碳核苷类似物的合成与生物活性

利用杂环金属盐法,通过呋喃碳核苷中间体,合成了哒嗪、哒嗪酮等碳核苷,讨论了反应机理;提高了呋喃汞盐法合成碳核苷的收率及立体选择性.     

香料香精行业废气中气味成分分析

采用气袋法-固相微萃取-气相色谱质谱联用技术,对香料香精行业废气进行采集、萃取和分析。通过对固相微萃取(SPME)的条件优化,选择CAR-PDM S-DVB纤维,在萃取时间1 h,解吸时间10 s的条件下,结合气相色谱质谱分别对香料香精企业A和B有机废气中气味物质进行分析。分别从企业A和B中检测到66和75种化合物,其主要气味成分包括:柠檬烯、雪松醇、薄荷醇、紫罗兰酮和硫醇等。方法可为香料香精行业有机废气中气味物质的分析及行业废气中气味治理提供参考。     

一种酚类抑制剂对亚硫酸镁氧化反应动力学的影响及作用机理

亚硫酸镁的氧化是湿式镁法烟气脱硫过程中的重要步骤. 通过实验筛选出一种新型酚类抑制剂(T), 可显著延缓亚硫酸镁的氧化反应速率. 在接近实际工况条件下, 研究了抑制剂浓度、亚硫酸镁浓度、氧分压、pH、温度等条件对亚硫酸镁氧化速率的影响. 结果表明, 抑制剂T、溶解氧及亚硫酸镁的分级数分别为－0.25, 0.5和0, 反应的表观活化能为48.2 kJ•mol^－1. 结合建立的三相反应模型, 对T抑制条件下的总反应过程进行了推断, 认为亚硫酸镁氧化的本征化学反应在贫氧区进行, 而总反应速率受氧的传质扩散过程控制. 与非抑制条件下的结果相比, T的存在降低了本征反应速率, 进而使氧的传质速率减小. 研究结果为利用抑制氧化手段实现脱硫副产物回收提供了有益参考.     

导电性聚呋喃的氧化合成及应用

总结了芳香族聚呋喃的氧化聚合方法,系统论述了聚合过程中影响聚呋喃性质的各种因素,推测了聚呋喃的链结构,介绍了聚呋喃的各种改进方法和效果。指出聚呋喃及其共聚物是一种电导率在10-11到10-1S.cm-1范围内有机半导体材料,其电聚合沉积膜具有奇特的电活性、优良的热加工性和特殊的表面形貌,可望在金属离子和有机物质的吸附与富集、传感探测等领域发挥作用。     

N-叔丁基苯基呋喃甲酰肼的合成研究

N-叔丁基苯基呋喃甲酰肼是具有良好生物活性的含呋喃环双酰肼类昆虫生长调节剂(IGRs)的重要中间体,可由酰氯与叔丁基肼发生亲核反应制得。通过反应条件探索,获得了同时制备N1-叔丁基苯基呋喃甲酰肼和N2-叔丁基苯基呋喃甲酰肼的合成方法,并用此法制备了10个未见报道的新化合物,其结构通过1HNMR、IR、MS及元素分析确证。本文还通过计算化学方法对其反应机理及在不同条件下所生成异构体的现象进行了初步探讨。     

超高效液相色谱-串联质谱法检测鸡肌肉组织中硝基呋喃类代谢物残留

硝基呋喃类抗生素主要指呋喃唑酮、呋喃西林、呋喃妥因和呋喃它酮,为一类广谱抗生素.此类药物广泛添加于动物饲料中,以防止细菌性传染和作为促生长剂,但是近年来研究结果表明,该类药物具有一种诱导有机体基因突变的物质,因此欧洲各国均已将硝基呋喃类抗生素列为违禁药物,我国在2002年发布的农业部第193号公告中明确将硝基呋喃类药物列为在所有食品动物禁用兽药.     

新型铱配合物化学发光探针测定亚硫酸盐的研究

研究发现酸性条件下,亚硫酸根对自制的新型环金属铱配合物[ (dpci)2Ir(pca)])(dpci=3,4-二苯基邻二氮杂萘,pca=吡啶-2-羧酸)-硫酸铈体系的化学发光有显著的增强作用,据此建立了检测亚硫酸根的新方法.在最佳条件下,亚硫酸根浓度与化学发光强度在5.0×10-7 ～3.0×10-4 mol/L范围内...     

生物质基呋喃衍生物选择氢解制备戊二醇和己二醇研究进展

生物质基呋喃衍生物来源广泛,利用生物糠醛、5-羟甲基糠醛及他们的衍生物选择氢解制备戊二醇、己二醇具有重要的研究价值和意义.根据原料和催化剂体系不同对生物质基呋喃衍生物选择氢解制备高碳二元醇的代表性工作进行了归纳总结,对影响催化剂活性和选择性的关键因素如活性金属、载体、助剂及反应溶剂等进行了分析讨论,对反应可能涉及的路径和机理进行了阐述,并对未来的研究方向和发展趋势作了展望.     

