α-羟基膦酸酯芳甲酸酯的合成、晶体结构和质谱裂解规律研究

α-羟基膦酸酯与各种取代苯甲酸或吡啶甲酸,通过酰氯或缩合剂的作用,合成了一系列的O,O-二烷基-α-苯基-α-(取代芳基甲酸酯基)-甲基膦酸酯的衍生物.它们的合成收率为61%～84%,这些化合物的结构经过核磁(1HNMR,13CNMR和31PNMR)、红外、质谱、元素分析或高分辨质谱确证,同时化合物C1的结构在晶体结构解析上进一步得到证实.利用多级质谱分析了化合物C2,C5和C8的质谱裂解规律,解释了重排离子的形成机制

Methodologic Study of HPCE Fingerprints of Radix paeoniae Alba and Radix paeoniae Rubra

目的确定赤芍和白芍的高效毛细管电泳分析方法,建立赤芍和白芍的高效毛细管电泳法(HPCE)指纹图谱。方法HPCE工作条件:采用未涂层熔融石英毛细管(内径75μm,有效长度50 cm),分离电压为25 kV,柱温25℃,二极管阵列检测器(DAD)检测波长为220 nm,缓冲液为30 mmol/L硼砂(pH=9.0)溶液。按此条件对来自不同产地的7种赤芍样品和8种白芍样品进行了分析。结果建立了赤芍和白芍HPCE指纹图谱,采用中药指纹图谱相似度计算软件,以系统生成的对照指纹图谱为对照模板对不同样品的图谱进行相似度计算。结论该方法简捷、有效,可以用于赤芍和白芍药材的质量控制。Objective To set up a modern High Performance Capillary Electrophoresis analysis method for separating and detecting Radix paeoniae Alba and Radix paeoniae Rubra and establish their fingerprints.Methods Seven samples of Radix paeoniae Alba and eight samples of Radix paeoniae Rubra were carried out by HPCE under the following conditions: bared fused silica capillary(50 cm ×75 μm i.d.),30 mmol/L borate(pH = 9.0) as buffer,the run voltage is +25 kV,detection wavelength of UV at 220 nm,and column temperature of 25℃.Results The fingerprints were confirmed and compared by the software of the similarity evaluation system for chromatographic fingerprint.Conclusion The results showed that the method of HPCE fingerprint is reliable and accurate to control the quality of two Chinese traditional medicines.国家自然科学基金重点项目(No.20235020);; 青岛“2004将才计划”(No.04-3-JJ-11);; 青岛市崂山区科技计划项目(No.LS-05-KJZX-76

在镉盐胁迫下用蛋白质组学技术筛选与鉴定海兔亚口腔神经节的差异蛋白质

以蓝斑背肛海兔(Notarcus leachii cirrosusStimpson,NLCS)的口腔神经节(Buccal ganglion,BG)为研究对象,按BG形态对称性,解剖成亚BG(sub-BG,SBG),并分为左SBG和右SBG,简称为LSBG和RSBG.用双向凝胶电泳(2D-PAGE)技术优化分离LSBG和RSBG全蛋白质,并采用蛋白质组学和数据库比对技术筛选与鉴定差异蛋白质.实验结果表明,LSBG和RSBG之间的差异蛋白质主要由活性多肽的前体蛋白或降解后大片段多肽组成,它们对维持BG的生理功能起着重要的作用.在急性镉盐(10μg/mL)胁迫下,NLCS的LS-BG和RSBG表达了由镉盐诱导的差异蛋白质,并采用蛋白质组学技术分别分离、筛选和鉴定,其主要的差异蛋白质有下调的肌球蛋白、钙结合蛋白、上调的热休克蛋白和硫氧还蛋白.这些蛋白质可能与BG细胞抗镉毒性有关,部分差异蛋白质适合于监测镉盐污染且开展毒理学研究的蛋白指示物

