银杏双黄酮高效液相色谱定量分析方法研究

建立HPLC法同时测定银杏植物中阿曼托黄素、白果素、银杏黄素异构体、金松双黄酮含量。银杏叶、外种皮、白果提取液的分析采用Elite Hypersil ODS2(4.0 mm×200 mm,5μm),以甲醇-有机酸水溶液为流动相,梯度洗脱,体积流量0.8 mL/min,检测波长330 nm,柱温35℃。4种成分在各自范围内均呈良好的线性关系(r≥0.9993),平均加样回收率98.3%~101.0%,RSD为1.74%~2.23%。银杏叶和外种皮中均含有4种单组分双黄酮,其中白果中双黄酮总量最低,银杏叶中最高。方法准确稳定、重复性好,可用于银杏中双黄酮类成分含量的测定。     

Enumeration of stereo,position and chiral isomers of polysubstituted giant fullerenes: applications to C180 and C240

Abstract

We have developed combinatorial generation function methods that combine M?bius inversion and character cycle indices for the enumeration of stereo, position and chiral isomers of icosahedral giant fullerenes C₁₈₀ and C₂₄₀. Techniques are also developed for the machine perception of symmetries of especially giant fullerenes. The techniques yield, symmetries, position, stereo and chiral isomers of giant fullerenes which we illustrate with applications to icosahedral C₁₈₀(I_h), and C₂₄₀(I_h). We have obtained combinatorial tables for the isomers of C₁₈₀X_k and C₂₄₀X_k. Our results point to errors in previous computations on C₂₄₀ permutations. We have also outlined applications to NMR and ESR spectroscopy.     

Alterations in ruminal bacterial populations at induction and recovery from diet-induced milk fat depression in dairy cows

Ten ruminally cannulated Holstein cows were used in a crossover design that investigated changes in ruminal bacterial populations in response to induction and recovery from diet-induced milk fat depression (MFD). Further, the effect on the ruminal microbiota of the cows with diet-induced milk fat depression inoculated with rumen contents from non-milk fat-depressed donor cows was evaluated. Milk fat depression was induced during the first 10 d of each period by feeding a low-fiber, high-starch, and high-polyunsaturated fatty acid diet (26.1% neutral detergent fiber, 28.1% starch, 5.8% total fatty acids, and 1.9% C18:2), resulting in a 30% decrease in milk fat yield. Induction was followed by a recovery phase, where all cows were switched to a high-fiber, low-starch, and low-polyunsaturated fatty acid diet (31.8% neutral detergent fiber, 23% starch, 4.2% total fatty acids, and 1.2% C18:2) and were allocated to (1) control (no inoculation) or (2) ruminal inoculation with donor cow digesta (8 kg/d for 6 d). Ruminal samples were collected at the end of induction (d 10) and during recovery (d 13, 16, and 28), separated to solid and liquid fractions, extracted for DNA, PCR- amplified for the V1-V2 region of the 16S rRNA gene, and analyzed for bacterial diversity. Results indicated that bacterial communities were different between fractions. In each fraction, differences were significant between the induction (d 10) and recovery (d 13, 16, and 28) periods; however, differences were less apparent with time during the recovery period. The MFD (d 10) was typified by a reduction in the relative sequence abundance of Bacteroidetes and an increase in the relative sequence abundance of Firmicutes and Actinobacteria across both fractions. At the genus level, relative sequence abundance of unclassified Lachnospiraceae, Butyrivibrio, Bulleidia, and Coriobacteriaceae were higher on d 10 and were positively correlated with trans-10,cis-12 CLA and the trans-10 isomer, suggesting their potential role in altered biohydrogenation reactions. A switch to the recovery diet resulted in a sharp increase in the Bacteroidetes lineages and a decrease in Firmicutes members on d 13; however, this shift appears to stabilize by d 28, indicating the restoration process for ruminal bacteria from an altered state is gradual and complex. Inoculation of 10% of rumen contents from non-MFD donor cows to MFD cows revealed this procedure had transient effects on only a few bacterial populations, and such effects disappeared after d 16 following cessation of inoculation. It can be concluded that alterations in milk FA profiles at induction are preceded by microbial alterations in the rumen driven by dietary changes.     

Configurational Isomers Induced Significant Difference in All-Polymer Solar Cells

The design of polymer acceptors plays an essential role in the performance of all-polymer solar cells. Recently, the strategy of polymerized small molecules has achieved great success, but most polymers are synthesized from the mixed monomers, which seriously affects batch-to-batch reproducibility. Here, a method to separate γ-Br-IC or δ-Br-IC in gram scale and apply the strategy of monomer configurational control in which two isomeric polymeric acceptors (PBTIC-γ-2F2T and PBTIC-δ-2F2T) are produced is reported. As a comparison, PBTIC-m-2F2T from the mixed monomers is also synthesized. The γ-position based polymer (PBTIC-γ-2F2T) shows good solubility and achieves the best power conversion efficiency of 14.34% with a high open-circuit voltage of 0.95 V when blended with PM6, which is among the highest values recorded to date, while the δ-position based isomer (PBTIC-δ-2F2T) is insoluble and cannot be processed after parallel polymerization. The mixed-isomers based polymer, PBTIC-m-2F2T, shows better processing capability but has a low efficiency of 3.26%. Further investigation shows that precise control of configuration helps to improve the regularity of the polymer chain and reduce the π–π stacking distance. These results demonstrate that the configurational control affords a promising strategy to achieve high-performance polymer acceptors.     

