生物活性环肽Paecilodepsipeptide A的全合成

首次采用逆合成法对昆虫病原真菌Paecilomyces cinnamomeus BCC 9616中分离的高活性抗肿瘤环己肽环肽Paecilodepsipeptide A进行了全合成. 采用标准肽化学合成方法,完成了五肽的合成;以酪氨酸甲酯盐酸盐为起始原料,得到O-异戊烯基-D-酪氨酸衍生物;通过五肽与O-异戊烯基-D-酪氨酸衍生物的酯化反应得到环化前体;采取大环内酰氨化和大环内酯化的策略进行关环,完成了天然产物Paecilodepsipeptide A的全合成,产率72%. 目标化合物经质谱与核磁共振光谱结构确证与天然产物一致.      

Patellamide A类似物的全合成研究

本文从D-(缬)噻唑氨基酸、L-异亮氨酸、L-丝氨酸、1-苏氨酸出发合成了PatellamideA类似物环肽(1)。D-(缬)噻唑氨基酸由D-缬氨酸和L-半胱氨酸按亚胺酯法合成。丝氨酸噁唑啉(11)由三苯基膦法合成,苏氮酸噁唑啉(17)由亚胺酯法合成。11和17去保护基后经DCC/HOBT法转变为线性肽(19a),19a用五氟苯酯法环化得得1.1和其丝氨酸噁唑啉的开环产物环肽都具有抗肿瘤活性。     

新型吲哚席夫碱类化合物的合成及其抗菌活性研究

以吲哚-3-甲酸甲酯为原料,通过偶联、肼解、消除等反应,合成了一系列具有对称结构的吲哚席夫碱衍生物,以期为新药筛选提供先导化合物.其结构均经~1H NMR,ESI-MS,IR及元素分析所证实.初步抗菌活性测定结果表明:化合物5e对枯草芽孢杆菌、金黄色葡萄球菌具有较强的抑菌效果;化合物5f对大肠杆菌的抑菌效果优于阿莫西林,对绿脓杆菌表现出与对照品阿莫西林相当的抑菌效果.     

3-二氢吡咯烷基螺环氧化吲哚及其衍生物的合成与表征

对3-二氢吡咯烷基螺环氧化吲哚及其衍生物进行了探索合成。在有机小分子碱三乙胺催化作用下,由N-2,2,2-三氟乙基靛红酮亚胺与丁炔二酸二甲酯在二氯甲烷(DCM)溶剂中于室温下发生3+2环合加成反应,高产率(83%~98%)获得3-二氢吡咯烷基螺环氧化吲哚。这一合成方法具有简单,高效,环保的特点。通过核磁共振氢谱和碳谱、高分辨质谱等手段对已合成的产物进行表征。     

荧光可调控的二噻吩乙烯-萘酰亚胺光致变色化合物的合成及性能研究

用Suzuki反应设计并合成了含二噻吩乙烯光致变色单元的萘酰亚胺荧光化合物。所有中间体及目标化合物经核磁(~1H NMR)、质谱(Ms)确证了化学结构,利用紫外-可见光吸收光谱(UV-Vis)、荧光发射光谱,荧光寿命研究了含二噻吩乙烯光致变色单元的萘酰亚胺荧光化合物在溶液中和薄膜中的光致变色性能,结果表明该化合物光致变色前后具有较高的可调控荧光对比度,高的光热稳定性和高的开关环量子产率,在超高密度光存储具有潜在的应用价值。     

4'-三氟甲基-3,2'-吡咯烷基双螺环氧化吲哚化合物的合成与表征

对具有高生物活性的4’-三氟甲基-3,2’-吡咯烷基双螺环氧化吲哚及其衍生物进行了探索合成。在有机小分子碱三乙胺催化作用下,由3-异硫氰基氧化吲哚与3-三氟亚乙基羟吲哚在二氯甲烷(DCM)溶剂中于室温下发生3+2环合加成反应,高产率(85%~96%)获得4’-三氟甲基-3,2’-吡咯烷基双螺环氧化吲哚。通过核磁共振氢谱和碳谱、高分辨质谱等手段对已合成的产物进行表征。这一合成方法具有简单,高效,环保的特点。     

