基于适配体的纳米金光学探针可视化法快速测定中药材中的啶虫脒

以农药啶虫脒适配体作为识别元件,以纳米金作为颜色指示剂,建立了一种基于啶虫脒适配体的纳米金光学探针特异测定中药材中啶虫脒含量的方法.用甲醇超声提取样品,离心后,上清液用无水MgSO4和N-丙基乙二胺净化.纳米金溶液和啶虫脒适配体溶液在室温下反应15 min后,加入样品溶液,继续反应20 min,最后加入200 mmol...     

基于纳米金适配体传感器的激光诱导检测凝血酶

利用激光可使纳米金修饰的双链DNA(dsDNA)去杂化和适配体的特异性,设计了一种新颖、稳定、可控且高灵敏的凝血酶检测方法。将两端分别修饰金纳米粒子与荧光标记物的核酸适配体与其互补链杂化制成稳定的dsDNA传感器,当凝血酶存在时,通过激光触发传感器去杂化释放适配体并与凝血酶结合,拉近金纳米粒子与荧光标记物的距离,产生猝灭使荧光信号发生变化。对激光照射时间、激光输出功率、温育时间等条件进行优化。在最优条件下,荧光强度变化值(ΔI)与凝血酶浓度在0.55~33 nmol/L范围内呈现出良好的线性关系,其线性回归方程为y=0.0082x+0.2714,相关系数R^2为0.98,血清中加标回收率为95.5~102.7%,且溶菌酶等无明显干扰。该方法可作为凝血酶的检测方法。     

采用纳米金和荧光标记的适配体检测凝血酶

将荧光染料分子标记的含29个碱基的可识别凝血酶的DNA适配体非特异吸附到纳米金表面,荧光发生猝灭,加入凝血酶后,凝血酶与适配体特异性结合,使适配体空间结构发生改变,荧光染料分子远离纳米金表面,荧光恢复,因此可以实现对凝血酶的检测。实验结果表明,这种检测方法简便、快速、特异性强,检出限为0.54 nmol/L(对应样品体积为200μL)。     

以甲苯胺蓝为电化学探针的核酸适配体传感器用于腺苷的检测

通过金硫键将腺苷适配体互补链(S1)和末端带羧基的DNA链(S2)修饰在金纳米粒子(GNPs)表面,以及甲苯胺蓝(TB)与S2的酰胺反应将TB标记在金纳米粒子表面形成甲苯胺蓝标记的DNA探针分子TB-S2-GNPs-S1,然后在玻碳电极表面电沉积一层金纳米粒子,以其为载体将末端带有巯基的腺苷适配体(Apt)固定在电极表面,以牛血清蛋白为封闭剂消除非特异性吸附,再通过TB-S2-GNPs-S1中的S1与Apt杂交将TB-S2-GNPs-S1负载到电极表面,成功建立了一种以甲苯胺蓝为电化学探针检测腺苷的适配体生物传感器。采用紫外可见光谱和扫描电镜对合成的金纳米粒子和TB-S2-GNPs-S1复合物进行表征。对电极的组装过程采用循环伏安法和电化学阻抗法(EIS)进行表征,对传感器的性能采用差分脉冲法(DPV)和电化学阻抗进行研究。该传感器在1.0×10-4~100.0 ng/m L范围内对腺苷具有良好的信号响应,相关系数(r)为0.994,检出限(S/N=3)为64.7 fg/m L。     

基于上转换荧光纳米粒子和金纳米粒子间荧光共振能量转移的高灵敏赭曲霉毒素A检测方法研究

制备了水溶性的上转换荧光纳米材料,在其表面修饰赭曲霉毒素A(OTA)适配体作为能量供体探针;在金纳米粒子表面修饰OTA适配体互补链作为能量受体探针,构建了OTA适配体传感器。在最优条件下,OTA的检测范围为0.001~10 ng/mL,检出限可达0.001 ng/mL。将其应用于啤酒样品中OTA的检测,当加标水平为0.01、0.1、1.0 ng/mL时,回收率为100%~119%,相对标准偏差为4.3%~4.9%,表明该方法可用于实际样品检测。该方法具有灵敏度高、特异性好、操作简单、成本较低等优点。     

基于纳米多孔硅烷薄膜的适体电化学传感器用于黄曲霉毒素B1的检测

构建了一个基于纳米多孔硅烷薄膜的适体电化学传感器,用于中草药中的黄曲霉毒素B1(AFB1)的灵敏检测。以溶胶-凝胶溶液电沉积再洗脱的方法在活化的玻碳电极表面制备了孔隙均匀,结构稳定的纳米多孔硅烷薄膜,并在此基础上沉积了金纳米粒子,为巯基修饰的适配体提供了大量的活性位点。利用AFB1与适配体的特异性结合能力,将适配体上吸附的信号分子亚甲基蓝（MB）与目标物AFB1形成竞争关系,以此来定量检测AFB1,线性范围在0.01～75μg/L,检出限为5.6 ng/L。方法应用于3种中草药（当归、黄芪、党参）的加标回收检测,结果满意。本传感器的构建为检测AFB1提供了一个新的思路。     

