活性炭负载杂多酸催化合成没食子酸甲酯的研究

以活性炭为载体负载磷钨杂多酸H7PW12O42·4H2O(PW12),催化合成没食子酸甲酯。对催化剂进行了X射线衍射(XRD)晶相分析、N2吸附和酸性表征(NH3-TPD)。讨论了磷钨杂多酸-活性炭催化合成没食子酸甲酯的催化性能。结果表明:在没食子酸0.52 mol、甲醇0.4 mol、PW12负载量为30%、反应时间4 h、催化剂用量为反应物总质量的5%时,没食子酸甲酯(MG)的收率可达到90.1%,该催化剂具有较高的催化活性、容易回收并可多次重复使用。     

黑曲霉全细胞生物催化制备没食子酸丙酯的研究

利用黑曲霉(Aspergillus niger)细胞作为全细胞生物催化剂,研究了催化没食子酸生成没食子酸丙酯的条件,探讨了有机溶剂、细胞预处理、底物浓度、反应时间和水分含量等因素在酶催化没食子酸丙酯合成中的影响,结果表明,苯是最佳溶剂,而菌丝体的含水量在80％时得率最高.在此基础上,选择菌丝量、没食子酸浓度、正丙醇体积分数和反应时间进行了正交试验,在200 r/min、40℃的转化条件下得到的较佳催化组合为:25 mL锥形瓶中加入10 mL苯、0.5g菌丝、7 mmol(0.012 7 g)没食子酸、7.3 ％(0.73 mL)正丙醇组成的有机催化体系中,反应18h,没食子酸丙酯得率达到36.4％.该过程无需要纯化或者固定化酶,实现了没食子酸丙酯低成本、高得率的催化.     

米根霉无载体固定化发酵产L-乳酸

通过研究米根霉NLX-M-1利用葡萄糖无载体固定化发酵产L-乳酸的影响因素,获得米根霉利用木质纤维基葡萄糖进行无载体固定化发酵的最优条件。优化的米根霉无载体固定化产L-乳酸条件:初始葡萄糖质量浓度100 g/L,(NH4)2SO4质量浓度2 g/L,接种量2%(体积分数),CaCO330 g/L,KH2PO40.1 g/L,MgSO4·7H2O 0.25 g/L,ZnSO4·7H2O 0.1 g/L。在优化条件下,以纯葡萄糖为碳源的米根霉发酵过程,形成平均直径1 mm的微球,L-乳酸产量为76.6 g/L,转化率为81.6%。以玉米秸秆酸爆渣酶解葡萄糖浓缩至60 g/L进行L-乳酸发酵,米根霉形成直径约1.2 mm的微球,L-乳酸产量为36.4 g/L,转化率为63.5%。     

脱木质素的催化效应

对4种杂多酸盐——Na4[PMo11VO40]、Na5[PMo10V2O40]、Na7[P2Mo17VO62]和Na2[P2Mo16V2O62]催化的硫酸盐浆酸性H2O2脱木质素的效果进行了考察，并对Na5[PMo10V2O40]催化H2O2脱木质素的温度效应进行了探讨。结果表明，4种杂多酸盐对硫酸盐浆H2O2脱木质素均有较强的催化活性，但它们也加速了碳水化合物的降解。卡伯值降低率和粘度降低率随杂多阴离子负电荷数的增加而降低。Na5[PMo10V2O40]催化的H2O2脱木质素过程似乎呈现出“异常”的温度响应，在60℃左右卡伯值降低率最大。随着反应温度的升高，纸浆的粘度降低率增加。对于杂多酸盐Na5[PMo10V2O40]催化的H2O2脱木质素工艺，温度定为60℃最佳。     

