氟喹诺酮类抗生素与赤藓红的共振瑞利散射光谱研究及其分析应用

在Ph4.0～5.0的BR缓冲介质中,赤藓红(Ery)与莫西沙星(MXFX)和加替沙星(GTF)等氟喹诺酮类抗生素(FLQs)相互作用形成1:1离子缔合物,体系反应导致共振瑞利散射(RRS)显著增强并出现新的RRS光谱.两种药物的反应产物具有相似的光谱特征,最大散射波长位于568nm处,并在342nm和378nm处有2个较小的散射峰.在342nm处一定浓度的抗生素与散射增强成正比,两种氟喹诺酮类药物的线性范围分别是0.02～2.7μg/mL(MXFX)和0.06～10.2μg/mL(GTF).据此建立了测定氟喹诺酮类药物的新方法,已用于胶囊和人尿液中的FLQs测定,并对反应机理和RRS增强的原因作了讨论.     

Aggregation-induced emission of tetraphenylethene derivative as a fluorescence method for probing the assembling/disassembling of amphiphilic molecules

The aggregation-induced emission (AIE) of a 1,2-diphenyl-1,2-di(p-tolyl)ethene (TPE) was explored as a novel fluorescence method for probing the assembling/disassembling of amphiphilic molecules. The fluorescence intensity was able to monitor the formation of micelles and determine the critical micelle concentration (CMC) of surfactants. The temperature-dependent micellization of the pharmaceutically important PEO-PPO-PEO copolymer, Pluronic F127, was further studied by using the TPE fluorescence spectrum intensity. Our results showed good agreement with those reported in the literature by using other methods. The special advantage of the AIE probe method was further explored to determine the assembling/disassembling process of the colored amphiphilic molecule, 1-[4-(3-phenylazophenoxy)butyl]triethylamine bromide (AzoC4), whose CMC value has not previously been described. Since the TPE fluorescence signal mainly comes from the aqueous phase, not from the inside of hydrophobic core, it provides a possible platform to study the CMC of those colored surfactants. Based on the novel fluorescence properties of TPE in the aggregated and dispersed states, one can conclude that the TPE method is a promising method for the determination of the CMC and critical micellization temperature (CMT), particularly having a special advantage to determine the assembling/disassembling process of colored amphiphilic molecules.     

Noise incorporated subwindow permutation analysis for informative gene selection using support vector machines

Selecting a small subset of informative genes plays an important role in accurate prediction of clinical tumor samples. Based on model population analysis, a novel variable selection method, called noise incorporated subwindow permutation analysis (NISPA), is proposed in this study to work with support vector machines (SVMs). The essence of NISPA lies in the point that one noise variable is added into each sampled sub-dataset and then the distribution of variable importance of the added noise could be computed and serves as the common reference to evaluate the experimental variables. Further, by using the non-parametric Mann-Whitney U test, a P value can be assigned to each variable which describes to what extent the distributions of the gene variable and the noise variable are different. According to the computed P values, all the variables could be ranked and then a small subset of informative variables could be determined to build the model. Moreover, by NISPA, we are the first to distinguish the variables into a more detailed classification as informative, uninformative (noise) and interfering variables in comparison with other methods. In this study, two microarray datasets are employed to evaluate the performance of NISPA. The results show that the prediction errors of SVM classifiers could be significantly reduced by variable selection using NISPA. It is concluded that NISPA is a good alternative of variable selection algorithm.     

A fully automated system with on-line micro solid-phase extraction combined with capillary liquid chromatography-tandem mass spectrometry for high throughput analysis of microcystins and nodularin-R in tap water and lake water

Microcystins and nodularins are cyclic peptide hepatotoxins and tumour promoters from cyanobacteria. The present study describes the development, validation and practical application of a fully automated analytical method based on on-line micro solid-phase extraction-capillary liquid chromatography-tandem mass spectrometry for the simultaneous determination of seven microcystins and nodularin-R in tap water and lake water. Aliquots of just 100 μL of water samples are sufficient for the detection and quantification of all eight toxins. Selected reaction monitoring was used to obtain the highest sensitivity. Good linear calibrations were obtained for microcystins (50-2000ng/L) and nodularin-R (25-1000 ng/L) in spiked tap water and lake water samples. Excellent interday and intraday repeatability were achieved for eight toxins with relative standard deviation less than 15.7% in three different concentrations. Acceptable recoveries were achieved in the three concentrations with both tap water matrix and lake water matrix and no significant matrix effect was found in tap water and lake water except for microcystin-RR. The limits of detection (signal to noise ratio=3) of toxins were lower than 56.6 ng/L which is far below the 1 μg/L defined by the World Health Organization provisional guideline for microcystin-LR. Finally, this method was successfully applied to lake water samples from Tai lake and proved to be useful for water quality monitoring.     