Evaluation of DPPH Free Radical Scavenging Capability of Hippocampus japonicus Kaup. and Their HPLC Fingerprint

目的采用体外1,1-二苯基苦基苯肼(dPPH)抗氧化模型对海马提取物的抗氧化性质进行评价,并建立小海马HPlC特征指纹图谱,用于小海马药材的鉴别及质量评价。方法利用离线dPPH抗氧化评价体系对海马不同提取物进行评价,结果表明,海马水提物抗氧化能力最强,在此基础上又探明了海马水提物抗氧化能力随时间和浓度的变化规律,为海马抗氧化活性提供了科学依据。依据抗氧化活性实验结果,建立了海马水提物HPlC特征指纹图谱分析方法。结果海马水提物大部分化合物达到基线分离,方法的精密度、重现性、稳定性良好;建立小海马药材HPlC指纹图谱,采用中药指纹图谱相似度计算软件,对小海马进行真伪辨别和质量评价。结论表明该方法简捷、有效,是小海马药材鉴别及质量控制的有效方法。OBJECTIVE To evaluate the antioxidant activity of the extracts of Haima,and to establish the HPLC fingerprint of Haima for the discrimination and the quality evaluation of Haima.METHODS Antioxidant properties of Haima extracts with different solvent were assayed in terms of antioxidant activity by scavenging activities on 1,1-diphenyl-2-picrylhdrazyl(DPPH).The effect of time and concentration of Haima extract on the antioxidant activity was also studied.Secondly,a chromatographic fingerprint method was developed.RESULTS The antioxidant activity of water extract of Haima was higher than all the other extracts of Haima.The developed HPLC method was simple,accurate and reliable for the development of Haima fingerprint.Ten Haima samples collected from different medicine store were analyzed and the Haima HPLC fingerprint was established.The similarity of the HPLC chromatogram was performed for authentication and quality control of Haima.CONCLUSION The HPLC fingerprinting techniques have high potential in authentication or source-tracing types of applications.国家自然科学基金重点项目(20235020);青岛市共建生物医药研发测试中心资助项目(LS-05-KJZX-76

A Novel Method for Preparation of Activated Alumina

[中文文摘]将结晶氯化铝与柠檬酸及淀粉等造孔剂混合,经直接干燥和焙烧制得了一种无定形活性氧化铝,并通过X射线粉末衍射、N2物理吸附及氨程序升温脱附等手段对活性氧化铝样品进行了表征,探讨了各组分对活性氧化铝样品性质所起的作用.与常规的活性氧化铝制备方法相比,这种制法省去了中和、老化、过滤和洗涤等步骤,缩短制备周期且过程容易控制.活性氧化铝具有适宜且可调节的比表面积和孔径分布,作为载体负载镍金属组分制成负载型催化剂后,对乙苯加氢饱和与加氢裂化表现出较高的催化活性.[英文文摘]A novel and simple method was developed to prepare alumina with suitable specific surface area and pore size distribution. First,AlCl3·6H2O and citric acid were heated without water in a water bath at 90 ℃ with stirring until a homogenous solution was obtained.Then starch was added into is solution.After the solution was dried at 110 ℃ and calcined at indicated temperature, activated alumina was obtained.The activated alumina was characterized by N2 adsorption,X-ray diffraction,and NH3 temperature-programmed desorption. Compared with the usual technology , this novel preparation did not include some steps such as aging , filtering , and washing. Moreover , the specific surface area and pore size distribution of the activated alumina could be controlled and modified by changing the preparation parameters. The supported Ni/ Al2O3 catalyst with the activated alumina as support showed higher activity for hydrogenation and hydrocracking of ethylbenzene.国家重点基础研究发展计划(973计,2004CB217805); 福建省“百千万人才工程”项目; 福建省自然科学基金(U0750016)