酸性离子液体催化合成乙酸龙脑酯

制备了酸功能化离子液体(3-磺酸基)丙基三乙基铵硫酸氢盐[N(Et)3(CH2)3SO3H]HSO4,并用FT-IR、1HNMR和13CNMR对其进行了表征.将其与氯乙酸组成的复合催化体系用于催化α-蒎烯一步酯化反应,详细考察了离子液体用量、反应温度、反应时间、反应物配比等因素对酯化反应的影响,得到了较佳的反应条件:n(α-蒎烯)∶n[N(Et)3(CH2)3SO3H]HSO4∶n(氯乙酸)∶n(乙酸)5∶0.6∶5∶14,反应温度30℃,反应时间10h.在该条件下α-蒎烯转化率为95.90%,乙酸龙脑酯选择性45.07%.并对催化体系的重复使用性进行了考察,重复使用5次时,α-蒎烯转化率仍达87.4%,乙酸龙脑酯选择性40.6%.     

钼钒同多酸催化降解纤维素制备甲酸的性能研究

以合成的钼钒同多酸Na6[α-Mo6V2O26]·16H2 O为催化剂,对甲苯磺酸为酸催化剂,在水相介质和O2气氛中,考察了钼钒同多酸将纤维素选择性转化为甲酸(FA)的催化性能.实验结果表明:合成的钼钒同多酸催化剂表现出较强的氧化性.在纤维素0.2 g,Na6[α-Mo6V2O26]·16H2O 0.1 g,对甲苯磺酸...     

磺烷基咪唑磷酸盐-氯乙酸复合催化体系在α-蒎烯水合反应中的应用

制备了一种酸功能化离子液体1-(3-磺酸基)丙基-3-甲基咪唑磷酸二氢盐((HSO3-pmim) H2 PO4),并用FT-IR、 1 H NMR、 13 C NMR对其进行了表征.将其同氯乙酸构成的复合催化体系磺烷基咪唑磷酸盐-氯乙酸((HSO3-pmim)H2 PO4-ClCH2 COOH)用于催化α-蒎烯水合反应,详细考察了水合反应的影响因素,得到了较佳的反应条件:n(α-蒎烯)∶ n((HSO3-pmim)H2 PO4)∶ n(氯乙酸)∶ n(水) 6∶ 1∶ 6∶ 30,反应温度 80 ℃,反应时间 8 h.在该条件下α-蒎烯转化率为 97%,松油醇选择性 47.1%.并对催化体系的重复使用性进行了考察,该催化体系不经处理直接重复使用5次时,α-蒎烯转化率仍达 83.7%,松油醇选择性 51.6%.     

不同钠盐对班克松种子萌发的影响

采用不同浓度的NaCl、Na2SO4和Na2CO3溶液处理班克松种子,测定发芽率、发芽势和发芽指数,研究钠盐胁迫对班克松种子发芽的影响。结果表明:低浓度(10、20 mmol·L-1)的NaCl、Na2SO4可以促进种子萌发,随着浓度增加,抑制作用加强,250 mmol·L-1的各项指标降到最低。Na2CO3溶液对种子萌发有较强的抑制作用,浓度相同时,Na2CO3胁迫下的各指标值均小于NaCl、Na2SO4。250 mmol·L-1时各项指标为0。由此可以得出,班克松种子具有耐盐性,但对不同钠盐的敏感性不同,对NaCl、Na2SO4的耐受性要高于Na2CO3。     