Nutritional and microbiological evaluations of chocolate-coated Chinese chestnut (Castanea mollissima) fruit for commercial use

In recent years, China has become an increasingly important and the largest chestnut producer in the world. This study aimed to evaluate the nutritional value and microbiological quality of the roasted freeze-dried Chinese chestnut (Castanea mollissima) (RFDC) coated with dark chocolate (DCC) and milk chocolate (MCC) for industrial use and commercial consumption. Chocolate coating significantly improved the nutritional value of chestnut. RFDC had high levels of starch (66.23%) and fibers (3.85%) while DCC and MCC contained significantly high amounts of sucrose, protein, fat and minerals. Furthermore, the protein content doubled in MCC rather than in DCC. This could be attributed to the different formulations in the two products. Milk powder and whey protein constituted the source of protein in MCC while cocoa powder added to MCC formulation constituted an additional source of minerals. The amino acid profile showed differences in amino acid composition related to the sample’s protein content, indicating their good nutritional quality. The moisture contents in all RFDC, DCC and MCC were suitable for industrial processing. These results provide information about the additional nutrients of chocolate-coated chestnut and confirm that the product is an interesting nutritional food. The combination of freeze-drying and chocolate-coating generally results in greater reductions on microbiological loads, extending shelf life of harvested chestnut for commercial application. This is an alternative strategy to add value to chestnut, minimizing the significant losses in harvested fruits and providing a wider range of choices of new products to the consumer disposal.     

P-5m八肽多克隆抗体的制备及应用

目的制备P-5m八肽的多克隆抗体并进行初步鉴定和应用,为研究P-5m八肽的功能及作用机制获得重要的实验工具.方法将9-氟甲氧羰基(Fmoc-)固相合成法合成的P-5m八肽纯化后与载体蛋白-血蓝素联接;取偶联后的多肽皮下注射免疫新西兰白兔,并加强免疫得到抗血清,以C18反相色谱分离柱分离纯化;通过间接ELISA方法测定血清效价;利用Transwell实验和Western blot方法初步鉴定多克隆抗体拮抗P-5m八肽抑制肿瘤细胞转移的效果.结果纯化后的抗体经间接ELISA测定效价均大于1∶160 000,表明获得高效价的多抗;通过Transwell实验证明该抗体能够封闭P-5m对肿瘤细胞侵袭的抑制能力;通过Western blot方法证实此抗体效价较高,特异性较强;该多克隆抗体能够封闭P-5m在SW620细胞中上调E-cadherin表达的作用,并阻遏P-5m对MMP-2和MMP-9表达的下调作用,与对照组比较差异具有统计学意义(P0.05).结论 P-5m多克隆抗体可用于Transwell和Western blot等实验,为研究P-5m八肽的功能及抗肿瘤转移作用机制提供实验依据.     

电性距离矢量预测有机污染物的生物富集因子

以电性距离矢量Mt表征165种非离子性有机物(NOC)的分子结构.利用多元回归方法建立了122种NOC的生物富集因子(lg BCF)与32个Mt的数学模型,其相关系数R为0.976.经逐步回归建立最佳四变量(M15,M17,M36,M91)模型,其R为0.960;并以Jackknife法检验,其LOO交互检验系数(q2)为0.915.这4个Mt参数揭示了影响NOC生物富集因子的主要因素,结果表明该模型具有良好的估算能力与鲁棒性.以111个NOC为训练集的生物富集模型作用于11个NOC的检验集,显示出良好的预测能力.     

