基于乙酰胆碱酯酶构建pH响应生物传感器用于Hg(Ⅱ)检测

以磁纳米颗粒和金纳米颗粒为载体,以核酸适配体和Hg~(2+)为生物识别单元,构建一种乙酰胆碱酯酶(AChE)联Hg~(2+)生物传感平台。分别对磁纳米颗粒进行适配体功能化,金纳米颗粒进行AChE修饰和适配体的功能化,通过目标物Hg~(2+)驱动富含碱基T的适配体形成T-Hg~(2+)-T结构,形成金-磁组装体,通过磁分离调控检测体系中AChE的浓度,AChE催化底物乙酰胆碱(ACh)水解引起反应体系的pH变化,从而实现目标物Hg~(2+)的定量检测。结果表明,方法检测范围为0.1～10 ng/mL,检出限为0.05 ng/mL。将该方法应用于自来水样品中Hg~(2+)的检测,当加标水平为0.1,1,10 ng/mL时,回收率为102.2%～113.2%,相对标准偏差为3.5%～4.1%。     

茶叶中的茶多酚荧光检测方法

以石墨烯量子点为荧光探针,基于二氧化锰纳米片与石墨烯量子点之间发生有效的荧光共振能量转移,构建了一种茶叶中茶多酚含量的荧光检测新方法。MnO2纳米片使石墨烯量子点的荧光淬灭,而茶多酚能与MnO2发生氧化还原反应,将其还原成Mn^2+,使体系荧光恢复。茶多酚含量与荧光强度增量在20~750μg/mL范围内成线性相关,线性方程为F=1.0574c-114.9,线性相关系数为R=0.9936。将该方法用于茶叶中茶多酚含量的检测,结果与国标法接近。方法有望应用于食品中其它抗氧化物质的实时检测。     

基于铜离子修饰金纳米簇“关-开”型荧光探针检测多巴胺

以11-巯基十一烷酸(11-MUA)为还原剂和保护剂,通过一步水热法合成了具有强烈荧光的水溶性金纳米簇(AuNCs),基于Cu~(2+)修饰的AuNCs@11-MUA构建了"关-开"型荧光探针用于多巴胺(DA)的选择性、高灵敏检测.向AuNCs@11-MUA溶液中加入Cu~(2+)离子后,AuNCs@11-MUA的荧光发生猝灭,体系的荧光信号处于"关闭"状态.在DA存在下,由于DA与Cu~(2+)具有更强的结合力,形成比Cu~(2+)/AuNCs@11-MUA复合体更稳定的络合物,可将Cu~(2+)从AuNCs@11-MUA表面移除下来,从而使其荧光得以恢复,体系的荧光信号呈"打开"状态.AuNCs@11-MUA探针的荧光恢复程度与DA的浓度在2.0×10~(-7)~5.0×10~(-5)mol/L范围呈良好的线性关系,检出限为8.0×10~(-8)mol/L(S/N=3).将该探针应用于人血清和尿液中DA的检测,回收率为93.2%~97.3%,相对标准偏差RSD4.08%,表明该方法可应用于人体内多巴胺的检测.     

基于纳米TiO2的化学发光法检测核黄素

纳米TiO2与NaOH溶液作用能产生化学发光辐射,在表面活性剂十六烷基三甲基溴化铵(CTAB)的存在下,核黄素的加入能增强纳米TiO2-NaOH溶液的化学发光强度。基于此,构建了纳米TiO2-NaOH溶液化学发光新体系,建立了纳米TiO2-NaOH-核黄素体系检测核黄素的化学发光新方法。在优化实验条件下,核黄素质量浓度在5.0×10-6～3.5×10-4g/mL范围内与化学发光强度呈良好的线性关系,检出限为3.0×10-6g/mL,对2.5×10-5g/mL的核黄素进行11次平行测定,相对标准偏差为2.9%。该方法用于维生素B2片剂的测定,其结果与药典方法测得一致。该文同时对化学发光反应的机理进行了初步探讨。     

基于氧化碳球的上转换荧光传感新方法检测银离子

本文构建了以上转换纳米粒子(Upconversion Phosphors,UCPs)为供体,氧化碳球为受体的荧光共振能量转移新体系用于Ag+的检测。氧化碳球对上转换荧光供体的发射具有良好的猝灭效果,当氧化碳球的浓度达到0.038mg/mL时,猝灭效率最大,达到78%。向该体系中加入Ag+后,在浓度为1～100nmol/L范围内,UCPs的荧光恢复程度与Ag+的浓度呈线性关系。该方法测定Ag+的检出限为0.98nmol/L。本实验首次尝试构建以氧化碳球为受体的荧光共振能量转移(FRET)传感器来检测Ag+,结合了UCPs的上转换发光特性和氧化碳球优良的猝灭能力以及良好的分散性,为Ag+的检测提供了一个新的方法。     

