Properties of methyltetrahydrophthalic anhydride‐cured epoxy resin modified with MITU

Methylimidazole‐terminated chain‐extended urea (MITU) containing polypropylene oxide spacer was synthesized and employed to modify epoxies composed of a diglycidyl ether of bisphenol‐A (E‐51) and methyltetrahydrophthalic anhydride (MTHPA). The curing behavior, viscoelastic property, impact response, and fracture surface morphology of the curing systems were systematically investigated. Differential scanning calorimeter (DSC) analysis reveals that the curing reactivity of the epoxy system is greatly enhanced with the addition of MITU. From the dynamic mechanical analysis, besides the low‐temperature β relaxation, shoulder at higher temperature side appears for the MITU‐modified systems. Meanwhile, the addition of MITU leads to the increase of loss factor (tan δ) over the temperature range of 0–75°C. Impact tests show that the modifier can be effective in toughening the epoxy resin at relatively low loading, and the scanning electron microscope (SEM) images of the fracture surface for the modified systems display signs of ductility. Copyright © 2008 John Wiley & Sons, Ltd.     

Investigation of the thermal and structural behaviour of diclofenac sodium-sugar ester surfactant systems

Sugar esters (SEs) have a wide range of hydrophilic-lipophilic balance (HLB) values (1–16) and hence can be applied as surfactants or as solubility or penetration enhancers. They can be used for hot melt technology and solvent method which are frequently applied techniques to preparation of solid dispersions. In this study drug-SE products were prepared by physical mixing, melt technology and solvent methods. The products were investigated by DSC, X-ray powder diffraction and dissolution tests. Diclofenac sodium (DS) as model drug and two SEs, P1670 (HLB=16) and S970 (HLB=9) were used for the preparation of the products. DSC curves revealed considerable melting range and enthalpy decreases for the DS-SE products. The dissolved drug molecules broke down the structures of the SEs but were not built into the crystalline phase of the carrier. The melt technology led to a solid dispersion while in the case of the solvent methods the DS was in molecularly dispersed form which resulted in faster dissolution. The drug release was influenced by the structures resulting from the various treatments, by the HLB and by the gel-forming behaviour of the SEs.     

Total solid-phase synthesis of the azathiocoraline class of symmetric bicyclic peptides

Thiocoraline is a potent antitumor agent isolated from the marine organism Micromonospora sp. This symmetric bicyclic depsipeptide binds the minor groove of DNA. Here we report two solid-phase strategies for the syntheses of azathiocoraline and its analogues. The thioester linkage was replaced by an amide bond to improve the compound's pharmacokinetic properties. The first strategy is based on a convergent (4+4) approach, whilst the second is a stepwise synthesis, cyclizations in both approaches occurring on the solid support. These two strategies were designed to overcome problems caused by the presence of consecutive noncommercial N-methyl amino acids, to avoid epimerization during cyclization and/or fragment condensation, and to form the disulfide bridge under solid-phase conditions. The heterocyclic moiety was added in the last step of the synthesis to assist the preparation of libraries of new compounds with potential therapeutic applications.     

A facile access to spiro furanone skeleton based on Pd(II)-mediated cyclization-carbonylation of propargylic esters

The oxidative cyclization-carbonylation of propargylic esters mediated by Pd(II) afforded cyclic orthoesters, which were hydrolyzed into γ-acetoxy-β-ketoesters. Based on the NMR experiments, it was presumed that the cyclization reaction was initiated by a nucleophilic attack of carbonyl oxygen to the alkyne carbon coordinated to palladium(II). When the γ-acetoxy-β-ketoesters were treated with a basic condition, Knoevenagel-Claisen type condensation took place, and spiro furanone derivatives were obtained in good yields. We applied these reactions to steroid derivatives, and steroid derivatives having a spiro furanone fragment were synthesized. Among them, the spiro furanone 4j had vasorelaxant and bradycardiac activities. Compounds 2i-4k had inhibitory effect on CYP3A.     

Spectrophotometric determination of 4,6-dinitro-o-cresol (DNOC) in soil and lemon juice

Although the use of once widely applied selective herbicide, 4,6-dinitro-o-cresol (DNOC), was cancelled by US-EPA in 1987, it is still found in soil and water due to its slow degradation in the environment. Since solid phase extraction-spectrophotometry combinations are much simpler and cheaper than chromatography/MS based methods and most routine laboratories lack such sophisticated instrumentation, it is desirable to establish novel sensitive, well-established, and field-applicable spectrophotometric methods for the rapid assay of DNOC in water and soil. For this purpose, two distinct spectrophotometric methods utilizing the periodate and copper(II)-neocuproine (Nc) reagents have been developed following Zn/HCl reduction of the pesticide in a microwave oven for 15 s, and validated for DNOC determination at mg L⁻¹ level. The LOD values were 1.6 and 0.2 mg L⁻¹ for periodate and Cu(II)-Nc methods, respectively. Statistical comparison of the developed methods was made with the aid of high performance liquid chromatography (HPLC) equipped with a C₁₈ (5 μm), 250 mm× 4.6 mm ID reversed phase column in conjunction with a UV (264 nm) detector, and a methanol (HPLC grade) +0.1% glacial acetic acid mixture mobile phase. Both spectrophotometric methods were directly applicable to soil since they were not interfered with common soil cations and anions, together with some pesticides. These methods were applied to real samples such as synthetically contaminated montmorillonite and lemon juice, and overall recovery efficiencies at the order of 95% or greater were achieved in the devised adsorption/elution procedures. An 8-hydroxyquinoline (oxine)-impregnated XAD copolymer resin stabilized with Fe(III) salt was used to preconcentrate DNOC at a concentration factor of 20 from lemon juice contaminated with 1 mg L⁻¹ DNOC, and the analyte retained at pH 2.5 was eluted with 0.025 M methanolic NaOH. Both the devised spectrophotometric methods and the proposed preconcentration column with optimized sorption and desorption conditions are novel for DNOC assay in the natural environment.     

