抗体固载于电聚合物膜的压电免疫型细菌传感器

采用电化学技术在镀银的压电石英晶体上沉积一层聚间苯三酚膜 ,用二乙烯基砜将其活化后 ,实现了特异性抗体 (抗肠道沙门氏菌抗体)在压电石英晶体上的固载 ,并用于肠道沙门氏菌的快速检测 ;其检出限为5×104cell/mL,检测时间为30min;该抗体固载技术简单易行 ,重复性好 ,并可用于价格低廉的镀银石英晶体 ,可望成为开发一次性压电型免疫检测探头的有效方法     

石英晶体微天平用于免疫球蛋白M免疫反应的动力学研究

在镀银电极的压电石英晶体表面涂覆甲基丙烯酸甲酯－甲基丙烯酸羟乙酯共聚物涂层，经ＣＮＢｒ活化后固定抗体，用石英晶体微天平技术监测ＩｇＭ抗原在压电石英晶体上的吸附与解吸过程，研究了免疫反应体系ＩｇＭ－抗人ＩｇＭ的反应动力学．结果表明：ＩｇＭ在压电石英晶体上的键合行为很好地符合Ｌａｎｇｍｕｉｒ吸附方程，免疫反应的结合常数Ｋａｓｓ为７．１０×１０￣７（ｍｏｌ／Ｌ）￣（－１）．在抗原过量情况下为一级反应。计算了ＩｇＭ免疫反应的活化能Ｅａ和不同温度下的反应速率常数ｋｆ．     

检测硫化氢阳性菌属压电石英传感器的研制

针对硫化氢阳性菌属在新陈代谢过程中释放出H2S的特性,设计了双面镀银的压电石英晶体探头,构建新型的生物传感器模式。信号探针修饰的Ag可与生物代谢产物H2S结合,通过压电石英晶体经典的气相质量响应的原理,实现了对硫化氢阳性菌属的检测。结果表明,该传感器能很好地区分硫化氢阳性、阴性菌属,培养基中最佳的半胱氨酸浓度为0.05%。该传感器的设计避免了培养基与探头之间的直接接触,减少了液相质量响应存在的干扰,成功实现了硫化氢阳性菌属的自动培养和检测。     

压电胰岛素-C肽微阵列免疫传感器研究

以AT切型、基频10MHz的镀金膜石英晶体作为换能器,将抗人胰岛素和C肽单克隆抗体固定在石英晶体电极表面,用2×5检测池固定夹具构建一种新型压电胰岛素-C肽微阵列免疫传感器.研究了抗体固定方法、抗体工作浓度、固定量、一致性以及传感器的响应参数如检测温度、时间和特异性等的影响.该微阵列传感器在胰岛素浓度为2.5～160.0mIU/L、C肽浓度为0.375～12.0ng/mL范围内响应特性良好,压电晶体频率偏移值与胰岛素和C肽浓度呈良好的线性关系.将此微阵列传感器用于人血清标本的测定,结果与放射免疫法符合(r为0.92和0.94).此微阵列传感器具有灵敏度高、特异性好,低密度阵列结构,检测通量较高,不需标记,操作简单、能实时在线检测和重复使用等优点,能用于临床实验诊断,具有临床推广应用价值.     

电化学石英晶体微天平研究普鲁士蓝修饰电极

石英晶体徽天平(Quartz Crystal Microbalance,简称QCM)是一种非常灵敏的质量传感器,其检测能力可达ng级。QCM在化学中的早期应用是检测大气中的徽量成分,目前仍较活跃。由于石英压电晶体浸入溶液后在晶体/溶液界面存在较大的能量损失而不能够稳定振荡,致使QCM的应用较长时间局限于气相。八十年代初石英压电晶体在液相中的振荡终获成功,开辟了QCM应用的一个全新领域。液相中振荡成功后,QCM很快应用于电化学研究。目前已发展成为一种全新的电化学传感器——电化学石英晶体微天平(EQCM),并已用于金属电沉积、电化学腐蚀、电分析等方面的研究。     

压电免疫传感器用于C2型葡萄球菌肠毒素的测定

报道了用蛋白Ａ－金电极法将抗体固化在３．５８ＭＨｚ和１０ＨｚＡＴ切割的石英晶体上，制作的可重复使用的压电免疫传感器，测定Ｃ２型葡萄球菌肠毒素。最适ＰＨ值为７，并用不同的方法测试了晶体片上的抗体固化情况。     

基于Nafion膜修饰的血吸虫抗体压电免疫传感器研究

将Nafion膜包埋血吸虫抗原固定在石英晶体微天平表面上,构制了用于测定血清中血吸虫抗体的压电免疫传感器.这种生物敏感膜由涂敷在石英晶片表面上的一滴Nafion+血吸虫抗原磷酸盐缓冲液干燥而成,它的构制和再生过程具有良好的重现性.用扫描电镜观察了这种生物敏感膜的形貌,并对传感器的构制参数、测量条件进行了优化,优化的传感器对血吸虫抗体的检测范围为0.2～6.0 mg/L.本传感器具有仪器简单、操作方便、灵敏度高、重现性好等优点,可判断血吸虫感染情况.     

甲胎蛋白压电免疫传感器的研究

以合成的甲基丙烯酸甲酯和甲基丙烯酸羟乙酯共聚作载体，在压电石英晶体表面涂覆共聚物涂层，经ＣＮＢｒ活化后固定ＡＦＰ抗体，研制成ＡＦＰ压电晶体免疫传感器，研究了固定化方法，载体量，抗原抗体结合时间，重现性选择性等实验条件和参数的影响，压电晶体的频移值与ＡＦＰ浓度在１００ｎｇ／ｍＬ～８００ｎｇ／ｍＬ的范围内有良好的线性关系，将此传感器初步用于人体血清样品的测定，并与放射免疫法对照，结果令人满意。     

基于酶催化银沉积质量放大的血吸虫压电免疫传感器的研究

发展了一种基于酶催化金属银沉积信号放大的新型高灵敏气相压电免疫传感检测技术.先将血吸虫抗原(SjAg)共价固定在石英晶体表面,制备得到血吸虫压电免疫传感器.检测时,在晶振上滴加不同浓度的待测血吸虫抗体,再将碱性磷酸酶标记的二抗通过夹心方式结合到传感器表面.然后利用碱性磷酸酶催化磷酸化的抗坏血酸酯水解从而还原硝酸银,使金属银沉积在晶振表面上,放大传感器的质量响应信号.实验结果表明该传感检测方法可显著提高气相压电免疫传感器的检测灵敏度,传感器对血吸虫抗体的响应线性范围在1～225 ng/mL,检测下限为1 ng/mL.     

基于Nafion膜修饰的血吸虫抗体压电免疫传感器研究

将Nafion膜包埋血吸虫抗原固定在石英晶体微天平表面上，构制了用于测定血清中血吸虫抗体的压电免疫传感器。这种生物敏感膜由涂敷在石英晶片表面上的一滴Nafion＋血吸虫抗原磷酸盐缓冲液干燥而成，它的构制和再生过程具有良好的重现性。用扫描电镜观察了这种生物敏感膜的形貌，并对传感器的构制参数、测量条件进行了优化，优化的传感器埘血吸虫抗体的检测范围为0．2～6．0mg／L。本传感器具有仪器简单、操作方便、灵敏度高、重现性好等优点，可判断血吸虫感染情况。     

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%.     

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.     

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.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

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.     

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.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.