基于金包裹磁性纳米粒子与适配体修饰CdTe纳米探针的凝血酶检测方法

构建了一个适配体修饰的CdTe纳米探针,利用磁性纳米粒子的分离技术,采用示差脉冲伏安法检测凝血酶。磁性纳米粒子作为分离材料,CdTe纳米粒子作为电化学探针,通过凝血酶的特异性识别,适配体从DNA双链中解旋,并与凝血酶结合形成G-四重体结构,达到检测凝血酶的目的,检出限达0.13pmol/L。该方法灵简便、灵敏、成本低,并成功用于实际样品的检测。此外,该方法可被广泛应用于蛋白质监测和疾病诊断。     

基于核酸适配体和纳米材料的凝血酶蛋白特异性识别电化学生物传感器

介绍了一种结合核酸适配体技术和纳米技术,以凝血酶蛋白为研究对象的高效、高灵敏、特异性识别蛋白质的电化学生物传感器. 利用金纳米颗粒标记的核酸适配体以及被固定在磁性纳米颗粒上的核酸适配体与凝血酶蛋白同时结合形成磁性颗粒/凝血酶/纳米金胶的三明治结构, 利用磁性分离, 将金胶纳米颗粒特异性地吸着到电极表面, 通过检测电极上金胶的电化学信号, 实现对凝血酶靶蛋白的检测. 这种生物传感器对凝血酶蛋白具有很高的特异性识别能力, 其检测不受其他蛋白质如牛血清白蛋白等存在的干扰, 可应用于实际血浆中凝血酶的检测. 由于利用磁性纳米颗粒使得分离、富集和测定在同一个自制的电化学反应池中进行, 其操作不仅简单, 而且检测的灵敏度得到提高. 该蛋白质生物传感器的线性范围为5.6×10^-12 ~ 1.12×10^-9 mol/L, 检测限可以达到1.42×10^-12 mol/L.     

核酸适配体传感器在黄曲霉毒素B1检测中应用研究进展北大核心CSCD

核酸适配体作为一种新型识别分子,具有亲和力高、稳定性强、制备成本低、特异性强等优点,但其自身不具有信号转换功能,它与靶标分子特异性结合过程,不可产生被检测的物理化学信号。因此,需将核酸适配体与靶标分子特异性识别结合过程转为易于被检测的物理化学信号变化的过程。根据信号转换方式的不同,可将适配体生物传感器分为荧光适配体传感器、比色适配体传感器、电化学适配体传感器和表面拉曼散射适配体传感器。本文对基于以上4种检测信号的核酸适配体生物传感器在黄曲霉毒素(AFB1)检测方面的应用进行综述,并概述该类传感器应用前景和当前面临的挑战。     

核酸适配体生物传感器在农残检测中的研究进展EI北大核心CSCD

由于核酸适配体具有特异性强、亲和力高、制备方便、易修饰、稳定性好、目标物多样性等特点,基于适配体的传感器研究工作一直是广大科研工作者的研究热点。相较于具有特异性识别的生物酶的使用,核酸适配体在农药残留检测中的应用正在发展中,具有广阔的前景。本文主要介绍近两年来核酸适配体生物传感器在农药分子检测领域的相关进展。     

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%.     

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.     

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.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones

Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.     

Knoevenagel condensation catalyzed by novel Nmm-based ionic liquids in water

A series of novel N-methyl morpholine (Nmm) based ionic liquids with 1,2-propanediol group were synthesized and used as catalysts for Knoevenagel condensation at room temperature in water. Under the effect of the catalyst, various aldehydes or aliphatic ketones could react with a wide range of activated methylene compounds well, including malononitrile, alkyl cyanoacetate, cyanoacetamide, β-diketone, barbituric acid, 2-arylacetonitrile and thiazolidinedione. Furthermore, most of the products could be separated just by filtrating and washing with water. Additionally, the catalyst is recyclable and applicable for the large-scale synthesis.     

Construction of polyheterocyclic spirotetrahydrothiophene derivatives via sulfa-Michael/aldol cascade reaction

A series of polyheterocyclic spirotetrahydrothiophene derivatives were obtained in moderate to excellent yields via a catalyst-free sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 under mild conditions. We also present the first asymmetric sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 with moderate to good enantioselectivities catalyzed by readily available chiral phase-transfer catalysts (PTCs).     

Suzuki-Miyaura reactions of the soluble guanylate cyclase inhibitor NS2028: a non-product specific route to C-8 substituted analogues

Both soluble guanylate cyclase (sGC) inhibitors ODQ 1 and NS2028 2 are synthesized via improved protocols. In the former case treating 3,4-dihydroquinoxalin-2(1H)-one oxime 8, which can be prepared in two steps from 1,2-benzenediamine, with 1,1′-carbonyldiimidazole (CDI) gives the dihydro-ODQ 10 that in the presence of KMnO₄ oxidises to give ODQ 1 in an overall yield of 46% starting from 1,2-benzenediamine. In the latter case, the synthesis affords NS2028 2 from 2-amino-4-bromophenol 3 in three steps with an overall yield of 85% and avoids the need for chromatography. Furthermore, Suzuki-Miyaura reaction conditions are described that enable the preparation of 8-aryl and 8-heteroaryl derivatives of NS2028 directly from NS2028 2. Finally, demethylation of the 8-(methoxyphenyl) substituted analogues afforded the 8-(hydroxyphenyl) derivatives 40-42. All new products are fully characterised.