基于不同电化学探针检测乳腺癌基因片段电化学传感器的研究

构建了以3种不同电活性物质(铁氰化钾平衡电对、亚甲基蓝和六氨合钌)为电化学信号探针,检测乳腺癌基因片段(乳腺癌DNA)的电化学传感器。利用吸附作用将探针ss DNA固定于金纳米-多壁碳纳米管-Nafion复合纳米材料修饰金电极表面,制备了DNA电化学传感器。采用循环伏安法、电化学阻抗法和微分脉冲伏安法,对DNA电化学传感器进行表征和定量分析。实验结果表明,在5 mmol/L K3[Fe(CN)6]-5mmol/L K4[Fe(CN)6]平衡电对电化学探针检测液中,乳腺癌DNA的线性范围为0.1~500.0 nmol/L,其检出限(S/N=3)为0.03 nmol/L。以20μmol/L亚甲基蓝为电化学探针检测液时,乳腺癌DNA的线性范围为1.0~500.0 nmol/L,检出限为0.3 nmol/L。利用50μmol/L六氨合钌电化学探针检测时,乳腺癌DNA的线性范围为1.0~500.0 nmol/L,检出限为0.3 nmol/L。3种电化学探针中,利用铁氰化钾平衡电对探针检测乳腺癌DNA的检出限最低,线性范围最宽。该传感器可用于其他DNA的检测分析。     

纳米金-Nafion修饰金电极电化学阻抗法测定人端粒DNA

报道了基于纳米金-Nafion修饰金电极检测人端粒DNA的电化学阻抗传感器。将纳米金与Nafion混合超声得到纳米金-Nafion纳米材料,将此纳米材料滴涂于金电极表面获得纳米金-Nafion修饰电极。再将探针人端粒ss DNA滴涂在修饰电极上制备电化学阻抗传感器。利用扫描显微镜对纳米材料的形貌进行了表征。利用循环伏安法和电化学阻抗法对传感器进行了表征及目标人端粒DNA的定量测定。在最优化实验条件下,电化学阻抗传感器响应信号(ΔRet)与目标人端粒DNA浓度的对数(lgc)在0.001~1.0 nmol/L范围内呈良好线性关系。检出限为3.0 pmol/L。对0.5 nmol/L的目标人端粒DNA 7次平行测定,相对标准偏差RSD为3.5%。     

基于核酸适体修饰的纳米通道分离β-雌二醇和雌酮的研究

建立了修饰金纳米通道分离β-雌二醇和雌酮的新方法。以聚碳酸酯膜为模板,基于模板合成-化学沉积原理,在其表面及膜孔内壁均匀沉积纳米金层,得到一定孔径的金纳米通道,利用扫描电镜(SEM)、透射电镜(TEM)等对其进行研究表征,制备得到均一、可靠的金纳米通道膜。在制备好的金纳米通道表面,通过分子自组装的方式将β-雌二醇核酸适体修饰在金纳米通道内,得到对β-雌二醇具有选择性的纳米通道。β-雌二醇较容易通过修饰后的纳米通道,而雌酮不易通过。考察了β-雌二醇和雌酮在β-雌二醇核酸适体修饰的金纳米通道的迁移特性,以此实现二者的分离。利用50 nm聚碳酸酯膜沉积金3 h,得到孔径约20 nm金纳米通道膜,在0.5 mmol/L Tris-HCl缓冲溶液(pH 7.4)中,进样池浓度为1.76×10!5mol/L的β-雌二醇和雌酮,分离度达到1.76。     

功能化纳米金增强的DNA电化学检测和序列分析

用冠以大量二茂铁的纳米金微粒 /抗生蛋白链菌素结合物为标记物 ,将其标记于生物素修饰的寡聚核苷酸片段上 ,制成了具有电化学活性和纳米金放大作用的DNA电化学生物传感器 .首先采用巯基DNA和巯基烷烃混合自组装膜制备了金修饰电极 ,将探针DNA分子固定在了电极表面 ,运用杂交原则结合靶点分子在电极表面形成了双螺旋的DNA链 ,然后借助抗生蛋白链菌素和生物素之间的强亲和作用 ,引入了功能化的纳米金 .通过伏安法测定了修饰在纳米金上的二茂铁的氧化还原电流 ,可以识别和测定溶液中互补的靶点DNA ,17 mer靶点DNA的浓度在 0 .0 0 1～ 10nmol/L范围内有线性关系 ,检测限可达 0 .75× 10 -12 mol/L .     