环肽Ascidiacyclamide异构体的合成

从缬氨酸,L-丝氨酸,L-苏氨酸,L-异亮氨酸出发合成了海洋环肽Ascidiacy-clamide的异构体cyclo-[-D,L-(Val)Thz-L-Ser-L-Ile-D,L-(Val)Thz-L-Thr-L-Ile-]-。其中噻唑氨基酸由Hantzsch方法合成,肽链由DCC-HOBT(DCC即二环己基碳化二亚胺,dicyclohexylcarbodimide;HOBT即1-羟基合水苯并噻唑,1-hydroxybenzotria-zolenydrate)缩合而形成。关大环采用叠氮方法。     

Short Report： Cyclic patterns of incidence rate for skin malignant melanoma： association with heliogeophysical activity

Background： Our previous studies revealed cyclicity in the incidence rate of skin malignant melanoma （SMM; ICD9, Dx： 172） in the Czech Republic （period T=7.50～7.63 years）, UK （T= 11.00 years） and Bulgaria （T= 12.20 years）. Incidences com- pared with the sunspot index Rz （lag-period dT=＋2, ＋4, ＋6, ＋ 10 or ＋ 12 years） have indicated that maximal rates are most likely to appear on descending slopes of the ;ll-year solar cycle, i.e., out of phase. We summarized and explored more deeply these cyclic variations and discussed their possible associations with heliogeophysical activity （HGA） components exhibiting similar cyclicity. Methods： Annual incidences of SMM from 5 countries （Czech Republic, UK, Bulgaria, USA and Canada） over various time spans during the years 1964-1992 were analyzed and their correlations with cyclic Rz （sunspot number） and aa （planetary geomagnetic activity） indices were summarized. Periodogram regression analysis with trigonometric approximation and phase-correlation analysis were applied. Results： Previous findings on SMM for the Czech Republic, UK and Bulgaria have been validated, and cyclic patterns have been revealed for USA （T=8.63 years, P〈0.05） and Canada （Ontario, T=9.91 years, P〈0.10）. Also, various ＇hypercycles＇ were established （T=45.5, 42.0, 48.25, 34.5 and 26.5 years, respectively） describing long-term cyclic incidence patterns. The association of SMM for USA and Canada with Rz （dT=＋6 and ＋7 years, respectively） and aa （dT=-10 and ＋9 years, respectively） was described. Possible interactions of cyclic non-photic influences （UV irradiation, Schumann resonance signal, low-frequency geomagnetic fluctuations） with brain waves absorbance, neuronal calcium dynamics, neuro-endocrine axis modulation, melatonin/serotonin disbalance and skin neuro-immunity impairment as likely causal pathways in melanoma appearance, were also discussed. Conclusion： The above findings on cyclicity and temporal assoc     

Biomimetic synthesis and optimization of cyclic peptide antibiotics

Molecules in nature are often brought to a bioactive conformation by ring formation (macrocyclization). A recurrent theme in the enzymatic synthesis of macrocyclic compounds by non-ribosomal and polyketide synthetases is the tethering of activated linear intermediates through thioester linkages to carrier proteins, in a natural analogy to solid-phase synthesis. A terminal thioesterase domain of the synthetase catalyses release from the tether and cyclization. Here we show that an isolated thioesterase can catalyse the cyclization of linear peptides immobilized on a solid-phase support modified with a biomimetic linker, offering the possibility of merging natural-product biosynthesis with combinatorial solid-phase chemistry. Starting from the cyclic decapeptide antibiotic tyrocidine A, this chemoenzymatic approach allows us to diversify the linear peptide both to probe the enzymology of the macrocyclizing enzyme, TycC thioesterase, and to create a library of cyclic peptide antibiotic products. We have used this method to reveal natural-product analogues of potential therapeutic utility; these compounds have an increased preference for bacterial over eukaryotic membranes and an improved spectrum of activity against some common bacterial pathogens.     