HS/GC-MS法分析胶基型嚼烟中的挥发性香味物质

运用静态顶空气相色谱-质谱法对22个胶基型嚼烟样品中的挥发性香味物质进行分析,并采用质谱数据库对挥发性香味物质进行定性分析。对顶空分析条件以及GC-MS条件进行了优化,提高了挥发性香味物质的测定灵敏度;对峰面积归一化结果大于0.1%的化合物进行定性分析,通过匹配度限定(≥85%)确认了65种挥发性香味物质;最后对样品进行了相似性分析和聚类分析。结果表明:22个胶基型嚼烟样品中的香味物质主要有酯类(18个化合物)、烯烃类(16个化合物)、醇类(9个化合物)、醛类(8个化合物)、酮类(7个化合物)、酚类(1个化合物)、酸类(1个化合物)、呋喃类(2个化合物)、烷烃类(2个化合物)、硫醚类(1个化合物),共10类化合物;不同胶基型嚼烟样品的品牌识别度高,同时口味对品牌识别有一定的影响作用。方法为进一步开发胶基型嚼烟制品提供了理论基础和技术支持。     

4-羰基-2-戊烯醛与硫代乙酸加成的研究

以2-甲基-2,5-二甲氧基-2,5-二氢呋喃水解产物与硫代乙酸加成并在不同条件下关环,制得了β-乙酰硫基呋喃、噻吩和毗咯的各种异构产物,提供了按需要制备不同α-甲基-β-巯基呋喃、噻吩和吡咯衍生物的途径。     

纸浆卡伯值的可见分光光度法在线测量

卡伯 (Kappa)值是纸浆质量的重要指标 ,而纸浆中的木素含量决定了纸浆的卡伯值。该文研究了用可见分光光度法在线测量酸法制浆过程蒸煮液中溶出的木素含量去预测纸浆中木素含量和纸浆卡伯值的方法 ;确定了合适的可见光光谱测量波段 (460～580nm) ;建立了纸浆卡伯值与蒸煮液吸光度 (A)的相关方程。结果显示卡伯值与A之间有良好的线性关系 ,为实现蒸煮过程纸浆卡伯值的在线测量提供了依据。     

张裕XO级白兰地挥发性成分的提取分离与鉴定

建立了一套对白兰地挥发性物质进行预处理的方法,并采用气相色谱-质谱法(GC-MS)较全面地鉴定了白兰地的挥发性成分。实验先采用液-液萃取方法提取张裕XO级白兰地的挥发性成分,然后将酸性成分与碱性和中性成分分离,再采用柱色谱分离手段将其分离为若干个级分并浓缩,采用气相色谱-质谱、标准品比对、保留指数(RI)值比较等方法对分离得到的各级分中的成分进行了鉴定,在白兰地中共鉴定出302种挥发性成分,包括醇30种、醛酮类35种、酸类20种、酯类104种、苯同系物及其衍生物24种、酚类14种、缩醛14种、呋喃类16种、萜烯类22种和其他物质23种。结果表明,采用这套预处理方法能将白兰地的挥发性成分较有效地分组和浓缩。     

Ion chromatographic measurement of sulfide, methanethiolate, sulfite and sulfate in aqueous and air samples

Simultaneous measurement of sulfur species was investigated using ion chromatography. Sulfide, methanethiolate, sulfite and sulfate are representative of sulfur species. The aqueous sulfur species were simultaneously measured using a two-detector system: suppressor-type conductivity detector for sulfite and sulfate, and fluorometric or electrochemical detector for the reduced sulfur compounds. The major sulfur-containing gases, hydrogen sulfide, methyl mercaptan and sulfur dioxide are collected into aqueous solution as the species listed above. Collection of sulfur gases using a membrane-based cylindrical diffusion scrubber was investigated. Atmospheric hydrogen sulfide and sulfur dioxide are measured by the diffusion scrubber collection and subsequent measurement by ion chromatography without an enrichment column. In addition to the two gases, methyl mercaptan was also determined using a dual scrubber system.     

Analysis of volatile compounds of rosemary honey. Comparison of different extraction techniques

Summary The analysis of the volatile fraction from honey requires the sugar matrix to be separated prior to the analysis by GC-MS. In this study, three extraction techniques, simultaneous extraction-distillation, liquid-liquid extraction and solid-phase extraction, were compared to the extraction of the volatile compounds of a rosemary honey. Analysis of these fractions by gas chromatography—mass spectrometry enabled the tentative identification of up to 122 volatile compounds (alcohols, ketones, aldehydes, acids, esters, terpenes, hydrocarbons, phenol, furan and pyran compounds). SDE extracts were rich in terpenes and esters, while the other two techniques avoided the formation of artefacts due to heating the sample.     

Estimation of the Effect of Diffusion and Transformation of Lignosulfonates on the Mechanism of Delignification in Sulfite Cooking of Spruce Wood

The contribution of diffusion and transformation of macromolecules to the mechanism of delignification of cell wall in sulfite cooking of spruce wood was quantitatively estimated from variation of the parameters of the Kolmogorov-Erofeev-Avrami equation and hydrodynamic radii of lignosulfonate macromolecules found in the cooking liquor.     

