基于DNAzyme与铀特异性反应的共振光散射法检测铀

建立了基于铀特异性DNA酶-Au NPs检测UO22+的共振光散射新方法。在p H 4.5的10 mmol/L MES缓冲溶液中,铀特异性DNA酶在铀作为辅助因子的条件下发生自身断链反应,释放出ss DNA,吸附在Au NPs表面,阻止Au NPs在高浓度盐下聚集,使体系的共振光散射强度降低。在2.08×10-9~2.00×10-8mol/L范围内,散射光强度的改变值与UO22+浓度呈良好线性关系,回归方程为ΔI=59.45+14761 c(μmol/L),r=0.9852,检出限为6.23×10-10mol/L,加标回收率为95.0%~106.5%,相对标准偏差为(RSD)1.9%~9.1%,方法成功用于实际样品检测。     

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。     

基于硫代黄素T诱导G-四联体构成的生物传感器检测铅离子

硫代黄素T(ThT)荧光分子在自由状态下荧光强度很弱, 通过在Tris-HCl缓冲液中加入Pb²⁺的适配体即富含G的DNA序列, 可与ThT荧光分子形成G-四联体结构, 使荧光信号迅速增强; 向溶液中加入Pb²⁺, Pb²⁺与其适配体有很好的结合特异性, 可生成更牢固的G-四联体结构, 使ThT分子被释放出来, 导致溶液的荧光强度降低, 基于此可检测溶液中的Pb²⁺离子. 实验中优化了缓冲溶液组成、 ThT荧光分子浓度、 Pb²⁺适配体浓度及反应时间等条件. 结果表明, 在10 mmol/L Tris-HCl(pH=8.3, 含2 mmol/L MgCl₂)缓冲溶液中, ThT荧光分子和Pb²⁺适配体的浓度分别为10 μmol/L和200 nmol/L, 反应10 min时, 随着溶液中Pb ²⁺浓度的增加, 荧光强度减弱. Pb²⁺浓度在20~1000 nmol/L范围内时, 荧光强度与Pb²⁺的浓度呈现良好的线性关系(R²=0.9941), 检出限为1 nmol/L. 实际水样测试结果表明, 该方法的回收率在98.8%~101.3%之间. 该传感器灵敏、 快速、 无需化学修饰荧光分子且成本低.     

基于石墨烯和蒽醌-2-磺酸钠的Pb2+核酸适体电化学传感器

构建了一种基于石墨烯(GR)-蒽醌化合物(AQMS)在核酸适体表面层层组装的Pb2+电化学传感器。将修饰有巯基的Pb2+核酸适体(apt)固定在金电极表面,然后利用GR与apt碱基之间的π-π作用,将GR吸附在apt修饰电极表面,并用于电活性分子AQMS的组装和电化学信号的放大。当目标分析物(Pb2+)存在时,Pb2+诱导apt转变为稳定的G-四联体结构,使得GR连同信号分子AQMS从电极表面脱落,电化学信号降低,从而实现对Pb2+的监测。结果表明,传感器对Pb2+具有很好的特异识别性,且Pb2+浓度在5.0×10!10~5.0×10!8mol/L的范围内,AQMS的峰电流变化值(ΔIpa)与Pb2+浓度对数(lgCPb2+)呈现良好的线性关系。根据3σ,计算得检出限达到6.0×10!11mol/L。     

基于Ru@SiO_2的微囊藻毒素电化学发光免疫传感器研究

本研究在玻碳电极(GCE)表面电沉积金纳米粒子(Au NPs),通过化学吸附将微囊藻毒素-(亮氨酸-精氨酸)(MC-LR)的单克隆抗体(anti-MC-LR)固定在电沉积了Au NPs的玻碳电极表面,以牛血清白蛋白(BSA)封闭非特异性吸附位点,制得免疫电极anti-MC-LR/Au NPs/GCE。采用微乳化法制备了掺杂三(2,2'-联二吡啶)钌(Ⅱ)配合物离子(Ru(bpy)2+3)的二氧化硅纳米粒子(Ru@SiO2),利用透射电镜和扫描电镜对所制备的纳米粒子进行表征。3-氨基丙基三乙氧基硅烷(APTS)进一步与Ru@SiO2反应,制得氨基功能化的Ru@SiO2,通过1-(3-二甲氨基丙基)-3-乙基碳二亚胺(EDC)和N-羟基琥珀酰亚胺(NHS)活化辣根过氧化物酶标记的MC-LR(HRP-MC-LR),并使其与氨基功能化的Ru@SiO2偶联,制得MC-LR-Ru@SiO2。采用直接竞争模式,在标记物MC-LR-Ru@SiO2存在下,以三丙胺作为共反应物,利用电化学发光法(ECL)测定溶液中的微囊藻毒素,免疫反应完成后,电化学发光强度(I)随着MC-LR浓度的增大而减小,且在0.100~100μg/L范围内,电化学发光强度差值(ΔI)与游离的MC-LR浓度的对数呈良好线性关系,检出限为0.007μg/L。对实际水样进行了加标回收实验,回收率为95.5%~105%。     