松树根际高效解磷青霉发酵条件的优化

土壤磷素供应不足是导致松林地力衰退的重要因素之一,通过研制解磷微生物肥料来分解土壤中难溶磷是改善土壤磷素供应状况的有效途径.在分离获得两株解磷微生物(瓜纳卡斯特青霉JP-NJ2菌株和嗜松青霉JP-NJ4菌株)的基础上,通过正交试验分别对瓜纳卡斯特青霉JP-NJ2菌株及嗜松青霉JP-NJ4菌株的液体发酵培养基部分组分进行了优化,并对其适宜发酵条件进行了研究,得出JP-NJ2菌株适宜发酵培养基为蔗糖10 g+ (NH4)2SO4 0.3 g+MgSO4·7H2O 0.3 g+NaCl 0.3 g+KCl 0.5 g+FeSO4·7H2O 0.03 g+MnSO4·7H2O 0.03 g+卵磷脂0.4 g+CaCO3 5 g+蒸馏水1 000 mL,初始pH 5.0,发酵培养周期为9d,溶氧量为80％;JP-NJ4菌株适宜发酵培养基为蔗糖8 g+ (NH4)2SO40.5 g+MgSO4·7H2O 0.3 g+NaCl0.3 g+KCl0.7 g+FeSO4 ·7H2O 0.03 g+MnSO4 ·7H2O 0.03 g+卵磷脂0.8 g+CaCO3 5 g+蒸馏水1 000 mL,初始pH 6,培养周期为11d,溶氧量为90％.研究结果为两株解磷青霉工业化生产提供了参考.     

竹炭-ZnO复合材料的制备及对苯酚的光催化降解作用

以硅酸钠为粘结剂用浸涂法制备了竹炭-ZnO复合材料,用FT-IR、电镜扫描(SEM)对其进行结构表征和形貌观察,研究了该复合材料对溶液中苯酚光催化降解去除效果.结果表明:制备竹炭-ZnO复合材料的最佳配比为m(竹炭) ∶m(ZnO)∶m(Na2 SiO3·9H2O) 为5∶2∶1;酸性条件下,竹炭-ZnO复合材料对苯酚的去除效果更好,H2 O2对苯酚溶液光催化降解有促进作用.当苯酚溶液的质量浓度为50mg/L时,复合材料最佳用量为2g/L,溶液中H2 O2最佳的添加量为1.95mmol/L,在紫外灯和太阳光下催化降解4h,苯酚去除率分别达到92.3%和76.4%.复合材料重复使用3次,对苯酚的去除率仍可以达到80%以上.     

没食子酸辛酯标准样品的研制

研究了没食子酸辛酯标准样品的制备、均匀性和稳定性及其定值试验。将没食子酸辛酯工业品用无水乙醇溶解,再用纯水稀释后重结晶,得到高纯度的没食子酸辛酯标准样品。没食子酸辛酯含量测定采用液相色谱面积归一化法。所研制的没食子酸辛酯标准样品通过了均匀性检验和稳定性检验(6个月)。经定值检测,该标准样品的质量分数为99.472 0%,不确定度为0.03%。     

Free radicals produced by the oxidation of gallic acid and catechin derivatives

Gallic acid and catechin derivatives were oxidized in alkaline solution (pH 10.0–13.0) with K₃[Fe(CN)₆] under anaerobic conditions, and electron spin resonance (ESR) spectra of the radicals produced were measured. Gallic acid, epicatechin gallate, gallocatechin gallate, epigallocatechin, and epigallocatechin gallate showed hyperfine structures. Gallic acid was found to be oxidatively C—O coupled in alkaline solution (pH 10.5–12.0). It was found that an unpaired electron delocalized over gallocatechin gallate and epigallocatechin molecules, but was localized on the galloyl group and the A-ring of epicatechin gallate and epigallocatechin gallate. The galloyl group of gallo-catechin gallate was readily alkali-hydrolyzed but those of epicatechin gallate and epigallocatechin gallate were resistant to alkaline hydrolysis.     