液相色谱-毛细管气相色谱/质谱离线联用分析烟草中的挥发性及半挥发性成分

建立了一种用于烟草样品中挥发性、半挥发性成分分析的液相色谱-毛细管气相色谱/质谱(LC-CGC/MS)离线联用方法。研究了LC-CGC/MS的分离机理。LC分析选用氨基分析柱(250 mm×2.0 mm, 5 μm)作为分析柱,正己烷-二氯甲烷-乙腈(90:6.6:3.4, v/v/v)作为流动相,对挥发性、半挥发性成分进行分离,收集得到5个馏分,并存放在5个氮吹瓶中。多次进样并收集相同时间段的馏分,氮吹浓缩至1 mL,然后分别进行CGC/MS分析,所用的CGC柱为DB-5MS(60 m×0.25 mm×0.25 μm)。结果显示,与直接采用CGC/MS分析相比,采用LC-CGC/MS分析复杂样本的效果更好,定性的可靠性更高。     

Cellulose destruction by electron-beam-induced heating

An efficient method for producing furfural and other furan derivatives from cellulose was proposed. Radiolytic destruction of cotton cellulose, sulfate and sulfite pine celluloses, and carboxymethylcellulose was studied under electron-beam-induced distillation conditions. The yield of the liquid distillate from cellulose of various origin was about 60%. Furfural and its derivatives with the molecular weight up to 140 were the predominant products. Grinding and preheating of cellulose increase the fraction of furan derivatives in the condensate. The liquid products are partially transformed into high-molecular-weight compounds that are distilled with difficulty and that are involved in the formation of wood charcoal in the yield of about 20%.     

Synthesis of an efficient bio-based plasticizer derived from waste cooking oil and its performance testing in PVC

In order to develop an efficient and sustainable plasticizer, the waste cooking oil and malic acid were used as the main raw materials in this study to synthesize a bio-based plasticizer (acetylated-fatty acid methyl ester-malic acid ester, AC-FAME-MAE) by environment-friendly methods, and the structure was characterized by FTIR and ¹H NMR. The properties of the poly (vinyl chloride) (PVC) with AC-FAME-MAE were tested and compared with those of the PVC plasticized with DOP (di-2-ethylhexyl phthalate) and EFAME (epoxy fatty acid methyl ester), respectively. The results of tensile test, TGA and leaching test showed that the mechanical properties, thermal stability and overall solvent resistance of PVC films with AC-FAME-MAE were significantly better than those of PVC films plasticized by DOP or EFAME. From the results of DMA, the plasticized efficiency of AC-FAME-MAE was as good as DOP. The application of AC-FAME-MAE has higher safety in the food industry based on the results of food simulation fluids experiment.     

Synthesis of anti-HIV lithospermic acid by two diverse strategies

An efficient and convergent route for the synthesis of the natural product (+)-lithospermic acid, which possesses anti-HIV activity, was accomplished. The (±)-trans-dihydrobenzo[b]furan core therein was prepared by two different strategies. The first strategy involved the use of a palladium-catalyzed annulation to generate an appropriately substituted benzo[b]furan ester followed by a stereoselective reduction of a carbon-carbon double bond with Mg-HgCl(2)-MeOH. The second strategy relied on an aldol condensation between a suitably substituted methyl arylacetate and 3,4-dimethoxybenzaldehyde, followed by cyclization. Finally, a total synthesis of (+)-lithospermic acid was completed via coupling of a trans-dihydrobenzo[b]furan cinnamic acid with an enantiomerically pure methyl lactate.     

Application of a solvent‐free solid injection technique coupled with GC–MS for discrimination between the secondary metabolites of wild and cultivated South Korean medicinal foods

Solvent‐free solid injection was applied to differentiate between wild and cultivated South Korean medicinal foods, including dureup (Aralia elata ), deodeok (Codonopsis lanceolata ) and doraji (Platycodon grandiflorus ). A number of compounds were identified in wild and cultivated dureup (53 and 46), deodeok (47 and 51) and doraji (43 and 38). Secondary metabolites, including butanal,2‐methyl‐, β ‐caryophyllene, neoclovene, α ‐humulene, γ ‐curcumene, β ‐bisabolene, and phytol, were identified in dureup with significantly (P < 0.05) different amounts between both types. In deodeok, squalene and other main components such as acetic acid, methyl ester, furan‐methyl‐furfural, 2‐furan‐methanol, and 5‐methyl‐furfural, were statistically different between the two types. Doraji has significantly different compounds such as furfural, 5‐methyl‐furfural, 2‐methoxy‐phenol, 2‐methoxy‐4‐(1‐propenyl)‐phenol, and 1‐(4‐hydroxy‐3‐methoxyphenyl)‐2‐propanone. Although we failed to confirm the key compounds, a new compound, namely desaspidinol, was synthesized for the first time and its retention index determined under the experimental conditions. This solventless, easy technique can be used as a simple way to discriminate between wild and cultivated types of medicinal plants via identification of volatile markers or specific fingerprints.