Production of natural fruity aroma by Geotrichum candidum

Based on its aromatic potential, Geotrichum candidum isolated from olive vegetation water was tested for the production of volatile compounds. When G. candidum was cultivated on media with glucose as the carbon source, flavor volatile compounds were produced and accumulated in the broth. Fruity flavoring compounds (pineapple-like) such as esters and alcohols were analyzed by gas chromatography coupled to mass spectrometry, including ethyl esters of acetic acid and butyric acid, methyl-3-butan-1-ol, and methyl-2-propan-1-ol. Their synthesis corresponded to the stationary growth phase of the strain. Production of the volatile compounds reached 9.5 g/L of 2-hexanoic acid ethyl ester and 1.6 g/L of benzaldehyde as the main concentrated molecules. Ethyl alcohol seems to be an intermediate metabolite in this pathway.     

双环戊二烯苯酚树脂的合成新工艺

以双环戊二烯（DCPD）和苯酚为原料,甲磺酸为催化剂,合成了双环戊二烯苯酚树脂。适宜工艺条件:苯酚与DCPD摩尔比为5、反应温度120 ℃、反应时间5 h、催化剂质量分数为1.5%,收率89%。所得的双环戊二烯苯酚树脂（DPR）经催化加氢法在H2气压力1.5 MPa、催化剂Pd/Al2O3用量为原料质量分数的0.5%、反应温度80 ℃条件下对树脂进行脱色处理。 得到浅黄色双环戊二烯苯酚树脂,收率89%,经IR和1H NMR表征分析其为目的产物,产物指标达到国际同类产品的质量标准。     

无定型聚芳醚酮的氯甲基化改性

采用硫酸作溶剂及催化剂,1,4-二氯甲氧基丁烷（BCMB）为氯甲基化试剂,在均相反应体系中对酚酞聚芳醚酮（PEK-C）进行氯甲基化改性。 采用无致癌性的BCMB作为氯甲基化试剂实现了环境友好,并且成本低,效率高。 试验结果表明,反应机理由苯环亲电取代与亲核取代2种反应构成。 为避免交联反应的发生,反应要在较低温度下进行（10~30 ℃）。 在此温度范围内可制得氯甲基化程度达3.4且完全线型的氯甲基化酚酞聚芳醚酮。 通过反应温度及时间可对树脂氯甲基化程度（χCH2Cl-）实施有效的调控。 CMPEK-C的结构由IR和1H NMR进行了表征,测定了CMPEK-C的Tg与χCH2Cl-之间的依赖关系及CMPEK-C的耐热及溶解性能。     

基于TG-FTIR的杨木热解过程中脲醛树脂影响机理的模型物研究

热解是废弃人造板高效回收利用的方式,人造板中所含胶黏剂是其不同于生物质的主要特征。为了有效环保地利用热解技术处理废弃人造板,解明人造板热解过程中其所含脲醛树脂胶黏剂(UF)对木材热解特性的影响,深入探索UF对人造板中木材各组分的作用机制,以杨木及木材的三种主要组分(纤维素、半纤维素、木素)为研究对象,创新性地依据杨木的化学组成,以纤维素、木聚糖和木素配制成模型物,并加入UF模拟人造板的构成。利用热重红外光谱联用(TG-FTIR)分析法,对比分析了加入UF前后模型物以及杨木各主要组分的热失重特性及气相演变规律。热重及红外结果表明,UF促进了纤维素热解过程中水和羧酸类物质的生成。UF与木素结合生成热不稳定的含氮结构,释放大量氨气,并且在200～300 ℃区间内参与了木素的热解并直接影响木素热解产物的生成。由此推测,在人造板热解过程中,木材三种主要组分中与UF作用的主要成分是木素。     

人参叶总皂苷大孔树脂分离纯化工艺的近红外光谱在线监测模型及其含量测定

利用近红外(NIR)光谱技术研究并建立可在线监测人参叶皂苷类成分的大孔树脂分离纯化工艺的方法。建立人参皂苷Rg₁,Re和Rb₁的高效液相色谱(HPLC)含量测定方法,收集人参叶提取物的40%乙醇大孔树脂洗脱液,采集其近红外光谱信息,并用已建立的HPLC法测定其中人参皂苷Rg₁,Re和Rb₁的含量,结合偏最小二乘法(PLS)建立上述三种成分及人参总皂苷的定量分析模型。建模过程中,以决定系数(R2),交叉验证均方根误差(RMSECV)为指标,确定用于建模的最优近红外波段和光谱预处理方法,结果表明人参皂苷Rg₁,Re,Rb₁及人参总皂苷模型的最佳建模波段均为12 000.8~7 499.8 cm-1,R2分别为0.988 7,0.960 3,0.990 5和0.970 1,RMSECV分别为0.059 7,0.072 2,0.004 88和0.075 5。将1个批次的人参叶提取物大孔树脂分离纯化工艺样品用于验证人参总皂苷定量分析模型的预测性能,总皂苷的NIR预测值和HPLC测定值的相关系数为0.992 8,平均预测回收率为100.52%,表明所建的模型预测效果良好。该法快速、简便、准确,可用于生产工艺过程中人参总皂苷的含量测定和质量控制。