Development of an isocratic HPLC method for catechin quantification and its application to formulation studies

The aim of this study was to develop a simple, rapid and accurate isocratic HPLC analytical method to qualify and quantify five catechin derivatives, namely (+)-catechin (C), (-)-epigallocatechin (EGC), (-)-epicatechin gallate (ECG), (-)-epicatechin (EC) and (-)-epigallocatechin gallate (EGCG). To validate the analytical method, linearity, repeatability, intermediate precision, sensitivity, selectivity and recovery were investigated. The five catechin derivatives were completely separated by HPLC using a mobile phase containing 0.1% TFA in Milli-Q water (pH 2.0) mixed with methanol at the volume ratio of 75:25 at a flow rate of 0.8ml/min. The method was shown to be linear (r(2)>0.99), repeatable with instrumental precision<2.0 and intra-assay precision<2.5 (%CV, percent coefficient of variation), precise with intra-day variation<1 and inter-day variation<2.5 (%CV, percent coefficient of variation) and sensitive (LOD<1μg/mL and LOQ<3μg/mL) over the calibration range for all five derivatives. Derivatives could be fully recovered in the presence of niosomal formulation (recovery rates>91%). Selectivity of the method was proven by the forced degradation studies, which showed that under acidic, basic, oxidation temperature and photolysis stresses, the parent drug can be separated from the degradation products by means of this analytical method. The described method was successfully applied in the in vitro release studies of catechin-loaded niosomes to manifest its utility in formulation characterization. Obtained results indicated that the drug release from niosomal formulations was a biphasic process and a diffusion mechanism regulated the permeation of catechin niosomes.     

Rapid selection of catechin-rich tea trees (Camellia sinensis) by a colorimetric method

A rapid and efficient colorimetric method based on the use of Fast Blue B-salt (FBB) was established to select catechin-rich tea trees (Camellia sinensis L.). The catechin levels measured by the colorimetric method under optimized reaction conditions correlated closely with estimations by high-performance liquid chromatography (HPLC) analysis. The FBB colorimetric method was successfully used to classify 160 tea trees on the basis of their catechin contents into rich and poor lines. HPLC analysis of the FBB-selected tea tree extracts showed them to contain (−)-epigallocatechin 186 mg/g in tea tree line HR-29, (−)-epicatechin 43.7 mg/g in HR-82, (−)-epigallocatechin gallate 4.32 mg/g in HR-29, and (−)-epicatechin gallate 0.22 mg/g in HR-52. Classification of tea trees from the Hadong region into catechin-rich and -poor trees was independent of the growing season. Thus the FBB colorimetric method could find application as a reliable tool in screening and selection of tea trees on the basis of their catechin content.     

多酚酸酯稳定剂对生物柴油室温稳定性的影响

室温条件下,测定了含不同多酚酸酯稳定剂的生物柴油过氧化值6个月内随时间的变化曲线.用于研究的23种稳定剂,包括:5种没食子酸烷基酯、6种没食子酸萜醇酯(没食子酸金合欢酯、没食子酸香叶酯、没食子酸芳樟酯、没食子酸橙花叔醇酯、没食子酸薄荷酯和没食子酸氢化松香酯)、3种合成抗氧化剂、2种天然抗氧化剂、3种双组分稳定剂、2种三组分稳定剂以及2种含协同增效剂的稳定剂.结果显示没食子酸甲酯对生物柴油的室温稳定化作用明显强于其它4种没食子酸烷基酯、6种没食子酸萜醇酯、3种合成抗氧化剂和2种天然抗氧化剂;没食子酸金合欢酯对生物柴油的室温稳定化作用强于其它5种没食子酸萜醇酯;双组分稳定剂和三组分稳定剂等复合组分稳定剂没有明显改善生物柴油的室温稳定性;含协同增效剂的稳定剂能提高生物柴油的室温稳定性,协同增效剂柠檬酸的作用特别明显;杂质铁和杂质铜会降低生物柴油的室温稳定性,且杂质铁的影响大于杂质铜.     

基质固相分散和HPLC-IT-TOF/MS联用研究漆树木材中多酚成分

采用基质固相分散(MSPD)技术进行漆树木中多酚化合物的提取,根据单因素试验得到优化工艺条件为:ZSM-22为吸附基质,吸附基质与样品的质量比为2:1,洗脱溶剂为体积分数70％甲醇,洗脱溶剂用量8 mL,研磨时间2 min.在此条件下,漆树木多酚提取得率为(466±2.05)mg/g(以没食子酸计).采用高效液相色谱-...     

