钛(Ⅳ)-槲皮素-氯酸盐体系极谱催化波的研究

在pH3.2氯乙酸盐缓冲底液中,用单扫极谱法可获得灵敏的钛(Ⅳ)-槲皮素-氯酸盐催化波,其二阶导数检测限达7.0×10^-9mol/L。已成功地应用于纯金属镁中10^-4%钛的测定,并测得电活性络合物的组成为Ti(Ⅳ)∶槲皮素＝1∶1,平行催化反应的速率常数k=4.8×10⁵(mol/L)^-1·s^-1。     

铟-荧光镓极谱络合吸附波的研究

在pH 5.5的0.1mol/L(CH₂)₆N₄-HCl底液中可获得铟(Ⅲ)-荧光镓体系灵敏的络合吸附波。测定铟的线性范围为1.0×10^-7～1.0×10^-5mol/L,检测限达8×10^-8mol/L, 测得电活性络合物的组成为铟∶荧光镓=1∶2,条件形成常数β=3.6×10¹³,表面电极反应速率常数k_s1、k_s2、k_s3分别为4.4、1.74、10.8s^-1,并研究了电极反应机理。     

不同羟基数目黄酮类药物与牛血清蛋白间相互作用

用荧光光谱法、分光光度法研究了3种黄酮类药物(染料木素、木犀草素和桑色素)与牛血清白蛋白(BSA)的相互结合作用.实验表明染料木素、木犀草素和桑色素与牛血清白蛋白的相互结合作用均为单一的静态猝灭过程,猝灭常数Ksv为4.22×104～4.83×105 L·mol-1,在溶液中结合作用强烈(结合常数KB为1.92×103～3.23×105 mol·L-1),形成稳定的配合物,求算了给体(BSA)与受体(黄酮类药物)作用距离r(3.35～4.80 nm).首次发现药物与BSA结合作用同羟基数目直接相关:随着药物分子中羟基数目(染料木素为3、木犀草素为4、桑色素为5)的增加,猝灭荧光峰位蓝移增大,作用距离r变小,结合作用逐渐加强;猝灭常数Ksv增大,更容易形成配合物;结合常数KB增大,形成的配合物更稳定.     

DNA/CTC双向捕集离子液体浮选分离测定废水中痕量Ni(Ⅱ)

在一定条件下,Ni(Ⅱ)在溶液中能够被脱氧核糖核酸(DNA)和金霉素(CTC)双向捕集,形成Ni-CTC-DNA三元缔合物.该缔合物具有良好的疏水性,利用离子液体[bmim]BF_4浮选体系可以将其从混合溶液中分离提取出来.研究了缔合物形成和离子液体浮选过程的影响因素,得到了三元缔合物生成和浮选分离的最优条件.线性回归方程为A=8.03×10⁵C-0.000 3,线性范围为4.7×105C-0.000 3,线性范围为4.7×10^(-8)(-8)⁶.5×106.5×10^(-3)mol/L,摩尔吸光率为8.03×10(-3)mol/L,摩尔吸光率为8.03×10⁵L·mol5L·mol^(-1)·cm(-1)·cm^(-1),检出限为1.8×10(-1),检出限为1.8×10^(-8)mol/L.该方法可用于工业废水中重金属镍离子的快速检测分析.     

钒(Ⅳ)-槲皮素极谱络合物吸附波的研究

在pH5.2的醋酸盐缓冲底液中,用单扫示波极谱法可获得灵敏的V(Ⅳ)-槲皮素络合物吸附波。钒浓度在1.0×10^-7 mol/L--1.0×10^-5 mol/L范围内与二阶导数波峰高成正比关系,检测下限为7.0×10^-8 mol/L。测得电活性络合物组成为V(Ⅳ)∶Qu=1∶1,条件稳定常数为3.3×10⁵。表面电极反应速率常数ks=3.9 s^-1。     

