聚酯酸酐的合成及其药物释放性能研究

将对羟乙氧基苯甲酸分别与已二酰氯、癸二酰氯和对苯二甲酰氯反应,制备了含酯键的二羧酸.经熔融缩聚,合成了主链含酯键的新型聚酯酸酐.通过¹H NMR、IR及元素分析对单体及聚酯酸酐的结构进行了表征.研究了聚酯酸酐的体外降解和药物释放性能,其降解速率和释药速率次序为:聚4,4'-(已二酰氧二乙氧基)双对苯二甲酸＞聚4,4'-(癸二酰氧二乙氧基)双对苯二甲酸＞聚4,4'-(对苯二甲酰氧二乙氧基)双对苯二甲酸.     

邻苯二甲酰亚胺-多胺缀合物的合成及其生物活性

以邻苯二甲酰亚胺、1,3-丙二胺、1,4-丁二胺为原料,合成了5个邻苯二甲酰亚胺-多胺缀合物．所合成的目标化合物经过^1H NMR、^13C NMR、MS、元素分析确认,并评价了它们对K562（人慢性原白血病细胞）、MB231（乳腺癌细胞）、LnCap（前列腺癌细胞）的生物活性．结果表明：5个目标化合物均不具备抗肿瘤活性,提示多胺衍生化不能提高邻苯二甲酰亚胺的抗肿瘤活性．     

高效液相色谱法测定荧光增白剂1，4-双（邻氰基苯乙烯基）苯反应产物的研究

1,4-双(邻氰基苯乙烯基)苯(BCSB)是一种用于聚酯和聚酰胺纤维的荧光增白剂,它与纤维的结合牢度强,洁白程度高。其合成一般经过邻氰基甲苯光氯化,邻氰基氯苄酯化,邻氰基苄基膦酸二乙酯与对苯二甲醛缩合等三步反应。所以BCSB产物     

催化氧化合成邻苯二甲醛工艺的响应面优化的研究

以制备的Co/Mo/γ-Al_2O_3为催化剂,采用过氧化氢催化氧化工艺合成邻苯二甲醛,在前期实验基础上,通过响应面法对邻苯二甲醛的合成工艺参数进行了优化,选用Box-Behnken对实验进行设计,研究了对反应有较大影响的反应时间、反应温度及过氧化氢加量三个因素对邻苯二甲醛收率的影响,得到最佳工艺条件并进行模型的建立。实验表明:过氧化氢催化氧化合成邻苯二甲醛的优化工艺条件为:邻苯二甲醇的加量为5g,30%过氧化氢加量15g,反应温度为81℃,反应时间为3h,催化剂为0. 3g,邻苯二甲醛收率可达51. 4%。使用傅里叶红外光谱、核磁共振氢谱、气相色谱对产品结构进行了分析表征。     

α-含氧取代酞菁的聚集性质研究

以3-硝基邻苯二腈为原料分别与苯酚和甲醇反应合成3-苯氧基邻苯二腈和3-甲氧基邻苯二腈, 这些α-取代的邻苯二腈以二甲氨基乙醇为溶剂, 在有无醋酸锌条件下环合, 分别形成α-四苯氧基锌酞菁、α-四苯氧基无金属酞菁、α-四甲氧基锌酞菁、α-四甲氧基无金属酞菁, 对产物结构进行了表征. 光谱分析结果表明, 此类锌酞菁在氯仿等非配位溶剂中能自发形成J型聚集体, 其Q带出现一个红移吸收带, 经UV-Vis光谱、荧光光谱及MALDI-TOF质谱分析表明, 该聚集体的形成机理为基于酞菁分子间的锌-氧自配位相互作用.     

无水氟化钾催化酰亚胺与氯乙腈的氰甲基化新方法

用邻苯二甲酰亚胺与二乙胺基乙腈反应进行氰甲基化制备N-氰甲基邻苯二甲酰亚胺,反应温度高、时间长、产率低(160℃、22小时、22.2％)。我们首次用无水氟化钾催化邻苯二甲酰亚胺与氯乙腈的氰甲基化反应,成功地制得了N-氰甲基邻苯二甲酰亚胺,取得了满意的     

酰亚胺及磺酰苯酰亚胺的氰甲基化新方法

二乙胺基乙腈分別与苯邻二酰亚胺、丁二酰亚胺或邻-磺酰苯酰亚胺反应后,可生成相应的N-氰甲基苯邻二酰亚胺、N-氰甲基丁二酰亚胺,N-氰甲基邻磺酰苯酰亚胺及O-氰甲基邻磺酰苯酰亚胺。酰亚胺或磺酰苯酰亚胺的氰甲基化反应活性,随氮负离子的稳定性及其酸性增强而增大。     

含二羟基二苯酮的系列热致液晶共聚酯的合成和表征──Ⅲ．含4，4＇－二羟基二苯砜结构的共聚酯

含二羟基二苯酮的系列热致液晶共聚酯的合成和表征──Ⅲ．含４，４＇－二羟基二苯砜结构的共聚酯董德文，池振国，倪玉山，丁孟贤（中国科学院长春应用化学研究所长春１３００２２）陈玉（东北师范大学分析测试中心长春１３００２４）关键词４，４＇－二羟基二苯酮，热致...     