1-没食子酸甘油酯的研制及其抗氧化性能的研究

在实验室条件下,以没食子酸和甘油为原料合成了1-没食子酸甘油酯(GG),做为油脂或油脂食品的抗氧化剂,保护油脂不因氧化腐败,延长贮存时间。合成途径是在日本高砂光正等人工作基础上进行了若干改进,使得率由45.7％提高到72.9％。以菜子油和豆油做底物,丙酯(PG)和2,6-二特丁基对甲酚(BHT)做对比抗氧化剂,用增重法评价其抗氧化性能,柠檬酸和酒石酸做增效剂,评价其增效作用,研究了浓度和分散度对诱导期的影响,探讨了结构因素对性能的影响。实验室结果表明:在本实验条件下,活性次序是GG>PG>BHT,随着浓度的增加,活性增大顺序是GG>PG>BHT。酒石酸对GG有增效作用,柠檬酸无效。溶解度对诱导期没有影响,说明了性能差异产生的原因。通过研究为简化合成途径,进行工业化生产提供了依据,并在此基础上为合成新型抗氧化剂找到一种可行方法。     

7种抗氧化剂对栝楼籽油的抗氧化作用

提取栝楼籽油脂,采用Schaal烘箱法,以过氧化值为指标,研究了BHA、BHT、Vc、VE、Vc棕榈酸酯、异Vc和PG7种抗氧化剂在标准添加计量下对栝楼籽油的抗氧化效果。结果表明,与不加抗氧化剂（CK）相比,7种抗氧化剂对栝楼籽油都有不同强度的抗氧化活性,其中BHA的抗氧化能力比其它6种抗氧化剂强的多。BHT的抗氧化能力略强于PG、Vc、异Vc、VE和Vc棕榈酸酯。     

Drought-induced changes in flavonoids and other low molecular weight antioxidants in Cistus clusii grown under Mediterranean field conditions

Mediterranean plants have evolved a complex antioxidant defense system to cope with summer drought. Flavonoids, and particularly flavanols and flavonols, are potent in vitro antioxidants, but their in vivo significance within the complex network of antioxidant defenses remains unclear, especially in plant responses to stress. To gain insight into the role of flavonoids in the antioxidant defense system of Cistus clusii Dunal, we evaluated drought-induced changes in flavonoids in leaves and compared the response of these compounds with that of other low molecular weight antioxidants (ascorbic acid, tocopherols and carotenoids). Among the antioxidant flavonoids analyzed, epigallocatechin gallate was present in the greatest concentrations (up to about 5 micromol dm(-2)). Other flavanols, such as epicatechin and epicatechin gallate, were found at concentrations below 0.25 and 0.03 micromol dm(-2), respectively. Neither of the antioxidant flavonols analyzed, quercetin and kaempferol, were detected in C. clusii leaves. Epigallocatechin gallate, ascorbic acid and alpha-tocopherol concentrations increased to a similar extent (up to 2.8-, 2.6- and 3.3-fold, respectively) in response to drought, but the kinetics of the drought-induced increases differed. Epigallocatechin gallate, epicatechin and epicatechin gallate concentrations increased progressively during drought, reaching maximum values after 30 days of stress. Ascorbic acid concentrations increased twofold after 15 days of drought, and maximum values were attained after 50 days of drought. In contrast, alpha-tocopherol concentrations remained constant during the first 30 days of drought, but increased sharply by 3.3-fold after 50 days of drought. The maximum efficiency of photosystem II photochemistry and the extent of lipid peroxidation remained constant throughout the drought period, whereas the redox state of ascorbic acid and alpha-tocopherol shifted toward their reduced forms in response to drought, indicating that the concerted action of low molecular weight antioxidants may help prevent oxidative damage in plants.