流动注射光度法测定水中总磷方法的改进

对全自动流动注射分析仪的分析流路进行了改进,将先消解后进样的模式改为先进样后消解的模式,提出了一种改进的流动注射光度法测定水中总磷含量的方法。总磷的质量浓度在0.01～2.0mg.L-1范围内与吸光度呈线性关系,检出限(3S/N)为1.4μg.L-1。方法用于水样中总磷的测定,经t-检验测定值与国标法测定值无显著差异。水样的加标回收率在93.0%～105.0%之间。     

优化金属辅助法腐蚀液组分制备多孔硅

金属辅助化学腐蚀法可以在无外加电路的条件下,在40%HF/30%H2O2/乙醇的混合溶液中完成多孔硅的制备,该方法简单快速。本文研究了金属辅助法腐蚀液体系各组分(HF、H2O2、乙醇)含量对多孔硅表面的SiHx成分和多孔层结构的影响,根据Si-H和Si-O的红外吸收峰强度的变化曲线优化了腐蚀液体系中各组分含量。在腐蚀液各组分体积比为V40%HF∶V30%H2O2∶V乙醇=2∶2∶1和腐蚀时间为4 min的条件下制备了形貌均匀、化学活性(SiHx成分)和多孔结构稳定性较好的多孔硅,并对金属辅助法与阳极蚀刻法制得的两种多孔硅进行比较,结果显示金属辅助法制备的多孔硅的化学活性和稳定性在后续的生物技术应用中具有明显的优越性。     

Pyridinium tribromide catalyzed condensation of indoles and aldehydes to form bisindolylalkanes

An efficient synthetic method for bis(indol-3-yl)alkane derivatives has been developed.In the presence of 5 mol%of pyridinium tribromide(PTB),the condensation of indoles and aldehydes proceeded smoothly under mild conditions,giving rise to the corresponding bis(indol-3-yl)alkanes in good to excellent yields.     

Synthesis and characterization of novel conjugated polymers based on 3-cyclobutene-1,2-dione moiety

Three novel conjugated polymers bearing 3,4-bis（4-hexylthiophen-2-yl）-3-cyclobutene-1,2-dione unit in their main chain have been synthesized successfully in good yields through Suzuki or Stille coupling reaction.Their molecular structures have been confirmed by FT-IR,¹H NMR and ¹³C NMR.All these copolymers exhibit broad and strong absorption bands in UV-vis region,and their optical band gaps are calculated to be 1.6-2.0 eV.suggesting that they have good coverage with the solar spectrum.These polymers have good thermostability and solubility in common organic solvents.Moreover,all these objective macromolecules possess high electron affinity of～3.8 eV determined from cyclic voltammetry measurement,implying that they are potential n-type polymeric photovoltaic materials.     

A New Pyridoxal Derivative for Transamination of N‐Terminus of Proteins

A new pyridoxal‐5‐phosphate (PLP) derivative FHMDP was developed for the transamination of different peptides with three most hindered amino acid residues (Leu, Ile, Val) as their N‐terminus. Compared to the previously reported reactions of PLP derivatives, the N‐terminus transamination could be accomplished efficiently with the new compound.     

Synthesis, Crystal Structure, and Herbicidal Activities of 2-Cyanoacrylates Containing 1,3,4-Thiadiazole Moieties

Three series of novel 2‐cyanoacrylates 7a – 7f , 9a – 9f , 10a – 10f containing 1,3,4‐thiadiazole ring moieties were synthesized as herbicidal inhibitors of photosystem II (PS II) electron transportation. Their structures were clearly verified by ¹H NMR, ¹³C NMR, elemental analysis (or HRMS analysis) and single‐crystal X‐ray diffraction analysis. Bioassay showed that a suitable group at the 3‐position of acrylates was essential for high herbicidal activity. In particular, compound 7e showed the best herbicidal activities and gave 100% inhibitory activity against rape and amaranth pigweed at a dose of 1.5 kg/ha. Introduction of substituent with higher polarity such as sulfinyl or sulfonyl to the 5‐position of 1,3,4‐thiadiazole decreased herbicidal activities.