含长碳链富勒烯衍生物的制备与表征

为了改善有机太阳能电池的光电特性,本文设计一种溶解性良好的富勒烯衍生物作为电池的受体材料。以对苯二酚和溴代正辛烷为原料制备对辛烷氧基苯酚中间体,再与丙二酸环亚异丙酯反应合成丙二酸单酯,进一步与十二醇酯化合成不对称丙二酸双酯,最后与富勒烯(C60)进行Bingel反应制备了含长碳链的富勒烯衍生物目标物,该化合物结构与电化学性质完全被表征。     

有机太阳能电池用受体材料的制备

本研究对富勒烯C60进行化学改性,合成的材料用于聚合物太阳能电池的受体材料。首先以对苯二酚和溴代正辛烷为起始原料,制备出对辛烷氧基苯酚,再与丙二酸亚异丙酯进行酯化反应,合成不对称性的丙二酸单酯,并进一步与含羟基化合物反应,生成不对称丙二酸双酯,最后与富勒烯C60进行Bingel反应制备出含长碳链的富勒烯衍生物。作为潜在的光电材料,其光电特性经CV和UV表征。     

聚合物太阳能电池富勒烯衍生物受体材料的制备及其表征

作为新能源,由于有机太阳能电池具有量轻、易于大面积柔性制备等特点,最近有机聚合物太阳能电池的开发得到了越来越多的关注,其光电转化效率最高值不断被刷新,这也带动了新材料的研发。本论文设计并合成了2个噻吩-富勒烯(C60)二元结构的化合物,用作电池的受体活性材料,进一步可开发成D-A型活性材料。通过利用活性的丙二酸亚异丙酯为起始原料,与十二醇进行酯化反应,高收率的制备了丙二酸单十二烷基酯中间体,再与5,5-二羟甲基环戊[c]并噻吩反应,生成对称的丙二酸双酯,最后与富勒烯C60进行Bingel反应制备2个富勒烯衍生物,其电化学性质被表征。     

基于稠环核的非富勒烯受体材料的光伏研究进展

有机太阳能电池因其生产成本低廉、质轻、易于大面积制备等明显优势,近年来已成为发展最为迅速的研究领域之一。其中,活性层材料是有机太阳能电池研究的基础和关键。在过去几十年当中,富勒烯及其衍生物一直是有机太阳能电池的重要研究方向,但其众多缺点限制了光伏性能的进一步提升。非富勒烯受体材料因分子结构、能级可调,近年,结构新颖、性能优异的非富勒烯受体材料相继被开发出来,掀起了有机太阳能电池领域的又一个研究热潮。通过对近几年基于引达省并二噻吩(ITIC类)受体和基于苯并噻二唑(Y6类)的发展进行综述,并在此基础上,对ITIC类和Y6类有机太阳能电池的研究进行了进一步讨论及展望,以期为未来非富勒烯受体材料的结构设计与优化提供参考思路。     

基于苯并噻二唑稠环核的非富勒烯受体研究进展

大量关于有机光伏电池受体材料研究工作显示,富勒烯受体材料及其衍生物是过去十几年的研究主流,但是其可见光吸收弱,成本较高,形貌稳定性差等缺点明显,而且基于富勒烯受体的有机太阳能电池效率也已接近理论极限,难以有所突破。因此,非富勒烯受体材料的设计合成受到广泛的关注,通过化学结构裁剪,器件工艺不断优化,其与聚合物给体材料所组成的有机光伏电池的效率已超过富勒烯衍生物,近两年报道以非富勒烯类小分子作为受体材料的器件效率不断攀升,已经超过17%。通过对近几年优秀的非富勒烯受体进行综述,了解近几年非富勒烯受体材料的研究进展,总结其不同设计策略及意义。     

含有π桥的非富勒烯小分子受体的研究

非富勒烯受体材料的设计合成受到广泛的关注,通过化学结构裁剪,器件工艺不断优化,其与聚合物给体材料所组成的有机光伏电池的效率已超过富勒烯衍生物,近两年报道以非富勒烯类小分子作为受体材料的器件效率不断攀升,已经超过17%。通过对近几年基于非富勒烯受体的高效有机光伏电池进行综述,了解近几年非富勒烯受体材料的研究进展,总结其不同设计策略及意义。     

甲氧基富勒醇的合成及其超分子组装和表征

将富勒烯(C60)与液溴反应制备溴代富勒烯,进而在碱性环境中与甲醇通过亲核取代反应制备得到两亲性富勒醇衍生物——甲氧基富勒醇。以环氧氯丙烷为交联剂,在碱性介质中合成水溶性的聚β-环糊精(β-CDP)。将甲氧基富勒醇与β-CDP通过研磨等方法进行超分子组装,得到甲氧基富勒醇与β-CDP的超分子组装体。采用FTIR、1 HNMR、TG-DTG对甲氧基富勒醇的结构进行表征,采用FTIR、SEM对β-CDP的结构进行表征,采用FTIR、SEM、DLS对组装体的结构进行表征。     