Gabriel合成法的研究与应用进展

本文先简单介绍了Gabriel反应,然后分别综述了苄位和烯丙位等活泼卤代烃、伯卤代烃、磺酸酯的Gabriel反应,邻苯二甲酰亚胺与环氧化合物的缩合、含邻苯二甲酰亚胺基的合成子、邻苯二甲酰亚胺与醇在Mitsunobu条件下的直接Gabriel反应等,最后对Gabriel反应的应用进行了总结和展望。指出应加强对Gabriel反应的系统研究,特别是脱邻苯二甲酰基的方法和基于Gabriel反应原理的替代方法的研究。     

模拟细胞色素P-450的仿生氧化反应的研究 T.氯合5,10,15,20-四苯基卟吩合铁(III)催化下不同亚碘酰芳烃及其衍生物的结构对环己烷充氧化反应的影响

在氯合5,10,15,20-四苯基卟吩合铁(Ⅲ)[TPPFe(Ⅲ)Cl]催化下,带有不同取代基的亚碘酰苯和亚碘酰苯的衍生物作充氧化剂对环己烷进行了仿生单充氧化反应的研究.取代亚碘酰苯中对位取代基的电子效应和间位取代基的电子及立体效应对氧化产物环己醇的产率有良好线性相关性.亚碘酰苯的衍生物苯亚碘酸二醋酐与苯亚碘酸单对甲苯磺酸酐对环己烷的充氧化能力和邻、间、对亚碘酰苯甲酸与邻亚碘酰苯甲酸酯相似,环己醇产率接近零.从而提出亚碘酰苯甲酸及邻亚碘酰苯甲酸酯存在分子内或分子间I(OH)OCO成键结构的论点.     

Synthesis,characterization, and biological evaluation of new polyester containing Schiff base metal complexes

The production of new biocidal polyester Schiff base metal complexes [PESB–M(II)] via polycondensation reaction between chelated Schiff base diol and adipoyl chloride is reported. The resulting polyesters were characterized by physico-chemical and spectroscopic methods. The analytical data of all the synthesized polyesters were found to be in good agreement with 1:1 molar ratio of chelated Schiff base diol to adipoyl chloride. Thermogravimetric analyses of synthesized polyesters were studied by TG in nitrogen atmosphere up to 1073 K and results indicate that Cu(II) polyester complex exhibited better heat resistant properties than the other polyesters complexes. Magnetic moment and UV–visible spectra were examined to explain the structure of all the polyesters which reveled that Mn(II), Co(II), Ni(II) have octahedral geometry while Cu(II) possess a distorted octahedral geometry. These newly developed polyesters were also tested for their antibacterial activity against several bacteria and fungi. Among all the tested compounds PESB–Cu(II) possess the highest bactericidal and fungicidal activity.     

Preparation and photocrosslinking behaviors of polyesters derived from trans-2,2′-dihydroxystilbene

The monomer, trans-2,2′-dihydroxystilbene (DHS), has been prepared by asymmetric photocleavage (254 nm) of coumarin dimer acid derived from coumarin dimer. Four new polyesters are successfully synthesized by interfacial polycondensation of the DHS with adipoyl chloride, azelaoyl chloride, sebacoyl chloride, and dodecanedioyl dichloride, respectively. The reduced viscosities of the polyesters decrease from 0.32 to 0.11 dL/g as the number of methylene unit in diacid chlorides increases from 4 to 10. From DSC investigation, it is found that the polyesters are semi-crystalline polymers with T_m = 39–192°C. Under 350 nm light, photocrosslinking behavior in solution and film-state is investigated by UV spectral change with irradiation time (350 nm). The photoreactive stilbene chromophores in the main chain dimerize to form cyclobutane derivatives, and lead to crosslinking of the polyesters. Photosensitivity in the film state has also been evaluated by their characteristic curves. Polyester from dodecanedioyl dichloride ( 5d ) exhibits the highest initial reaction rate and ultimate crosslinking ratio. © 1995 John Wiley & Sons, Inc.     

