Catalytic performance of methacrylate‐based poly‐4‐(dialkylamino)‐pyridines: activity prediction via NMR shifts

The synthesis of the 4‐(dialkylamino)pyridine derivative 3‐(4‐(pyridin‐4‐yl)piperazin‐1‐yl)propyl methacrylate and its copolymerization with n‐butyl methacrylate are presented. The catalytic activity was evaluated in the acylation of tert‐butanol with acetic anhydride yielding tert‐butyl acetate. It is observed that the activity of polymer‐attached 4‐(dimethylamino)pyridine analogues correlates remarkably well with the chemical shift of the β‐pyridyl protons. Differences in catalytic efficiency result from distinct electronic densities of the pyridine ring, while embedding the catalytically active moiety into a polymeric structure has nearly no deleterious effect on the performance. © 2015 Society of Chemical Industry     

Two photoluminescent polymers based on fluorene and 2,4,6‐triphenyl pyridine: Synthesis and electroluminescence

Two fluorene and triphenyl pyridine‐based linear and dendronized copolymers, P1 and P2 , were synthesized and fully characterized by ¹H‐NMR, ¹³C‐NMR, and matrix assistant laser desorption/ionization time‐of‐flight mass spectra, respectively. The absorption, photoluminescence (PL) behavior, and energy band gaps of P1 and P2 relative to those of polyfluorene end‐capped with benzene ( P0 ) were examined through UV–vis, photoluminescent spectra, and cyclic voltammetry. The UV–vis absorption and PL emission behavior of P0 and P1 were hardly affected by molecular architecture, while those of P2 were strongly correlated with the dendronized molecular frameworks. Cyclic voltammetry studies indicated the lower highest occupied molecular orbital energy level and wider band gap of P2 thin solid film relative to those of P0 and P1 . The new polymers were thermally stable up to 410°C. The better luminance and external quantum efficiencies of P1 relative to those of P0 in polymer light‐emitting diode (PLED) applications are due to improved electron injection, charge trapping and recombination at the pyridine sites. Through the experiments, it is found that the triphenyl pyridyl segments and excimers‐formation make pronounced contribution to long wavelength emission in P1 ‐based blue light‐emitting materials, and the analogous materials containing 2,4,6‐triphenyl pyridyl unit of P1 constitute highly attractive materials for white PLED applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Highly efficient synthesis of benzopyranopyridines via ZrP2O7 nanoparticles catalyzed multicomponent reactions of salicylaldehydes with malononitrile and thiols

ZrP₂O₇ nanoparticles as an efficient catalyst have been used for the preparation of benzopyrano[2,3-b]pyridines from the four-component condensation reaction of salicylalde-hydes, thiols, and 2 equiv. of malononitrile under reflux conditions in ethanol in excellent yields and short reaction times.     

Novel taste-masked orally disintegrating tablets for a highly soluble drug with an extremely bitter taste: design rationale and evaluation

The purpose of this study was to evaluate the taste masking potential of novel solid dispersions (SDs) using Eudragit^® EPO as the excipient when incorporated into the orally disintegrating tablets (ODTs) for delivering a highly soluble drug with an extremely bitter taste. The pyridostigmine bromides (PB) SDs (PBSDs) were prepared by solvent evaporation–deposition method. The physicochemical properties of PBSDs were investigated by means of differential scanning calorimetry and Fourier transformed infrared spectroscopy. The dissolution test showed that only about 8% of PB was released from PBSDs in the simulated salivary fluid in 30 s. Therefore, PBSDs were considered taste-masked and selected for formulation of PBODTs. A central composite design was employed for process optimization. Multiple linear regression analysis for process optimization revealed that the optimal PBODTs were obtained, when the microcrystalline cellulose and crospovidone were 17.16 and 5.55 (%, w/w), respectively, and the average in vivo disintegration time was 25 s. The bitterness threshold of PB was examined by a sensory test, and the threshold value was set as 3?mg in each tablet. Taste evaluation of PBODTs in 18 volunteers revealed considerable taste masking with bitterness below the threshold value. PBODTs also revealed rapid drug release (around 99%, 2?min) in the simulated gastric fluid. The mean PB plasma concentration–time profiles of PBODTs and that of the commercial tablets were comparable, with closely similar pattern. Bioequivalence assessment results demonstrated that PBODTs and the commercial tablets were bioequivalent. In conclusion, PBODTs are prepared successfully, with taste masking and rapid disintegration in the oral cavity.     

CuBr2‐induced charge screening on photoactive nanocolloidal polypyrrole:poly(styrene sulfonate) composite multilayer thin‐film counter electrodes for high‐efficiency dye‐sensitized solar cells