Synthesis and phase behavior of ω-(cholesteroxycarbonyloxy)-alkyl 3,3,5,5-tetramethyl-3,5-disila-4-oxacyclohexyl-carboxylate

Four new organosilane compounds containing cholesteryl group were synthesized by esterification of 3,3,5,5-tetramethyl-3,5-disila-4-oxa-cyclohexane-1-carboxylic acid and ω-hydroxyalkyl, cholesteryl carbonate in the presence of DCC and DMAP. Their structures were characterized by¹H-NMR, IR and elemental analysis. Their phase behaviors were investigated by differential scanning calorimetry (DSC) and polarized microscopy. Results showed that these four organosilane compounds were all liquid crystalline and longer spacer was advantageous to orientation of organosilane heterocycle and cholesteryl group. Biography: TANG Hong-Ding (1972-), male, Ph. D candidate, Research direction: orgenosilicon materials     

Qualitative and quantitative relationships between affinity constants from model study and real adsorption data

Linear polymers bearing the same functional groups as their corresponding adsorbents could be used as models to study the ad-sorption behaviors. However, the relationships between the data from model study and real adsorption have not been fully interpreted. In this work, three adsorbent (CP1-Zn²⁺, CP2-Zn²⁺ and CP3-Zn²⁺) and their corresponding linear models (P1-Zn²⁺, P2-Zn²⁺ and P3-Zn²⁺) were synthesized. The affinity constants (Ka) between these models and target peptide DFLAE (DE5) were obtained by isothermal titration calorimetry (ITC). Adsorption capacities and adsorption affinities were carried out by static adsorption and adsorption isotherm. The qualitative and quantitative relationships between affinity constants from model study and the real ad-sorption data were explored. This study was significant to bridge the model study with the real adsorption.     

Bilirubin sensor based on CuO-CdO composites deposited in a nafion/glassy carbon electrode matrixes

Copper oxide-cadmium oxide nanocomposites(CuO-CdO NCs) were synthesized by solvothermal technique in a basic medium. CuO-CdO NCs were characterized using conventional techniques, such as Fourier Transform Infrared Spectroscopy(FTIR), UV–Visible Spectroscopy(UV/Vis), Field-Emission Scanning Electron Microscopy(FESEM), X-ray electron dispersive spectroscopy(XEDS), X-ray photoelectron spectroscopy(XPS), and powder X-ray diffraction(XRD). A selective and enzyme-less Bilirubin(BLR) sensor was developed with a thin-layer of NCs onto a glassy carbon electrode(GCE, surface area = 0.0316 cm~2) using 5% nafion binders at room conditions. Improved electrochemical performances of higher sensitivity, lower detection limit,linear dynamic range(LDR), and long-term stability of preferred BLR were achieved by a reliable currentvoltage(I-V) approach. The calibration curve was found linear(R~2= 0.9347) in a wide range of BLR concentration(10.0 pM ~ 10.0 mM). Based on the signal to noise ratio value of 3, the sensitivity and limit of detection(LOD) of the sensor were calculated as 95.0 pA μM~(-1) cm~(-2) and 1.0 ± 0.1 pM respectively.Solvothermally synthesized CuO-CdO NCs/GCE is an excellent advancement of developing a selective and sensitive BLR sensor by electrochemical approach and practically implemented in real sample applications.     

Preliminary Evaluation of a Candidate Multi-Epitope-Vaccine Against the Classical Swine Fever Virus

A multi-epitope-vaccine MEVABc consisting of two linear neutralizing determinants （BCI： aa693-716; A6： aa844-865） located on antigenic unit B/C and unit A of glycoprotein E2 was prepared to evaluate whether a combination strategy is effective in the design of peptide vaccines. After immunization, pig sera collected every one to two weeks were evaluated by enzyme linked immunosorbent assay. C-straininduced anti-sera and hyper-immune sera cannot recognize overlapping peptides that cover the E2 N-terminus, while MEVAgC is able to elicit high levels of peptide-specific antibody response. When compared with previously studied peptide vaccines PV-BC1 and PV-A6, the same dose of either component in the MEMABc increases the BC1- or A6-specific antibodies （to 1/3-1/2 of the levels of the separate vaccines）. However, the synergy between the antibodies may make MEVAgc much more potent. Moreover, anti-C-strain immunity pre-existing in pigs does not disturb the sequent MEVABc vaccination. Thus, MEVABc can be administrated to pigs which already possess anti-classical swine fever virus immunity. MEVAgC is a promising candidate marker vaccine.     