7-氟喹啉衍生物的合成及抗肿瘤活性研究

以间氟苯胺和乙氧基亚甲基丙二酸二已酯为原料,经conrad-Limpach-Knorr合成法,合成苯氨基亚甲基丙二酸二乙酯,再经过环化、水解、脱羧得到7-氟-4羟基喹啉(5),化合物5经过氯化到7-氟-4氯喹啉。7-氟-4氯喹啉与间甲氧基苯胺或邻甲氧基苯胺反应生成7-氟-4-苯氨基喹啉化合物(J1和J2)。其结构经1H-NMR和ESI-MS确证。用MTT法对所合成的化合物进行体外抗肿瘤活性的评价,用分子对接观察化合物与表皮生长因子受体EGFR蛋白的作用模式。     

丙二酸二乙酯与邻苯二甲酸二烯丙酯复合改性酚醛树脂

以甲醛和苯酚为原料、有机酯[由丙二酸二乙酯和DAP(邻苯二甲酸二烯丙酯)组成]为改性剂,制备碱性PF(酚醛树脂);然后采用DMA(动态热机械分析)法、DSC(差示扫描量热)法、FT-IR(红外光谱)法和TGA(热失重分析)法等对改性PF的固化机制、反应动力学等进行了表征和分析。研究结果表明:随着有机酯用量的不断增加,改性PF的储能模量、损耗模量和损耗因子(tanδ)无明显的规律性,固化温度随之下降;有机酯可促进改性PF的凝胶固化,并且是通过快速促进PF分子的活性中间体亚甲基醌来实现的。有机酯用量虽对改性PF的耐热性影响不大,但相应胶合板的胶接强度有所降低;当m(有机酯)=12 g、m(丙二酸二乙酯)∶m(DAP)=1∶1时,改性PF的综合性能相对最好。     

防晒剂对甲氧基肉桂酸异辛酯的合成

以对甲氧基苯甲醛和丙二酸为原料,吡啶为催化剂,通过Knoevenagel反应合成了对甲氧基肉桂酸,然后与异辛醇通过酯化反应合成了防晒剂对甲氧基肉桂酸异辛酯。实验主要考察了Knoevenagel反应的原料配比、催化剂用量、反应温度及时间诸因素对产品收率的影响。结果表明:在n(对甲氧基苯甲醛)∶n(丙二酸)∶n(吡啶)=1∶1.2∶1.4、反应温度85℃、反应时间6 h的优化条件下,对甲氧基肉桂酸收率为66.3%。目的产物结构经红外光谱、紫外光谱、质谱进行了表征。     

有机碱催化Knoevenagal法合成肉桂酸及其工艺优化

本文以苯甲醛和丙二酸为原料,吡啶等有机碱为催化剂,利用Knoevenagal反应合成肉桂酸,从而降低了反应温度,提高了产率和产品纯度,简化了合成工艺。同时,比较和分析了不同弱碱催化剂对肉桂酸合成产率的影响,结果表明吡啶的催化效果最好,并通过正交试验探讨了有机碱催化作用下,不同工艺参数对肉桂酸产率的影响,确定反应的最佳工艺条件为:以吡啶为催化剂,反应物苯甲醛/丙二酸摩尔比取1:3,催化剂用量0.02mol,反应时间为90min,肉桂酸产率可达90%。     

Synthesis of a novel organosoluble,biocompatible, and antibacterial chitosan derivative for biomedical applications

Electrospun materials have a number of applications in the tissue engineering field. However, the limited solubility of chitosan (CS), especially in organic solvents, makes its electrospinning with other synthetic organosoluble polymers impossible. In this article, we report the synthesis of a novel organosoluble derivative of CS through the application of a simple synthetic methodology. CS was reacted with 1,3‐diethyl‐2‐thiobarbituric acid (DETBA) with triethylorthoformate in the presence of methanol and acetic acid (4:1). The functional groups in the synthesized materials were confirmed by Fourier transform infrared and solid‐state NMR spectroscopy, whereas X‐ray diffraction revealed the level of crystallinity. The CS derivative (CS–DETBA) was tested for its cytotoxic effects on human gastric adenocarcinoma AGS cells and was found to be nontoxic. The prepared derivative showed a much enhanced inhibitory effect on the growth of three bacterial strains, Escherichia coli, Pseudomonas aeruginosa, and Staphylococcus aureus, over that of CS itself. Overall, CS–DETBA showed good solubility in a range of organic solvents, such as dimethyl sulfoxide and N,N‐dimethylformamide, and was blended with polycaprolactone (PCL) to form films and electrospun nanofibers. The morphologies of the synthesized materials were analyzed by field emission scanning electron microscopy, and the fiber diameter was 360 nm under optimum conditions. This study demonstrated that the CS–DETBA–PCL blend could be a potential material for tissue engineering and biomedical applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45905.     