木犀草素对脉络膜恶性黑色素瘤细胞的影响

为探讨木犀草素调节Wnt/β-catenin信号通路对人脉络膜恶性黑色素瘤细胞(MuM-2C)凋亡、迁移和侵袭的影响,采用CCK-8法测定0,5,10,15,20,25μmol/L浓度木犀草素处理24 h后的MuM-2C活力,以筛选合适的药物作用浓度.将体外培养的MuM-2C随机分为3组：对照组、木犀草素组及木犀草素+氯化锂组,木犀草素组以15μmol/L木犀草素处理,木犀草素+氯化锂组以15μmol/L木犀草素和10μmol/L的氯化锂联合处理.采用流式细胞技术和Hoechst 33258染色检测MuM-2C的凋亡情况,采用划痕实验和Transwell实验检测各组MuM-2C的迁移、侵袭情况,采用免疫荧光检测各组MuM-2C中凋亡蛋白BAX与BCL-2表达,采用免疫印记检测各组MuM-2C中EMT标志蛋白(E-cadherin, N-cadherin, Vimentin)和Wnt/β-catenin信号相关蛋白(Wnt1,β-catenin)表达,结果表明：不同剂量木犀草素均可抑制MuM-2C生长,并在一定范围内随剂量升高而作用增强;与对照组比较,木犀草素组细胞核形态固缩而大小不一,...     

基于双链DNA的苯酚传感器的研究

首先在玻碳电极(GCE)表面电聚合硫堇,得到聚硫堇修饰玻碳电极(PTh/GCE),然后在PTh/GCE上依次电沉积普鲁士蓝-金纳米复合物(PB-Au)和金纳米粒子(GNPs),最后利用滴涂法固定双链DNA,制备一种基于双链DNA的苯酚传感器(dsDNA/GNPs/PB-Au/PTh/GCE).利用循环伏安法和电化学交流阻抗技术对传感器的制备过程进行了表征,研究了亚甲基蓝(MB)和[Fe(CN)_6]^(3-/4-)的协同指示剂作用,测试了苯酚传感器的响应性能,考查了传感器的一致性和抗干扰能力,最后对某制药厂的含酚废水进行了检测.结果表明,在1×10(3-/4-)的协同指示剂作用,测试了苯酚传感器的响应性能,考查了传感器的一致性和抗干扰能力,最后对某制药厂的含酚废水进行了检测.结果表明,在1×10^(-3)(-3)¹×101×10^(-8)mol/L范围内,MB峰电流与苯酚浓度呈现良好的线性关系,相关系数为0.995 8,检出限为2.36×10(-8)mol/L范围内,MB峰电流与苯酚浓度呈现良好的线性关系,相关系数为0.995 8,检出限为2.36×10^(-13)mol/L,该传感器一致性好,并具有一定的抗干扰能力,在环境监测领域具有广阔的应用前景.     

雷公藤甲素与人血清白蛋白间的体外结合特性

采用平衡透析法研究雷公藤甲素与人血清白蛋白的结合率,结果表明当雷公藤甲素的浓度分别为3.60,7.20和36.0μg/m L时,其与人血清白蛋白的结合率分别为(24.2±2.0)%,(18.4±0.4)%和(6.30±0.3)%.应用荧光淬灭法研究雷公藤甲素与人血清白蛋白间的相互作用机制,结果表明TP与HSA之间的结合为静态淬灭过程,在300,305和310 K温度下结合常数分别为1.3×10~4,7.8×10~3和3.8×10~3L/mol,主要作用力为范德华力.     

木犀草素在电沉积石墨烯修饰电极上的电化学研究及测定

将正己基吡啶六氟磷酸盐与石墨粉混合制备一种离子液体修饰碳糊电极,用电化学还原的方法将氧化石墨烯沉积于该电极表面得到电化学沉积石墨烯修饰电极.通过循环伏安法和示差脉冲伏安法研究了木犀草素在该修饰电极上的电化学行为.在p H为2.0的磷酸缓冲液中对木犀草素溶液进行循环伏安扫描,出现了一对良好的氧化还原峰,考察了扫速和p H等条件对电化学反应的影响.在最佳条件下木犀草素的浓度在4.0×10-8mol/L~4.0×10-6mol/L之间与氧化峰电流呈良好的线性关系,检测限为1.0×10-8mol/L.     