SiO2介导的5 nm金颗粒的高效富集及其催化活性研究

粒径小于10 nm的金纳米颗粒（Au NPs）具有高的表面积与体积比,因此具有极强的催化活性,在催化领域应用广泛.传统湿法合成的金纳米颗粒浓度过低,需要进一步富集才能满足实验要求.然而,小粒径Au NPs在浓缩过程中容易聚集,失去催化活性.在保持催化活性的同时,浓缩小粒径的AuNPs是一个挑战.本工作用500 nm硅烷化修饰的SiO₂颗粒,通过静电相互作用吸附5 nm Au NPs,在室温下自组装形成Au NPs@SiO₂复合物.Au NPs的负载效率可达99.5%,每个SiO₂上负载的Au NPs高达800～1000个,大大提高了Au NPs有效浓度,并且富集到SiO₂表面的Au NPs不会团聚.催化活性研究结果显示,制备得到的Au NPs@SiO₂的催化活性是同浓度Au NPs的3倍.该复合物颗粒重复使用5次后,催化转换效率仍能保持在80%左右.该复合物颗粒能稳定保存一个月,结构和催化活性不变.并且,通过调节Au NPs在SiO₂表面的组装密度,可精确调控Au NPs@SiO₂催化活性.本工作提供了一种制备高浓度小粒径Au NPs的简单方法,并大大提高了Au NPs催化活性,该方法在富集其它小粒径纳米颗粒中具有广泛应用.     

原子吸收光谱法测定改性梨渣吸附Pb(Ⅱ)的研究

通过原子吸收光谱法研究了在不同pH、吸附剂量、Pb2+浓度和吸附时间条件下磷酸酯化改性梨渣吸附Pb2+的行为。结果表明:溶液初始pH 4.2时,Pb2+的吸附达到最大值;酯化梨渣≥10 g/L能除去Pb2+为30 mg/L溶液中的91%的Pb2+。酯化梨渣对Pb2+的吸附符合Langmuir等温模型,其最大吸附能力为43.99 mg/g。Pb2+达到吸附平衡的时间为40 min,准一级反应动力学方程可描述酯化梨渣对Pb2+的吸附过程。     

基于蘑菇状的金/聚苯胺纳米复合材料的亚硝酸根传感器

通过原位聚合法制备了金纳米颗粒(Au NPs)掺杂的聚苯胺(PANI)纳米复合材料，该复合材料修饰的电极(Au/PANI/GCE)对亚硝酸根(NO₂^-)的氧化具有明显的电催化活性，其独特且均匀分散的蘑菇状结构可以掺杂更多的Au NPs，提供较多的活性位点和较大的比表面积，有助于提高电化学催化NO₂^-的效果。导电聚合物PANI中可质子化的苯胺(PhNH³⁺)与溶液中带负电荷的NO₂^-产生静电吸附可促进电子的传递。Au/PANI/GCE对NO₂^-的检出限为0.6876μmol/L，线性范围为10～2400μmol/L，线性相关系数R²=0.9957，该传感器为实际湖水样品中亚硝酸盐检测提供了新方法。     

巯基功能化膨润土吸附Pb2+的动力学和热力学研究

研究了自制巯基功能化膨润土(TFB)对Pb2+的吸附行为,考察了溶液的pH值、离子强度、吸附时间和温度对吸附平衡的影响,并对吸附过程进行了动力学与热力学研究.结果表明,常温下,吸附时间为60min、0.1mol/L的KNO3、pH=6.0、5.0g/L TFB对200mg/L的Pb2+的吸附率达到85.4％以上,TFB对Pb2+的吸附动力学符合准二级动力学方程;TFB对Pb2+的吸附热力学符合Langmuir等温线方程和Dubinin-Radushkevich (D-R)等温线方程,表明吸附主要发生在TFB表面的活性区域,属于单分子层吸附,其吸附平均活化能E在8-16kJ/mol范围内,表明该吸附过程为化学吸附,不同温度下的吸附热力学的吉布斯自由能以及熵变和焓变表明该吸附过程为自发放热反应.     

基于 G-四联体门控制效应的铅离子适配体传感器

将富鸟嘌呤(G)序列核酸适配体与门控制效应相结合,通过控制门的开关实现信号放大,构建了新型电化学生物传感器,用于铅离子(Pb2+)的高灵敏检测。首先将单-6-巯基-β-环糊精(6-SH-β-CD)自组装在金电极上,形成有序排列的分子自组装膜,且分子之间留有空隙,可作为探针通过的门结构。随后将发夹结构的富含 G 序列的核酸适配体修饰在环糊精次面端口,制得可特异性识别 Pb2+的电化学生物传感器。富 G 序列适配体结合 Pb2+后可折叠形成 G-四联体结构(G4-Pb2+),覆盖住电极表面的探针通道,产生关门效应,使探针氧化还原电流强度减小,进而形成门控制效应,利用该效应可进行 Pb2+的定量检测。门控制效应显著提高了信噪比和检测的灵敏度,在1×10-13~5×10-11 mol/ L 浓度范围内,Pb2+浓度的负对数与 DPV 响应电流呈良好的线性关系,检出限为3.6×10-14 mol/ L(DL=3δb / K)。传感器用于实际水样品中 Pb2+的测定,结果令人满意。     

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%.     

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.     

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.     

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.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

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.