三氧化二铝PLOT柱气相色谱法分离氢同位素自旋异构体

氢同位素核自旋异构体正-仲态比例影响氢同位素的低温物性,有必要对其比例进行测定。本文利用活性三氧化二铝多孔层开管(Porous Layer Open Tubular,PLOT)柱实现了正-仲氢同位素(氕、氘)的基线分离,发展了一种可在液氮温度下测定同核分子正-仲态比例的色谱分析技术。研究结果表明,与传统三氧化二铝填充柱相比,高效PLOT柱实现了正、仲氕(o-H_2、p-H_2)以及正、仲氘(o-D2、p-D2)的基线分离(分离度R_s大于1.5),当流量为5 m L·min-1时,分离度R_s(p-H_2,o-H_2)=6.9,R_s(o-D2,p-D2)=1.8。正仲态分离度与进样量、流量均有关系。根据峰面积的积分结果,常温(298 K)下正、仲氕比例为2.77:1,正、仲氘比例为1.78:1,与理论测算值基本符合。HD与o-H_2实现了部分分离,R_s(o-H_2,HD)=0.5,根据理论预测,实现HD与o-H_2的基线分离(R_s达到1.5),理论塔板数需要达到3.9×105。     

化学计量学-荧光分析法同时测定甲酚的3种同分异构体

利用化学计量学中的主成分回归法(PCR)和荧光分析法相结合,并用遗传算法(GA)对其进行优化,建立了同时测定甲酚混合物中3种同分异构体的新方法。在p H 4.92的磷酸氢二钠-磷酸二氢钾缓冲介质中,邻、间、对甲酚浓度在3.00~12.0μg/m L范围内,以λ=274 nm为定激发波长,测定300~335 nm波长范围内的荧光光谱,分别使用PCR和GA-PCR两种校正模型对光谱数据进行解析,并同时对3种异构体进行定量分析。研究结果表明,两种方法对邻、间、对甲酚进行预测的平均回收率分别为89.0%、107.5%、100.4%和100.6%、99.1%、98.0%,均方根预测误差分别为0.71、0.49、0.15μg/m L和0.17、0.16、0.21μg/m L,精密度试验的相对标准偏差均小于1.0%,且经GA优化后的PCR方法的加标回收率得到了明显改善,均方根预测误差减小50%,具有更好的准确度。     

Oral and intestinal digestion of oligosaccharides as potential sweeteners: A systematic evaluation

The utilisation of oligosaccharides by oral microorganisms and intestinal enzymes are important factors in determining their effectiveness as alternative sweeteners. In this study, classes of naturally occurring sugars were assessed using in vitro models for oral and intestinal digestibility, in order to test the influence of chemical structure on functional properties. Amongst the classes of sucrose isomers, α-glucobioses, β-glucobioses and sucrose-based oligosaccharides, structures were identified that were not utilised by the common oral bacterium Streptococcus mutans, and would therefore contribute to the non-cariogenic potential of a sweetener. Analysis of the rate and products of digestion by a rat glucosidase mixture was used to determine the relative intestinal digestibility. The results showed that oligosaccharides containing a (1 → 6)-β-Glc group, including gentiobiose and gentiobiitol, together with melezitose, a sucrose-derived oligosaccharide containing a α-Glc-(1 → 3)-Fru moiety were resistant to digestion by both S. mutans and mammalian intestinal enzymes, highlighting their potential as dietary sugar substitutes.     

Tunneling in High-K Isomeric Decays

We have systematically investigated highly-K-forbidden transitions observed in the Hf, W and Os region, using the γ-tunneling model in which low-K and high-K states interact through a process of quantum tunneling. The measured hindrance factors are compared with the values calculated using the γ-tunneling model. Isotope dependences of γ-tunneling probabilities particularly for neutron-rich nuclei and the relation to stimulated decays of isomers are discussed.     

A study on the aromaticity and kinetic stability of fullerene C38 isomers and their molecular ions

The aromaticity of the fullerene C₃₈ isomers and their molecular ions is examined by the topological resonance energy (TRE) method. The aromaticity order obtained by the TRE method is compared with relative energies found in DFT calculation results reported in literature. It is found that all C₃₈ isomers exhibit antiaromaticity when in the neutral state. However, they are highly aromatic in the hexaanionic states. The minimum bond resonance energy (min BRE) method is utilized to estimate the kinetically stability of the C₃₈ isomers and their molecular ions. According to the min BRE method, C₃₈ isomers are only have kinetic stability in penta- and hexavalent molecular anionic states.