氮掺杂碳量子点荧光探针快速检测山梨酸钾

山梨酸钾属于酸性食品防腐剂,能有效地抑制霉菌、酵母菌和好氧性细菌的活性,延长食品的保存时间,并保持食品原有的风味.本研究通过一步水热法合成了水溶性良好的荧光氮掺杂碳量子点（NCQDs）,基于山梨酸钾能有效地猝灭NCQDs而构建了快速检测山梨酸钾的荧光探针.在最佳实验条件下,山梨酸钾浓度在3.0×10^-5～1.0×10^-4mol/L和1.0×10^-7～3.0×10^-5mol/L范围内与NCQDs荧光猝灭强度呈现良好的线性关系,检出限为9.5×10^-8mol/L.我们已将其用于苏打水及白醋中山梨酸钾含量的测定,回收率分别为98.25%～102.7%和98.33%～101.8%.     

Organic media enhanced spectrofluorimetric determination of L-ascorbic acid

A novel spectrofluorimetric method for the determination of L-ascorbic acid is proposed. It is based on the inhibition of L-ascorbic acid on the formation of 2,3-diaminophenazine, which is an oxidation product ofo-phenylenediamine catalyzed by laccase. The fluorescence (at λ_cx/λ_cm=464 nm /530 nnm) was enhanced strongly in the presence of organic media. The mechanism ofo-phenylenediamine oxidation reaction catalyzed by laccase in the presence of L-ascorbic acid is discussed. L-ascorbic acid is determined in the ethanol, 1,4-dioxane and acetone over the linear range of 4.0×10⁻⁷≈1.2×10⁻⁴ mol/L, 4.0×10⁻⁷≈8.0×10⁻⁵ mol/L and 4.0×10⁻⁷≈1.0×10⁻⁴ mol/L with a detection limit of 1.20×10⁻⁵ mol/L, 1.19×10⁻⁵ mol/L and 1.24×10⁻⁸ mol/L, respectively. The method has been successfully applied to the simple and rapid determination of L-ascorbic acid in pharmaceuticals and milk powder. Supported by National Natural Science Foundation of China and the Special Funds of State Education Committe for Doctorate Research Huang Zuyun: born in Aug. 1963. Ph.D     

Chemiluminescence determination of thiourea using tris (1,10-phenanthroline)-ruthenium (II) KMnO4 system

The light emission produced by thiourea in oxidation process by permanganate in acidic solution in the presence of Ru(phen) ₂ ^{3 +} is used to determine 1.0×10⁻⁵ −1.0×10⁻⁵ mol/L thiourea. The limit of detection is 9.8×10⁻⁹ mol/L and the relative standard deviation is 1.1% for a 1.0×10⁻⁵ mol/L thiourea solution (n=10). The method was applied satisfactorily to the determination of thiourea. Foundation item, Support by Ministry of Education, Wuhan University and Alumni Association of it Biography: Wu Feng-wu(1963-), Male, Ph. D, research direction: analytical chemistry.     

Chemiluminescence determination of tetracycline and oxytetracycline in pharmaceutical preparations using Ru (bipy)3 2+-cerium (IV) system

A new chemiluminescence (CL) method for the determination of tetracycline and oxytetracycline is developed, based on the CL reaction of tetracycline and oxytetracycline with Ru (bipy)₃ ²⁺ and Ce (IV). In sulfuric acid medium, the CL emission is generated upon continuous oxidtion of Ru(bipy)₃ ²⁺ by cerium (IV). The emission intensity is greatly enhanced when tetracycline and oxytetracycline are introduced into the reaction system after acid degradation. Under the optimum conditions, the calibration curves are linear over the range of 8.0×10⁻⁸∼4.0×10⁻⁶ mol/L for tetracycline and of 2.0×10⁻⁷∼4.0×10⁻⁵ mol/L for oxytetracycline, with the detection limits are 4.2×10⁻⁸ mol/L for tetracycline and 1.5×10⁻⁷ mol/L for oxytetracycline, respectively. The proposed method was used for the determination of tetracycline and oxytetracycline in pharmaceutical formulations with good results. Foundation item: Supported by the National Natural Science Foundation of China and the Natural Science Foundation of Hubei Province. Biography: HAH He-you (1962), male, Associate profeddor, Ph.D graduate candidate. Present address, Department of Chemistry, Huainan Teacher's College, Huainan.     