大海马不同萃取物的抗肿瘤和抗氧化活性研究

目的 检测新鲜大海马样品的抗肿瘤和抗氧化活性。方法 采用大海马新鲜样品进行冷冻干燥,以75%乙醇提取,并进一步以乙酸乙酯、正丁醇和水对提取物进行不同极性部位组分的萃取,对各萃取物分别开展抗肿瘤和抗氧化活性检测和比较,其中抗肿瘤活性检测采用人胶质瘤细胞LN229,抗氧化活性检测采用DPPH法、ABTS法和FRAP法。结果 大海马乙醇提取物的水相萃取物对人胶质瘤细胞LN229没有灭活作用,但正丁醇相和乙酸乙酯相萃取物均显示出显著的抗肿瘤活性,其中乙酸乙酯相萃取物的抗肿瘤活性较高;大海马的三种萃取物均具抗氧化活性,其中乙酸乙酯相萃取物在DPPH法和FRAP法所得结果中均表现出最高的抗氧化活性,水相萃取物在ABTS法中显示出最高的抗氧化活性。结论 研究结果为海马活性成分尤其是中低极性活性成分在海洋药物和保健品领域的开发提供重要参考。海南省重大科技计划(ZDKJ2016009-02);;\n海南省应用技术研发与示范推广专项(ZDXM2015006

监测流动水体污染程度的生物标志物研究进展

利用生物监测流动水体污染程度一直是环境科学研究领域中的热点课题之一。本文综述酶、蛋白细胞和核酸等生物标记物在监测流动水体污染程度方面的研究进展,描述铁蛋白反应器监测流动海水中重金属离子污染的特点,并介绍近年来蛋白组学技术在筛选监测环境污染程度生物标志物中的应用进展

Analysis of pre-S/S gene in occult hepatitis B virus infection from blood donors in Dalian,China

目的了解大连地区无偿献血者隐匿性肝炎乙型病毒感染(ObI)的情况和PrE-S/S区基因的变异情况。方法对大连市血液中心2010年12月2日-2013年5月31日的无偿献血者血液标本进行常规ElISA(HbS Ag、抗-HCV、抗-HIV和抗-TP)和HIV/HbV/HCV联合nAT筛查,对于单独核酸检测反应性的献血者加以跟踪或回溯,结合乙型肝炎血清学标志物的试验、鉴别试验、病毒定量试验和半巢式PCr来确定ObI,同时对ObI的PrE-S/S区基因序列与对照组(HbS Ag+序列,gEnbAnk)做比对分析。结果共筛查158 232份血液标本,确定了其中的69份ObI,流行率为1∶2 293(69/158 232)。41例ObI获得PrE-S/S区基因序列:b型6例、C型34例、d型1例;与对照组相比,ObI在S区的氨基酸序列的变异明显(Pb=0.013;PC=0.003),主要变异位点为b型的V14g/A、y161f/S、V168A、P217l和C型的E2g/A/V、T118r/k/A/M、P127T/l/H/S、E164d/g、l175S、S174n。结论大连地区献血者ObI在HbV基因组S区的氨基酸序列存在多个位点的变异,这些变异与ObI的产生存在某种关系,且这种关系受基因型的影响。Objective To understand the prevalence of occult infection of hepatitis B virus(OBI) and the mutations of pre-S / S gene from blood donors in Dalian.Methods From December 2nd,2010 to May 31 st,2013,samples from blood donors in Dalian Blood Center were screened with enzyme-linked immunosorbent assay(ELISA) for HBs Ag,anti-HCV,antiHIV and anti-TP and triplex nucleic acid detection(NAT) for HIV RNA,HBV DNA and HCV RNA.A follow-up was conducted on donors who were tested negative by ELISA but reactive by NAT.OBI was determined by testing the specimens from the follow-up or archive with serological markers of hepatitis B virus,identification examinations,quantitative and semi-nested PCR.The sequences of pre-S / S gene of OBIs and the control group were analyzed(HBs Ag +,Genbank).Results158 232 blood samples were screened,69 of which were OBIs.The prevalence rate of OBIs was 1 ∶ 2 293(69 /158 232).The pre-S / S gene sequences were analyzed in forty-one cases of OBI:6 were type B,34 were type C,and 1 was type D.Comparing the amino acid sequences between the experimental and control groups,there were statistical significance in the S region of OBI(PB= 0.013;PC= 0.003).The main mutation sites of amino acids for type B were V14 G / A,Y161 F / S,V168 A and P217 L while for type C were E2 G / A / V,T118 R / K / A / M,P127 T / L / H / S,E164 D / G,L175 S and S174 N.Conclusion There were multiple mutation loci on the amino acid sequence of OBI from blood donors in Dalian.A particular relationship existed between these mutations in S region from HBV genome and the mechanism of OBI,which was influenced by genotypes.大连市科技计划指导性项目(大卫科发[2013]50号); 大连市医学重点学科优秀卫生专业技术人才培养资助项目(大卫科发[2013]383号