NiO/MnO_2分级纳米片阵列复合材料的制备与超电容性能

通过化学浴沉积和水热法在泡沫镍上制备了NiO/MnO_2分级纳米片阵列复合材料,XRD和SEM测试表明NiO纳米片垂直生长在泡沫镍上,交叉形成网状阵列结构;MnO_2纳米介孔泡沫进一步生长在NiO纳米片两侧,与NiO形成了壳核式的复合结构。循环伏安和恒流充放电测试发现,NiO/MnO_2分级纳米片阵列复合材料的电化学性能相比复合前得到明显改善,在1 A·g~(-1)的电流密度下,比电容提高至1 297 F·g~(-1);2 A·g~(-1)下循环1 000次,比电容保持率高达97%,比电容和循环性能的改善是由于分级纳米片阵列复合结构方便了电解液传质,扩大了活性材料与电解液的接触,促进了赝电容反应,提高了NiO和MnO_2的结构稳定性。     

木质素碳纳米酶的制备及用于检测人尿液中多巴胺

以木质素磺酸钠为碳源,水热法合成了MoS2掺杂的碳纳米酶(Mo, S-CDs),并基于其过氧化物酶特性,将其用于检测人尿中多巴胺的含量。对纳米酶的形貌进行了表征。结果显示,Mo, S-CDs为球型,直径在2 nm左右,在水中能够较好的分散;红外图谱结果表明Mo, S-CDs表面官能团丰富;X射线光电子能谱表明Mo, S-CDs中存在Mo, S, C, O元素。Mo, S-CDs具有稳定、高效的过氧化物酶催化活性,可催化H₂O₂与3,3’,5,5’-四甲基联苯胺(TMB)反应,生成氧化产物oxTMB。蓝色的oxTMB可被多巴胺还原回TMB,导致系统在oxTMB特征峰处的吸光度下降。因此,基于Mo, S-CDs对H₂O₂的传感能力构建了多巴胺-Mo, S-CDs的催化传感体系,并用于检测人尿液中多巴胺的含量。多巴胺浓度在0.5～20μmol/L范围内有良好的线性关系,检出限为0.0639μmol/L,回收率为96.5%～101.7%,相对标准偏差(RSD)<5%。     

基于MnO_2纳米线-还原石墨烯复合修饰电极的多巴胺电化学检测

通过电化学还原法制备MnO_2纳米线/还原石墨烯复合修饰电极(MnO_2-RGO/GCE),用于多巴胺(DA)的检测。采用扫描电镜和X-射线粉末衍射对不同的修饰电极微观形貌进行了表征,优化了电化学还原条件和测定DA实验条件。此外,还研究DA在裸电极及RGO或MnO_2-RGO修饰电极上的循环伏安响应。MnO_2-RGO/GCE复合修饰电极实现AA、DA和UA氧化峰的有效分离,AA-DA和DA-UA的氧化峰电位差分别为268和128 m V。检测DA的线性范围为0.06~1.0μmol/L和1.0~80μmol/L,检出限为1.0 nmol/L(S/N=3)。制备的MnO_2-RGO/GCE成功用于人血清样品的多巴胺含量分析。     

CuNPs/PAA/GR纳米新材料修饰玻碳电极检测猪肉中的莱克多巴胺

采用一种温和且简单的原位生长法将铜纳米粒子和石墨烯非共价键合,形成一种对莱克多巴胺催化活性高的复合纳米新材料Cu NPs/PAA/GR。该材料用扫描电镜表征形貌,用阻抗表征修饰电极。不同扫速和p H值条件下,以其修饰玻碳电极构建的电化学体系受吸附控制,莱克多巴胺在该电极表面的反应机理属两电子转移过程。体系中电化学参数为:电子转移数(n)=1.7,修饰电极的有效面积为3.57 cm2,为裸电极的12.6倍,电极吸附量(Гs)为1.98×10-12mol/cm2。采用微分脉冲伏安法进行检测,莱克多巴胺的浓度在1~30μmol/L范围内呈良好线性关系(r2=0.990 2),检出限(S/N=3)为18.3 nmol/L。该传感器经济易制备、灵敏性高、稳定性与重现性好。将该传感器用于猪肉中莱克多巴胺的检测,其回收率为97.0%~102.5%,相对标准偏差为2.8%~3.2%。     

基于上转换荧光纳米颗粒-聚多巴胺纳米颗粒的生物传感器检测癌胚抗原

以上转换荧光纳米颗粒(Upconversion nanoparticles,UCNPs)为能量供体,聚多巴胺纳米颗粒(Polydopamine nanoparticles,PDA NPs)为能量受体,构建基于荧光共振能量转移的传感平台检测肿瘤标志物癌胚抗原(Carcinoembryonic antigen,CEA)。相比于传统的均相结构UCNPs,此传感器中夹层结构UCNPs(Sandwich-structure UCNPs,SWUCNPs)具有更高的能量转移效率。将CEA适配体标记于SWUCNPs表面,当向溶液中加入PDA NPs,体系的荧光猝灭效率最高可达95%。加入CEA后,体系的荧光恢复,恢复程度与CEA浓度在1.0~250.0 ng/mL范围内呈良好的线性关系,检出限为0.86 ng/mL(S/N=3)。此传感体系具有较高的选择性,在缓冲溶液与血清样品中均显示出良好的重现性。本传感器采用的能量受体PDA NPs合成简单、无需标记、猝灭能力强、分散性良好,研究结果可为基于UCNPs的传感体系构建提供新的方法学模型。     

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.     

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.     

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.     

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%).