Study on state of terbium ion in liposome by one-order derivative fluorescence quenching method

The state of Tb³⁺ is investigated in liposome. When the concentration of PC is below CMC (critical micell concentration), most of Tb³⁺ is associated with PC, the binding constant is about 3.35×10³ L/mol. When the concentration of PC is beyond CMC, most of Tb³⁺ is dimerized, the dimerization constant is about 3.92×10⁴L/mol. In PC−CH−H₂O system, the binding constant of Tb³⁺−CH complex 2.93×10⁴L/mol is obtained. Biography:Mu Xiao-jing (1974-), female, MS.     

光谱法研究6-糠氨基嘌呤与牛血清白蛋白的相互作用

利用荧光光谱法、紫外光谱法、荧光寿命和圆二色光谱法等方法研究了6-糠氨基嘌呤(KT)与牛血清白蛋白(BSA)之间相互作用机理.结果表明,KT可以显著猝灭BSA的内源荧光,其猝灭机制为静态猝灭,猝灭常数Ksv在288 K和303 K时分别为1.45×104和1.42×104L/mol,Stern-Volmer曲线是两段相交于cKT=8.0×10-5mol/L的回归曲线,说明KT与BSA之间存在两类结合位点.数据处理及热力学参数计算表明:低浓度KT-BSA(cKT8.0×10-5mol/L)的结合主要是疏水作用,结合位点数约为1;较高浓度KT(cKT8.0×10-5mol/L)主要以氢键、范德华力与BSA结合,结合位点数为3.7.紫外光谱和圆二色光谱实验结果表明,KT的存在使BSA二级结构发生了改变.     

Determination of isocarbophos by cathodically sweeping oscilliopolarography

Determination of isocarbophos by cathodically sweeping oscilliopolarography is described. In a 1.0×10⁻⁵ mol/L sodium dodecylbenzene sulfonate (SDS)+0.1 mol/L HAC-NaAC (pH=4.0) buffer medium, isocarbophos and its alkaline hydrolysate exhibited sensitive second derivative wave at −0.50 V and −0.48 V respectively. The peak current was linearly proportional to the concentration of isocarbophos in the range of 5.40×10⁻⁶−1.05×10⁻⁴ mol/L by detecting isocarbophos directly. The detection limit was 3.60×10⁻⁶ mol/L with the relative standard derivation (RSD) of 7.3%. By employing an alkaline hydrolysis, the peak current was linearly proportional to the concentration of isocarbophos in the range from 7.70×10⁻⁷ mol/L to 1.24×10⁻⁴ mol/L, and the detection limit was 5.80×10⁻⁷ mol/L with RSD of 3.1%. The hydrolysis procedure and the electrode reaction were studied by voltammetry. Foundation item: Supported by the Foundation of Chinese-France Cooperation Program on Advanced Research Biography: ZHANG Wu-ming (1929-), female, Professor.     

Determination of some carbonyl carboxylic acids using chemiluminescent reaction of Ru(bipy)3 2+−Ce(IV)

A coupled chemiluminescence method for the determination of some carboxylic acids was developed, based on their enhancement the chemiluminescence light emission of the reaction of tirs (2,2′-bipyridine) ruthenium(II) and Ce(IV) in sulfuric acid medium. The conditions for their determination were optimized. The following detection limits were obtained: oxalic acid, 2.67×10⁻⁸ mol/L; propandioic acid, 1.20×10⁻⁶ mol/L; pyruvic acid, 1.35×10⁻⁸ mol/L; citric acid, 5.10×10⁻⁸ mol/L; barbituric acid, 2.48×10⁻⁷ mol/L. The proposed method was successfully applied to determination of oxalic acid. The coupled chemiluminescent reaction mechanism and rate equation are proposed. Foundation item: Supported by the National Natural Science Foundation of China and the Natural Science Foundation of Hubei Province Biography: HAN He-you (1962-), male, Associate professor, phD, graduate candidate     