Preparation and Characterization of Presulfidation-Free MoNiP/Al_2O_3 Catalyst for Thiophene Hydrodesulfurization

[中文文摘]在Mo-Ni-P-O浸渍液中添加一定量的极性有机物如柠檬酸等,采用共浸渍法制备了一种不需预硫化和焙烧也具有较高加氢脱硫活性的MoNiP/Al2O3催化剂,并用N2吸附、程序升温还原、X射线光电子能谱、红外光谱和元素分析对催化剂进行了表征.结果表明,柠檬酸的添加削弱了金属组分与载体间的相互作用,有利于金属组分在载体表面的分散,且改善了催化剂的还原性,使催化剂在与含硫反应物料接触过程中自发硫化,从而有利于催化剂加氢脱硫活性的提高.[英文文摘]A new type of MoNiP/Al2O3 catalyst for thiophene hydrodesulfurization was prepared by the co-impregnation method, wherein a suitable amount of citric acid was added in the Mo-Ni-P-O impregnation solution. The catalyst exhibits high activity for thiophene hydrodesulfurization under presulfidation- and calcination-free conditions. The catalyst was characterized by N2 adsorption, temperature-programmed reduction, X-ray photoelectron spectroscopy, infrared spectroscopy, and elemental analysis methods. The effect s of cit ric acid on the structure and activity of the MoNiP/ Al2O3 catalyst were studied. The result s show that the addition of cit ric acid weakens the interaction between the active metal components and support , improves dispersion of active metal component s on the support surface , and promotes the reduction and sulfidation of the catalyst by sulfur-containing feedstocks. Therefore, the hydrodesulfurization activity of the catalyst is improved.国家重点基础研究发展计划(973计划, 2004CB217805); 厦门大学科技创新项目(XDKJCX20051002)

A New Mathematics Model of the Temperature Programmed Analysis Technology

以表面作用包括表面吸/脱附以及表面反应本征速率方程为基础,提出新的程序升温分析技术(TPAT)的数学模型。与经典的理论模型相比,这种新的TPAT理论模型更接近实际的程序升温分析实验过程。设计和进行特定催化剂的TPd、TPr及TPO实验,得到相应的程序升温谱图,采用新的TPAT理论模型模拟上述谱图,计算出相应的表面作用活化能等重要热力学参数。结果表明,新的理论模型具有良好的模拟性能,平均相对误差(Ard)小于1%。Based on the surface effect including surface adsorption/desorption and intrinsic kinetics rate equation,a new mathematical model of the temperature programmed analysis technology was proposed.This model is different from the classical TPAT theory models,which indicates much more coincidence with the actual reactions than other models.TPAT(TPD,TPR and TPO) experiments were designed and carried out to receive their profiles.Based on these profiles of TPAT and the simulated experiments,the novel theory model was designed and the thermodynamics parameters(such as activation energy,etc.) were deduced and calculated by this model.The results show that this model has excellent simulation with the actual experiments,and the average relative errors are easily controlled less than 1%