Expression, purification and characterization of a phyAm-phyCs fusion phytase

The phyA^m gene encoding acid phytase and optimized neutral phytase phyCs gene were inserted into expression vector pPIC9K in correct orientation and transformed into Pichiapastoris in order to expand the pH profile ofphytase and decrease the cost of production. The fusion phytase phyA^m-phyCs gene was successfully overexpressed in P. pastoris as an active and extracellular phytase. The yield of total extracellular fusion phytase activity is （25.4±0.53） U/ml at the flask scale and （159.1±2.92） U/ml for high cell-density fermentation, respectively. Purified fusion phytase exhibits an optimal temperature at 55 ℃ and an optimal pH at 5.5-6.0 and its relative activity remains at a relatively high level of above 70% in the range ofpH 2.0 to 7.0. About 51% to 63% of its original activity remains after incubation at 75 ℃ to 95 ℃ for 10 min. Due to heavy glycosylation, the expressed fusion phytase shows a broad and diffuse band in SDS-PAGE （sodium dodecyl sulfate-polyacrylamide gel electrophoresis）. After deglycosylation by endoglycosidase H （EndoHf）, the enzyme has an apparent molecular size of 95 kDa. The characterization of the fusion phytase was compared with those ofphyCs andphyA^m.     

IS4 peptide forms ion channel in rat skeletal muscle cell membrane

A 22-mer peptide, identical to the primary sequence of domain I segment 4 (IS4) of rat brain sodium channel I, has been synthesized. IS4 peptide can incorporate into cultured rat skeletal myotube membranes and form ion channels. With patch clamp cell-attached technique single channel currents through IS4 channels can be recorded. The single channel conductances of IS4 channels are distributed heterogeneously. With different holding potentials, the mean open time, the mean closed time and the mean open probability are different respectively. IS4 channels are selective for Na⁺, Li⁺ and K⁺, but not for Cl⁻.     

A new second-order Mehrotra-type predictor-corrector algorithm for SDO

In Zhang's recent works,a second-order Mehrotra-type predictor-corrector algorithm for linear optimization was extended to semidefinite optimization and derived that the algorithm for semidefinite optimization had O(n~(3/2)log(X~0)~T·S~0/ε) iteration complexity based on the NT direction as Newton search direction. In this paper, we extend the second-order Mehrotra-type predictor-corrector algorithm for linear optimization to semidefinite optimization and discuss the polynomial convergence of the algorithm by modifying the corrector direction and new iterates. It is proved that the iteration complexity is reduced to O(n~(3/2)log(X~0)~T·S~0/ε), which coincides with the currently best iteration bound of Mehrotra-type predictor-corrector algorithm for semidefinite optimization.     

Synthesis of the CuInSe2 thin film for solar cells using the electrodeposition technique and Taguchi method

The Taguchi method was used to obtain the optimum electrodeposition parameters for the synthesis of the CuInSe₂ thin film for solar cells. The parameters consist of annealing temperature, current density, CuCl₂ concentration, FeCl₃ concentration, H₂SeO₃ concentration, TEA amount, pH value, and deposition time. The experiments were carried out according to an L₁₈(2137) table An X-ray diffractometer (XRD) and a scanning electron microscope (SEM) were respectively used to analyze the phases and observe the microstructure and the grain size of the CuInSe₂ film before and after annealing treatment. The results showed that the CuInSe₂ phase was deposited with a preferred plane (112) parallel to the substrate surface. The optimum parameters are as follows: current density, 7 mA/cm 2 ; CuCl₂ concentration, 10 mM; FeCl₃ concentration, 50 mM; H₂SeO₃ concentration, 15 mM; TEA amount, 0 mL; pH value, 1.65; deposition time, 10 min; and annealing temperature, 500℃.