Synthesis and characterization of new aromatic polyesters containing cardo decahydronaphthalene groups

Three cardo bisphenols containing decahydronaphthalene group viz., 4,4′-(octahydro-2(1H)-naphthylidene)bisphenol, 4,4′-(octahydro-2(1H)-naphthylidene)bis-3-methylphenol and 4,4′-(octahydro-2(1H)-naphthylidene)bis-3,5-dimethylphenol were synthesized starting from commercially available 2-naphthol and were utilized for synthesis of new aromatic polyesters by phase transfer-catalyzed interfacial polycondensation with isophthaloyl chloride, terephthaloyl chloride and a mixture of isophthaloyl chloride and terephthaloyl chloride (50:50 mol %). Inherent viscosities and number average molecular weights (M_n) of polyesters were in the range 0.35-0.84 dL/g and 13,300-48,500 (Gel Permeation Chromatography, polystyrene standard), respectively. Polyesters were readily soluble in organic solvents such as dichloromethane, chloroform, tetrahydrofuran, meta-cresol, pyridine, N,N-dimethylformamide, N,N-dimethylacetamide, and 1-methyl-2-pyrrolidinone at room temperature and could be cast into tough, transparent and flexible films from their chloroform solutions. Wide-angle X-ray diffraction measurements revealed the amorphous nature of polyesters. The glass transition temperature of polyesters was in the range 207-287 °C. The temperature at 10% weight loss (T₁₀), determined from thermogravimetric analysis of polyesters, was in the range 425-460 °C indicating their good thermal stability.     

Aryudene Polymers. II Synthesis and Characterization of some New Polyesters of Diarylidenecyclopentanone

New polyesters formed by interfacial polycondensation of 2,5-bis(4-hydrox-ybenzylidene)cyclopentanone (I) and 2,5-bis(4-hydroxy-3-methoxybenzyli-dene)cyclopentanone (II) with 4,47prime;-diphenic, isophthaloyl, terephthaloyl, adi-poyl, suberoyl, and sebacoyl dichlorides were obtained. The yield and the values of the reduced viscosity of the produced polyesters were found to be affected by the type of organic phase, the quantitative ratio of organic to aqueous phase, the concentration of the hydrogen chloride acceptor, and the contribution of benzyltriethylammonium chloride as a catalyst. In order to characterize these polymers, the necessary model compounds were prepared from I, II, and benzoyl chloride. The resulting polyesters were confirmed by IR, elemental analysis, viscometry, DTA, DSC measurements, and thermogravi-metric analysis. The crystallinities of all polyesters were examined by x-ray analysis, and the electrical properties of the polyesters were tested.     

Methylene-bridged aromatic polyesters. Synthesis,characterization, and radiation-induced crosslinking

Aromatic polyesters connected by methylene groups were synthesized. Two pairs of aromatic diacid chlorides, 3,3′-methylenedibenzoyl chloride and 4,4′-methylenedibenzoyl chloride were each polymerized via interfacial polycondensation with 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 3,3′-methylenediphenol, and 4,4′-methylenediphenol. For comparison, 3,3′-carbonyldibenzoyl chloride and 4,4′-carbonyldibenzoyl chloride were similarly polymerized with bisphenol A. Substitution of meta,meta' oriented phenylene groups for para,para' oriented phenylene groups had a significant and cumulative effect in reducing the glass transition temperatures of the polymers, thereby enhancing their processability. In air the methylene groups of the polyesters undergo oxidation and crosslinking at elevated temperatures. Electron beam irradiation of thin films of the methylene-linked polyesters at room temperature resulted in some chain extension and crosslinking, as evidenced by increased solution viscosity and gel formation. Irradiation at a temperature near or above the glass transition temperatures of the polymers greatly enhanced the tendency for the polymers to crosslink.     

Macro-azo-initiators composed of various polyesters: Their syntheses,thermal properties,and application to block copolymerization

Various aliphatic polyesters such as poly (ethyleneadipate), poly (tetramethylene adipate), poly (caprolactone), and poly (carbonate) were condensed with 4,4'-azobis-4-cyanopentanoyl chloride to prepare macro-azo-initiators. Their thermal properties, observed by differential scanning calorimetry, showed similar decomposition behavior to each other. Block copolymers containing each of these polyesters as a block segment combined with polystyrene or poly (methylmethacrylate) have been derived by the polymerization of monomers initiated with these macro-azo-initiators. © 1994 John Wiley & Sons, Inc.     

