that the length and density of graft chain had a great influence on the memory effect of the PDLCs. Low-driving-voltage and weak-memory-effect PDLCs could easily be obtained with a graft polymer matrix.     

Preparation of modified polymer blend and electrical performance

In this study, a modified binary polymer blend made up of polycarbonate and polystyrene blend has been prepared by loading of aluminum oxide (Al₂O₃) as a dopant. The role of alumina with polymer blend system was addressed in view of interfacing criteria. The filler concentration of modified blend was taken as 5, 10, and 15%. The morphological, thermal, and electrical properties were characterized by various techniques. Optical microscopy confirms the homogenous dispersion of Al₂O₃ in blend. The presence of alumina was detected by subatomic level using atomic force microscope (both two and three dimensional approach). The differential scanning calorimetric thermographs demonstrate decreasing softing point as function of alumina loading. The dielectric properties such as dielectric constant, loss, and electrical modulus were studied under DC bias. The effect of DC bias exhibits significant changes at low amount of Al₂O₃. The dielectric polarization supports Maxwell Wagner (MW) theory due to low frequency response. 15% Al₂O₃ gives the highest dielectric constant (ε′) value (3.5?×?10⁵) at 10 Hz. The polymer modified blend with Al₂O₃ may be used as a one of the best dielectric medium.     

一种锌配合物用于炭疽生物标志物的检测

采用溶剂热合成方法,合成了一种新型金属配位聚合物{[Zn₂(L)(H₂O)(DMA)]·DMA·2.3H₂O}_n (1),其中L^4-为完全脱去质子的N,N''-二(4-羧基苄基)-5-氨基间苯二甲酸,DMA为N,N-二甲基乙酰胺。单晶X射线衍射结果显示,该配合物属于三斜晶系,空间群为P$overline{1}$,a=0.989 6(5) nm,b=1.370 5(5) nm,c=1.382 1(5) nm,α=80.067(5)°,β=76.729(5)°,γ=76.611(5)°,结构是由二维金属有机层通过π…π相互作用而扩展成的三维超分子骨架。红外光谱验证了锌离子与L^4-配体成功配位。粉末X射线衍射(PXRD)实验证实了配合物1具有较高的纯度。热重分析结果显示配合物1在室温至416.9 ℃区间内具有较好的热稳定性。在273 nm的激发光下,配合物1在437 nm处有较强的荧光发射,可以在30 s内快速检测乙醇溶液中的炭疽生物标志物——吡啶-2,6-二甲酸,具有选择性高、抗干扰能力强、检测限低(约为15 μmol·L^-1)等特点。结合PXRD图和紫外可见吸收光谱揭示了其检测机理为晶体骨架坍塌而诱导的荧光猝灭。     

Facile one‐pot method of initiator fixation for surface‐initiated atom transfer radical polymerization on carbon hard spheres

An efficient and novel one‐pot process is developed to immobilize the atom transfer radical polymerization (ATRP) initiators onto the surface of fully pyrolyzed carbon hard spheres (CHSs) via a radical trapping process from the in situ thermal decomposition of bis(bromomethylbenzoyl)peroxide. The CHSs do not require any additional preparative treatment prior to the initiator immobilization. Styrene and methyl methacrylate are polymerized onto initiator‐immobilized CHSs by surface‐initiated atomic transfer radical polymerization (SI‐ATRP). Samples are characterized using Fourier transform infrared, thermogravimetric analysis, scanning electron microscopy, and transmission electron microscopy. These methods of characterization confirmed that all the CHSs are coated with a uniform layer of grafted polymer. This efficient, one‐pot immobilization of ATRP‐initiators represents an exceptionally simple route for the rapid preparation of various polymer‐coated carbon‐based nanomaterials using SI‐ATRP. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3314–3322     

Imide‐functionalized naphthodithiophene based donor‐acceptor conjugated polymers for solar cells

Donor‐acceptor conjugated polymers containing a new imide‐functionalized naphthodithiophene (INDT) as the acceptor unit and a 2,2'‐bithiophene with varied substituents as the donor unit have been synthesized. The bandgaps of these polymers depend strongly on the dihedral angle of the 2,2'‐bithiophene unit. The 3,3'‐dialkoxy substitution (polymers PDOR / PBOR ) leads to near planar bithiophene conformation due to the well‐known S–O short contact, while the 3,3'‐dialkyl substitution (polymer PDR ) results in significant twisting due to the steric effect. Consequently PDOR / PBOR shows the lowest bandgap of 1.82/1.85 eV while PDR has a bandgap of 2.38 eV. Bulk‐heterojunction solar cells of the polymer/fullerene blends have been fabricated. Preliminary results show that PBOR gives the best device performance with power conversion efficiencies as high as 2.45% in air without any thermal annealing treatment, indicating the promising potential of INDT‐containing conjugated polymers for efficient solar cells. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3818–3828     

Chiral and water‐soluble poly(2‐oxazoline)s

We describe the synthesis and characterization of the first water‐soluble and chiral poly(2,4‐disubstituted‐2‐oxazoline)s. While poly(2,4‐dimethyl‐2‐oxazoline)s are water soluble up to 100 °C, aqueous solutions of poly(2‐ethyl‐4‐methly‐2‐oxazoline) exhibit a lower critical solution temperature. This is discussed in context with its constitutional isomers poly(2‐oxazoline)s and poly(2‐oxazine)s. Circular dichroism spectroscopy revealed strong Cotton effects, which are also responsive to temperature in aqueous solution. It is therefore hypothesized that structures, comparable to polyproline helices, are formed in aqueous solution. In contrast to polyproline, poly(2,4‐disubstituted‐2‐oxazoline)s are highly water soluble and therefore represent very interesting pseudo‐polypeptides that may be useful to develop responsive biomimetic biomaterials. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Synthesis of two dihydropyrroloindoledione‐based copolymers for organic electronics

Two novel dihydropyrroloindoledione (DPID)‐based copolymers have been synthesized in a two directional approach and characterized (gel permeation chromatography (GPC), ultraviolet‐visible (UV–vis), cyclic voltammetry, and computational models). These planar, broad absorption copolymers show promise for use in organic electronics, with deep energy levels and low bandgaps. The two‐directional Knoevenagel condensation used demonstrates the versatility of DPID as a useful yet underexploited conjugated unit. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Synthesis and characterization of polythiophene block copolymer and fullerene derivative capable of “three‐point” complementary hydrogen bonding interactions and their application in bulk‐heterojunction solar cells

We report the synthesis and characterization of a polythiophene block copolymer (P4) selectively functionalized with diaminopyrimidine moieties and a thymine tethered fullerene derivative (F1). Self‐assembly between P4 and F1 through “three‐point” complementary hydrogen bonding is studied by ¹H NMR spectroscopy and differential scanning calorimetry. A large Stern‐Volmer constant (K_SV) of 1.2 × 10⁵ M^?1 is observed from fluorescence quenching experiments, revealing strong complexation between these two components. Solar cells employing P4 and F1 at different weight ratios as active layers are fabricated and tested; corresponding thin film morphologies are studied in detail by optical imaging and atomic force microscopy. Correlations between polymer complex structures, film morphologies, and device performance are discussed. Thermal stability of benchmark poly(3‐hexylthiophene) bulk heterojunction solar cells is found to be improved by the addition of a few weight percent of P4/F1 complexes as compatibilizers. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3339–3350