Electrocatalytic oxidation of H<Subscript>2</Subscript>O<Subscript>2</Subscript> at a carbon paste electrode modified with a nickel (II)-5, 11, 17, 23-tetra-tert-butyl-25, 27-bis(Diethylcarbamoylmethoxy) calix[4] arene complex and its application

Electrochemical behavior of a carbon paste electrode (CPE) modified with nickel(II)-5, 11, 17, 23-tetra-tert-butyl-25, 27-bis(diethylcarbamoylmethoxy) calix[4]arene (Ni (II)-L) complex and its electrocatalytic activity towards the oxidation of hydrogen peroxide were investigated by cyclic voltammetric technique in a 5.0×10⁻² mol/L NaClO₄+1.0×10⁻³ mol/L NaOH solution. It was found that Ni(II)-L acts as an effective catalyst for the oxidation of hydrogen peroxide. The modified electrode exhibited a linear response over a hydrogen peroxide concentrations in the range of 2.0×10⁻⁵−1.0×10⁻⁴ mol/L with a detection limit as low as 1.0×10⁻⁶ mol/L. The relative standard deviation was 3.5% for 5 successive determinations of H₂O₂ at 1.0×10⁻⁵ mol/L. The modified electrode was used successfully in rainwater analysis. Foundation item: Supported by the Natural Science Foundation of Hubei Province (98J040). Biography: Li Chun ya(1972-), Ph. D. candidate, research direction: electroanalysis and electrosynthesis.     

中东孔隙型低渗灰岩储层酸液体系缓速性

酸液的缓速性是影响酸液有效作用距离的关键因素,是优选酸压工作液的重要依据。采用旋转岩盘进行了普通盐酸、胶凝酸和乳化酸与伊朗雅达油田Sarvak储层灰岩岩心的酸岩反应实验,构建了反应动力学方程和变温动力学方程。结果表明,普通盐酸的反应速率明显快于胶凝酸和乳化酸,温度对反应速率影响显著,温度越高,反应速率越快。95 ℃下,普通盐酸、胶凝酸和乳化酸的反应速率常数分别为6.1745×10_^-5 (mol/L)_^-0.8543/(cm_².s)、7.8397×10_^-6 (mol/L)_^-0.6260/(cm_².s)、7.6348×10_^-7 (mol/L)_^-1.3931/(cm_².s),反应级数分别为0.8543、0.6260、1.3931;酸液浓度为20 %时,反应活化能分别为19.31 kJ/mol、25.34 kJ/mol、31.53 kJ/mol;乳化酸的缓速性相对最好,其次为胶凝酸,预测乳化酸和胶凝酸的有效作用距离更大;同时乳化酸反应级数较大,现场配液时需要考虑浓度对反应速率的影响。     

Study on peptide-peptide interaction using high-performance affinity chromatography and quartz crystal microbalance biosensor

The specific interaction between sense and antisense peptides was studied by high-performance affinity chromatography （HPAC） and quartz crystal microbalance （QCM） biosensor. Fragment 1-14 of human interferon-β （hlFN-βwas chosen as sense peptide and its three antisense peptides （AS-IFN 1, AS-IFN 2, and AS-IFN 3） were designed according to the degeneracy of genetic codes. The affinity column was prepared with sense peptide as ligand and the affinity chromatographic behavior was evaluated. Glu-substituted antisense peptide （AS-IFN 3） showed the strongest binding to immobilized sense peptide at pH 7.5. A quartz crystal microbalance-flow injection analysis （QCM-FIA） system was introduced to investigate the recognition process in real-time. The equilibrium dissociation constants between sense peptide and AS-IFN 1, AS-IFN 2 and AS-IFN 3 measured 2.08×10^-4, 1.31×10^-4 and 2.22×10^-5 mol/L, respectively. The mechanism study indicated that the specific recognition between sense peptide and AS-IFN 3 was due to sequence-dependent and multi-modal affinity interaction.