Ring-expansion polycondensation of 2-stanna-1,3-dioxepane (or 1,3-dioxepene) with dicarboxylic acid chlorides

2,2-Dibutyl-2-stanna-1,3-dioxepane 1 (or 1,3-dioxepene 2) were prepared from 1,4-butane (or 1,4-butene) diol and dibutyltin dimethoxide. They were polycondensed at 80°C in n-heptane with adipoyl-, suberoyl, sabacoyl chloride and with decane-1,10-dicarbonyl chloride. In the case of suberoyl chloride and 2,2-dibutyl-2-stanna-1,3-dioxepane reaction time, temperature and stoichiometry were varied to optimize both the molecular weight and the fraction of cyclic polyesters. With a slight excess of the dicarboxylic acid chlorides, only macrocyclic polyesters were obtained in all cases. The resulting cyclic polyesters were characterized by viscosity measurements, by ¹H and ¹³C NMR and by MALDI-TOF mass spectrometry.     

Phenazasiline-containing polyamides and polyesters

A Phenazasiline ring was incorporated into a polymer backbone by polycondensation of 2,8-dichloroformyl-5,10-dihydro-5-methyl-10,10-diphenylphenazasiline (V) with aromatic diamines or bisphenols, and phenazasiline-containing polyamides and polyesters were obtained. The polyamides were prepared by low-temperature solution polycondensation in N-methyl-2-pyrrolidone (NMP) in the presence of lithium chloride. The polyesters were synthesized by interfacial polycondensation in a mixture of 1,2-dichloroethane and aqueous alkali in the presence of tetrabutylammonium chloride as an accelerator. These reaction conditions gave the corresponding polymers with high viscosities. The phenazasiline-containing polyamides exhibited good solubilities in polar aprotic solvents such as dimethylformamide, dimethylacetamide, and NMP, and also in m-cresol, although the polyesters showed limited solubilities in organic solvents. Under nitrogen, the phenazasiline-containing polyamides and polyesters showed little degradation below 400°C and had good heat resistance.     

Synthesis and characterization of new soluble cardo polyesters derived from 1,1‐bis‐[4‐(4‐chlorocarboxyphenoxy)phenyl]‐4‐tert‐butylcyclohexane with various bisphenols by solution polycondensation

A new cardo diacid chloride, 1,1‐bis‐[4‐(4‐chlorocarboxyphenoxy)phenyl]‐4‐tert‐butylcyclohexane ( 4 ), was synthesized from 1,1‐bis‐[4‐(4‐carboxyphenoxy)phenyl]‐4‐tert‐butylcyclohexane in refluxing thionyl chloride. Subsequently, various new polyesters were prepared from 4 with various bisphenols by solution polycondensation in nitrobenzene using pyridine as a hydrogen chloride quencher at 150 °C. These polyesters were produced with inherent viscosities of 0.32–0.50 dL · g^?1. Most of these polyesters exhibited excellent solubility in a variety of solvents such as N,N‐dimethylformamide, tetrahydrofuran, tetrachloroethane, dimethyl sulfoxide, N,N‐dimethylacetamide, N‐methyl‐2‐pyrrolidinone, m‐cresol, o‐chlorophenol, and chloroform. These polymers showed glass‐transition temperatures (T_g's) between 144 and 197 °C. The polymer containing the adamantane group exhibited the highest T_g value. The 10% weight loss temperatures of the polyesters, measured by thermogravimetric analysis, were found to be in the range of 426–451 °C in nitrogen. These cardo polyesters exhibited higher T_g's and better solubility than bisphenol A‐based polyesters. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2951–2956, 2001     

Determination of end groups as a function of molecular size for aliphatic polyesters by derivatization of end groups and size-exclusion chromatography with infrared detection

End groups of poly(ethyleneglycol sebacate) having number average molecular weights less than 2500 were characterized as a function of molecular size by derivatizing end groups separately to form 3,5-dinitrobenzoyl and p-nitrobenzyl esters. A hydroxyl end group was reacted with 3,5-dinitrobenzoyl chloride (DNBC) and a carboxyl end group was reacted with O-(p-nitrobenzyl)-N,N′-diisopropyl isourea (PNBD). After separation of these derivatized polyesters by size-exclusion chromatography, the effluent was monitored by using a highly sensitive infrared detector. Concentrations of polyesters were monitored at 1740 cm^?1 for a carbonyl group in the main chain, polyesters derivatized with DNBC at 1560 cm^?1 for a hydroxyl end group (characteristic absorption band for the nitro group of DNBC), and polyesters derivatized with PNDB at 1537 cm^? for a carboxyl end group (a characteristic absorption band for the nitro group of PNBD). By this technique, three types of polyesters having different end groups were characterized: a diol-type polyester, a mixture of polyesters of a diol type and a mono-ol/monocarboxyl type, and a mixture of polyesters of a dicarboxyl type a mono-ol/monocarboxyl type.