Ultraviolet-light-filtering behavior of fullerene-amine derivative/chitosan blended membranes

The aminated fullerene/chitosan blended membranes with novel ultraviolet-light-filtering properties have been prepared by mixing chitosan with fullerene ethylenediamine or ethanolamine derivative in a solution containing 2% acetic acid, then casting the mixture on a glass plate. The effects of fullerene-amine derivative and chitosan structures on light transmission properties of the blended membranes are investigated systematically. The fullerene derivative kind, aminated fullerene content and crosslinking degree of chitosan greatly affect their light-filtering properties, while deacetylation degree, molecular weight and carboxymethylation of chitosan only have slight influence. Further, a possible mechanism for the UV filtering property was discussed. The strong interactions, especially electron donor-acceptor occur in condensed state may play a significant role in the unique optical property.     

Synthesis and characterization of malonic acid-doped polyaniline

The conductive form of polyaniline was synthesized by the anodic and chemical oxidation of aniline in malonic acid medium. The conductivity of polyaniline doped with malonic acid changed from 1.62×10–6 to 2.5×10–5Scm–1 depending on the way it was synthesized. The polymer growth rate was observed to be very slow in malonic acid compared with H2SO4. Thermogravimetric data revealed that the maximum thermal reaction rate of PANI doped with malonic acid was at 200°C and 520°C compared with 290°C and 530°C of the polymer doped with H2SO4.     

阿魏酸的合成及抗氧化性能的研究

以香草醛和丙二酸为原料、乙酸铵为催化剂、DMF为溶剂、苯为带水剂,合成了阿魏酸。在V（苯）∶V（DMF）=2∶1、乙酸铵用量为6%（以香草醛质量计）、n（香草醛）∶n（丙二酸）=1∶1.4、反应时间为4h的优化条件下,阿魏酸产率达到71.02%。阿魏酸的抗氧化性实验结果表明,阿魏酸对食用油脂有一定的抗氧化能力,其在油脂中的抗氧化能力优于维生素E。     

La(OTf)_3催化合成2,2-二甲基-1,3-二噁烷-4,6-二酮

研究了在三氟甲基磺酸镧(La(OTf)3)的催化条件下,以丙二酸和丙酮为原料,乙酸酐为缩合剂合成了2,2-二甲基-1,3-二噁烷-4,6-二酮。考察了酸酮摩尔比、反应温度、反应时间及催化剂用量等因素对反应的影响。确定了其最佳反应条件为:取0.1 mol丙二酸,n(丙二酸)∶n(丙酮)=1.0∶1.1(mol/mol),催化剂用量为0.2 g/0.1 mol丙二酸,反应温度30℃,反应时间为3.0 h,在上述反应条件下,产品收率可达77.1%。     

无溶剂下微波辐射合成阿魏酸

以香草醛为反应底物,丙二酸为试剂,醋酸铵为催化剂,采用微波辐射技术,经Knoevenagel-Doebner反应,在无溶剂条件下合成了阿魏酸。研究了酸、醛和醋酸铵用量,微波功率和辐射时间对阿魏酸收率的影响。得到较佳工艺条件为:40 mmol香草醛、48 mmol丙二酸、4.8 mmol醋酸铵,微波功率400 W,辐射15 min。在此条件下产率为86.9%,阿魏酸的质量分数超过98%。     

Chemical Corrosion of E-Glass Fibers in Oxalic and Other Organic Acids

Corrosion of E-glass fibers in aqueous organic acids has been investigated. Oxalic acid is particularly severe and causes almost total strength loss after exposure for only a few days. Of particular importance is that oxalic acid is a degradation product of the plastic matrix of glass reinforced plastic materials. Other organic acids, such as glyoxylic and malonic acids, also corrode the glass fibers, and these too are likely degradation products of plastic. The proposed mechanism of corrosion is an ion exchange reaction in which metal ions on the glass surface are replaced by hydrogen ions from the acid. This is enhanced by complex formation of the leached cation with the anion associated with the acid. Some cations are leached more extensively in some acids compared with others, and boron has been implicated in the corrosion by organic acids.