基于单链核酸-纳米金-汞模拟酶的汞离子检测方法研究

将汞离子(Hg2+)沉积到吸附单链核酸(ssDNA)的纳米金(AuNPs)表面后,可以提高纳米金的模拟过氧化物酶活性,基于此原理可实现Hg2+的高灵敏检测。研究发现ss DNA能够促进Au NPs-Hg2+的类似过氧化物酶活性,且随着ss DNA浓度的增加,该作用呈增强趋势。在优化反应条件下,将ss DNA-Au NPs-Hg2+模拟过氧化物酶用于Hg2+的检测,Hg2+的检测线性范围为10~1 000 nmol/L,检出限可达3.0 nmol/L。该检测方法具有简便快速、成本低、稳定性高等优点,有望用于环境、食品等样品中Hg2+的检测。     

基于G-四联体的纳米探针比色检测铅离子

基于纳米探针和G-四联体建立了简便快速检测铅离子的方法. 纳米探针采用金纳米粒子自组装修饰富G寡核苷酸制得, 在铅离子存在下, 纳米探针上的富G寡核苷酸形成G-四联体, 导致纳米探针凝聚变色. 在优化条件下, 比色检测铅离子的线性范围为48~480 nmol/L, 检出限为20 nmol/L; 大多数金属离子无明显干扰, 而有明显干扰的汞离子可采用与之特异结合的寡核苷酸有效消除. 将该法成功用于环境水样中铅离子的检测, 重现性(RSD<3.0%)与回收率(98.4%~101.5%)良好.     

催化发夹组装诱导的金纳米颗粒聚集比色检测卡那霉素

建立了基于催化发夹组装诱导的金纳米颗粒聚集检测卡那霉素的方法。利用卡那霉素与适配体的特异性结合释放出引发链,引发吸附于金纳米颗粒表面的催化发夹组装,形成大量双链结构,导致金纳米颗粒在高盐浓度条件下发生聚集。通过凝胶电泳和透射电镜对催化发夹组装和金纳米颗粒的聚集进行了表征并对实验条件进行了优化。结果表明,37℃条件下,发夹探针浓度为160 nmol/L,NaCl浓度为20 mmol/L时,方法的线性检测范围为4.0～160 nmol/L,检测限为1.6 nmol/L。将该方法用于牛奶样品中卡那霉素的加标回收实验,回收率为97.5%～109.0%,相对标准偏差在1.9%～3.0%之间。     

基于纳米金探针和基因芯片的DNA检测新方法

运用荧光纳米金探针和基因芯片杂交建立一种新的DNA检测方法. 荧光纳米金探针表面标记有两种DNA探针: 一种为带有Cy5荧光分子的信号探针BP1, 起信号放大作用; 另一种为与靶DNA一部分互补的检测探针P532, 两种探针比例为5∶1. 当靶DNA存在时, 芯片上捕捉探针(与靶DNA的另一部分互补)通过碱基互补配对结合靶DNA, 将靶DNA固定于芯片上; 荧光纳米金探针通过检测探针与靶DNA及芯片结合, 在芯片上形成“三明治”复合结构, 最后通过检测信号探针上荧光分子的信号强度来确定靶DNA的量. 新方法检测灵敏度高, 可以检测浓度为1 pmol/L的靶DNA, 操作简单, 检测时间短. 通过改进纳米金探针的标记和优化杂交条件, 可进一步提高核酸检测的灵敏度, 这将在核酸检测方面具有重要的应用价值.     

基于金纳米粒子的动态光散射法检测溶液中的汞离子

发展了种基于汞离子(Hg2+)适配体(Aptamer)免标记金纳米粒子的动态光散射(DLS)法,用于灵敏、选择性的检测溶液中的Hg2+。Aptamer 5’-TTTCTTCTTTCTTCCCCCCTTGTTTGTTGTTT-3’与Hg2+的特异性结合使金纳米粒子失去保护,在含有100 mmol/L NaCl的缓冲溶液中发生聚集,金纳米粒子的平均水合粒径变大。在pH=7.43,110 nmol/L Aptamer,100 mmol/L NaCl,Hg2+与Probe DNA孵育时间为30 min的实验条件下,金纳米粒子水合粒径的变化值("D)与Hg2+的浓度成正比。检出Hg2+的线性范围为0.1 nmol/L~5μmol/L,检出限达0.1 nmol/L。湖水及矿泉水两种水样加标实验表明本方法能够用于实际水样中Hg2+的检测。     

基于四链体核酸构型转变快速检测Pb~(2+)的比色传感器

基于特定盐浓度条件下金纳米颗粒的聚集程度受附着于金纳米表面DNA浓度的影响,以及铅离子(Pb~(2+))能引起特定DNA构象变化而使其不能附着在纳米金表面的特点,设计了一种新型的Pb~(2+)生物传感器。当Pb~(2+)浓度在0.05~10 nmol/L的范围内时,体系的吸光度A712/A520随Pb~(2+)浓度对数值的变化而呈现线性关系,线性常数为0.994,检出限为0.03 nmol/L。在实际样品检测中,其回收率在98.6%~106.0%之间。     

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.