芯片式流通池用于顺序注射可更新表面荧光免疫法测定人血清中的IgG

采用芯片式流通池作为非均相免疫反应和原位固相荧光检测的场所,用双岔光纤将芯片式流通池与荧光光度计耦联,以双抗夹心式非均相免疫反应的模式,研究建立了测定人血清中IgG的顺序注射可更新表面非均相免疫分析新方法.     

巯基苯类为标记分子免疫检测的FT-SERS光谱研究

以对巯基苯甲酸、苯硫酚为标记分子,与金纳米粒子生成具有SERS信号的标记金溶胶．在一定条件下,标记金溶胶与抗体羊抗小鼠IgG形成SERS标记免疫金溶胶．用组装金纳米粒子的玻璃表面吸附抗体,通过对相应抗原小鼠IgG的识别,形成固相抗体/抗原对,再将SERS标记免疫金溶胶组装到固相抗体/抗原对上,形成“固相抗体-待测抗原-标记抗体(即标记免疫金溶胶)”夹心复合物,进而通过拉曼标记分子的SERS信号进行免疫检测．     

非竞争性毛细管电泳免疫分析乙肝表面抗原

用硫脲标记乙肝抗体(抗-HBs),基于抗原．抗体高选择性识别,建立了非竞争性毛细管电泳免疫分析乙肝表面抗原的新方法。研究了混合温育时间、缓冲溶液酸度和浓度、进样时间的影响。在5mmol／L Tris-20mmol／L H3BO3-3mmol／L EDTA(pH7．0)的运行缓冲溶液中,游离的标记抗体和抗原抗体复合物在15min内完全分离。HBsAg在4．0—50mg／L范围内与复合物的峰面积呈良好的线性关系;相对标准偏差小于6％;检出限为3．0mg／L。该方法用于乙肝病人血清和正常人血清中HBsAg的测定,结果令人满意。     

测定人血清白蛋白的荧光光纤流动免疫分析系统

用新型荧光光纤免疫传感流动分析测试系统,对人血清白蛋白（HSA）进行测试;将偶联于微晶纤维素表面形成的HSA固相抗体与待测HSA（抗原）、荧光标记抗原（FTTC－HSA）竞争性结合。经稀碱液处理,固相载体与抗原抗体复合物分离,用新型荧光光纤免疫传感流动分析系统测定解析液的荧光值,以求得待测HSA的含量;该法检出限为0．1g/L,日内RSD0．91％－6．4％,日间RSD1．8％－8．0％,加标回收率91％－120％;用该法测定注射用HSA,与临床检验常用的溴甲酚绿化对照,具有良好的相关性（r=0.9808)。     

流动注射在线光化学荧光法测定药物制剂中叶酸的含量

叶酸接受紫外光照后可转变成最大激发波长为274nm、最大发射波长为466nm的强荧光化合物。对光化学反应介质进行考察，发现在NaC03—NaHC03缓冲体系中所产生的光化学荧光最强，据此建立了流动注射在线光化学荧光分析法。试样在水载流的携带下与PH9．5的Na2C03—NaHC03缓冲溶液汇流后，通过一个盘绕在6—W低压汞灯上的PTFE编结式光化学反应器。在反应器中所生成的荧光化合物直接通入荧光计的流通池测定荧光强度。在最佳条件下，动态线性范围可达0．001-4mg／L，检测限为0．16μg/L，采样速率达80／h，11次测定浓度分别为0．01和0．1mg／L的叶酸标准溶液所得到的RSD分别为1．0％和0．2％。所建立的方法已成功地用于片剂中叶酸含量的测定。     

金自组膜免疫芯片的研制

用光刻掩膜真空沉积技术在石英晶片上沉积上一层 8列× 6行的金膜阵列 ,用金表面N 乙酰半胱氨酸分子自组装及EDC偶联技术将人IgG、兔IgG和鼠IgG固定在石英膜阵列上来制备免疫芯片。用FITC荧光标记兔抗羊IgG、夹心法可同时测定羊抗人IgG、羊抗兔IgG和羊抗鼠IgG。用样点荧光强度与空白比Rf 作定量指标。在抗体浓度 0 .5～ 1 0 0mg L内 ,Rf与抗体浓度的对数成线性关系。最低可检出 0 .5mg L的羊抗兔IgG。测定仅需样品 1 5 0 μL ,2～ 3h,适合于快速微量分析     

微加工芯片式流通池在顺序注射可更新表面反射光谱检测中的应用

提出了一种以湿法蚀刻技术制备的用于流动注射（FI）或顺序注射（SI）进样可更新表面检测的芯片式流通池,并将此流通池与SI系统及检测器相匹配,用于顺序注射可更新表面（SI－RST）反射光谱法检测。流通池由两片玻璃封接而成,流通池通道蚀刻在玻璃基片上。流通池通过多股双岔光纤分别与光源、检测器相耦合,以实现对微珠表面的反射光谱法检测。将此SI－RST反射光谱法检测系统用于对锌的检测,并测定人发试样中微量锌的含量。     

耐尔蓝-十二烷基苯磺酸钠-蛋白质体系的荧光反应及其分析应用

研究了耐尔蓝-十二烷基苯磺酸钠体系的吸收光谱和荧光光谱特性，并以此体系建立了测定蛋白质的新型荧光探针。在优化实验条件下，对人血清白蛋白和γ-球蛋白测定的线性范围均为0．16mg/L，检出限分别为0．020mg/L和0．036mg/L。该方法用于人血清中总蛋白含量的测定，与临床测定结果相吻合。     

对氟苯酚-过氧化氢-辣根过氧化物酶体系酶联荧光免疫分析研究──Ⅰ.对氟苯酚直接法及铝-钙指示剂偶合法测定人血清中乙肝表面抗原和表面抗体

对氟苯酚在辣根过氧化物酶（HRP）的催化下可被H2O2氧化，生成本酚及F-。测定对氟苯酚荧光猝灭程度及用铝－钙指示剂荧光体系检测酶促反应释放的F－，可分别建立HRP及其标记物的两种分析方法。铝－钙指示剂偶合法测定HRP的线性范围为0．031～31U／L，检测限（3δ）为0．0093U／L。两种方法分别用于测定人血清中乙肝表面抗原及抗体，结果令人满意。     

活化高分子膜免疫电极检测乳腺癌抗原

报道了一种灵敏度高和使用简便的免疫电极,用于测定乳腺癌抗原（CA15－3）。CA15－3抗体固定在用羟胺活化的聚氯乙烯（PVC）－牛血清白蛋白（BSA）基体膜上。当抗体膜与CA15－3血清结合形成抗原体复合物膜后,将该复合物膜固定在自制Ag-AgCI基体电极顶端,利用毫伏计测定膜电位。该法可在15－240U／mL范围测定CA15－3,线性关系良好,回归方程：△E=-8、84 13、97Ig[CA15-3],相关系数0．9998。人血清中其他常见抗原对CA15－3测定基本无干扰。同时,探讨了免疫膜的电位响应机理。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.