Nanocolloidal polypyrrole (PPy):poly(styrene sulfonate) (PSS) particles were synthesized by chemical oxidative polymerization using 15 wt% of PSS. The highly processable polymer composite (PPy:PSS) was spin‐coated at 4000 rpm on fluorine‐doped tin oxide glass and subsequently employed as a counter electrode (CE) for dye‐sensitized solar cells (DSCs). PPy:PSS multilayer (one, three, five) CEs were treated with CuBr₂ salt, which enhances the efficiency of the DSCs. Optical studies reveal that a bulkier counterion hinders interchain interactions of PPy which on salt treatment shows a moderate redshift in absorption maxima. Salt‐treated PPy:PSS films exhibit lower charge transfer resistance, higher surface roughness and better catalytic performance for the reduction of I₃^?, when compared with untreated films. The improved catalytic performance of salt‐treated PPy:PSS multilayer films is attributed to charge screening and conformational change of PPy, along with the removal of excess PSS. Under standard AM 1.5 sunlight illumination, salt treatment is shown to boost the efficiency of multilayer PPy:PSS composite film‐based DSCs, leading to enhanced power conversion efficiency of 6.18, 6.33 and 6.37% for one, three and five layers, respectively. These values are significantly higher (ca 50%) than those for corresponding devices without CuBr₂ salt treatment (3.48, 2.90 and 2.01%, respectively). © 2016 Society of Chemical Industry     

Regioselective synthesis of pentacyclic heterocycles by the thermal and Lewis acid catalyzed Claisen rearrangement

[6,6]- and [6,5]-fused hithero unreported pentacyclic heterocycles have been regioselectively synthesized from 4-(4′-aryloxybut-2′-ynylthio)thiocoumarin in good yields by the application of thermal as well as catalytic Claisen rearrangement.     

一种新型吡啶Gemini表面活性剂的合成及表面活性

以3-氨基吡啶和固体光气为原料,一锅法合成中间体1,3-二(3-吡啶基)脲,然后再与溴代十二烷进行季铵化反应,生成了新型的吡啶阳离子Gemini表面活性剂。通过单因素试验法优化了反应条件,得到较佳工艺条件为:n(3-氨基吡啶)∶n(固体光气)=5∶1,二氯甲烷作反应溶剂,反应5h,得到产率为78%的中间体;n(中间体)∶n(溴代十二烷)=1∶10,110℃反应5 h,得到产率为90%的吡啶Gemini表面活性剂。通过FT-IR,~1H NMR,13C NMR和ESI-MS对所得产物的结构进行了表征,并对其表面活性进行了研究。结果表明,该Gemini表面活性剂的临界胶束浓度(cmc)为1.67×10~(-4)mol/L,γcmc为30.7 m N/m。     

氯尼达明的合成工艺改进

以苯肼及2,4-二氯甲苯为起始原料,苯肼经乙酰化,然后与水合氯醛、盐酸羟胺及硫酸钠反应生成N-乙酰氨基肟基乙酰苯胺,再经Beckmann重排,缩环,水解生成1H-吲唑-3-羧酸;2,4-二氯甲苯与NBS,在AIBN的催化下生成2,4-二氯溴苄,然后与1H-吲唑-3-羧酸反应生成氯尼达明。通过单因素实验和正交实验考察了N-乙酰氨基肟基乙酰苯胺的合成工艺,确定了最佳工艺条件:物料配比n(N-乙酰苯肼)∶n(水合氯醛)∶n(硫酸钠)=1∶1.3∶8.5,反应温度为90℃,反应时间为13 min,在该条件下,产物收率达86.9%,氯尼达明的总收率为31.2%。产物结构经红外、核磁和质谱进行了表征确定。     

高效疏水电荷诱导色谱介质的基团修饰及其色谱行为的初步研究

以粒径10μm、孔径300球形硅胶为载体,以γ-缩水甘油醚氧丙基三甲氧基硅烷(KH-560)为中间偶联剂,将4-巯基吡啶键合至硅胶上,制备了高效疏水电荷诱导色谱介质。通过单因素实验,探讨了反应温度、反应时间、KH-560的浓度对活化密度的影响,结果表明,在反应温度为75℃,反应时间为10 h条件下,KH-560的利用率大,可获得较宽范围的活化密度,此外还考察了缓冲液pH、反应温度、反应时间、4-巯基吡啶浓度对偶联密度的影响。结果表明,在pH=7.5的缓冲液,反应温度40℃,反应时间6 h下,4-巯基吡啶利用率高,通过控制4-巯基吡啶的浓度,可获得较宽范围的配基密度。最后,于高效液相色谱条件下,通过等度洗脱,考察了流动相pH对牛血清蛋白和溶菌酶保留因子的影响。并通过梯度洗脱,分离了不同等电点的牛血清蛋白和溶菌酶,验证了该介质的高效疏水电荷诱导色谱行为。     

Carbon nanotube–polyaniline composites

The last decade has seen a growing interest in hybrid electrically conducting nanocomposites. This article aims to provide a detailed overview of the present status of research in carbon nanotube–polyaniline (CNT/PANI) composites, from processing to structural and property evaluations. CNT/PANI are synthesized by electrochemical and chemical processing. When chemical methods are used, the main challenge is to obtain processable CNT/PANI in the emeraldine salt (ES) form composites. Stable dispersions of ES–CNT in organic media are prepared using the post doping method, inverse emulsion polymerization, or ex situ polymerizations. On the contrary, stable water dispersions of CNT/ES are prepared using hydrophilization of a preformed CNT/ES composite, direct synthesis of micelle–CNT hybrid templates, interfacial polymerization, covalent functionalization of CNT with a water soluble polymer, or using electrostatic interactions between two oppositely charged ES and CNT aqueous colloids. Moreover, the strategies for the synthesis of ternary CNT/PANI composites incorporating noble metal nanoparticles, metal oxide, or graphene sheets are also presented and analyzed in depth. Finally, we give a review of potential applications, including chemical sensors, capacitors, fuel cells and electronic devices.