柔性纤维生物电子复合材料与器件

可穿戴和可植入的纤维生物电子器件可以实现对人体生理体征的实时监测和精准调控,在健康监测和疾病诊疗等领域发挥了革新作用.然而,传统的纤维生物电子器件柔性不足而与生物软组织的力学性能不匹配,难以形成稳定的器件/组织界面,最终无法实现长期稳定工作.本文重点介绍了近年来课题组针对上述问题在柔性纤维生物电子复合材料与器件方面的研究进展.首先制备了具有杂化结构和芯鞘结构的柔性高分子复合纤维电极,并面向柔性生物电子器件要求,对纤维材料的电学和力学性能及生物安全性进行表征.进一步,基于所制备的复合纤维电极,发展出一系列可穿戴和可植入的纤维生物电子器件,具有传感、能源、调控等功能,并通过建立稳定的器件/组织界面,实现了在体长期工作,在生物医学研究和智慧医疗等领域展现出良好的应用前景.最后,展望了柔性纤维生物电子领域的未来发展方向.     

可穿戴生物电化学传感器的研究与应用进展

随着物联网的发展,可穿戴生物电化学传感器受到了广泛关注。可穿戴传感器件采用液体导体、导电聚合物薄膜、水凝胶等材料作为柔性电极,集优异的机械性能与传感性能于一体,为人们的生产和生活带来了极大的便利,已被广泛用于医疗诊断、健康监测和环境监测等领域。然而,目前可穿戴生物电化学传感器在美观隐形性和生物亲和性等方面仍存在一些问题。本文从可穿戴传感器件的制备工艺及柔性材料入手,概括分析了近年来可穿戴生物电化学传感器件的研究与应用进展,对其所面临的挑战与困难进行了总结,并展望了可穿戴生物电化学器件未来的发展方向,为进一步改进可穿戴传感器件的集成方法、提高其传感性能以及实现智能化信号传输等提供了参考。     

抗坏血酸在预阳极化嵌入式超薄碳糊电极上的电化学行为

以镍铬合金为基体,直接在其表面嵌入碳糊构建了嵌入式超薄碳糊(IUCP)前驱膜,然后对其表面进行电化学处理,制备了预阳极化嵌入式超薄碳糊电极(PAIUCPE).扫描电镜表征其形貌,伏安法检验其电化学性能,并以抗坏血酸(AA)为目标物考察PAIUCPE对AA的电化学响应情况,该电极制备非常简单、实验成本极其低廉,可直接用于...     

基于三维有序金掺杂纳米二氧化钛的DNA生物传感器研究

用模板法在氧化铟锡(ITO)电极上制备具有三维有序多孔结构的金掺杂纳米二氧化钛修饰电极(3DOM GTD/ITO),扫描电镜(SEM)结果表明,制备的修饰电极三维结构规整有序、孔径均一。将标记有二茂铁(Fc)的DNA探针修饰到3DOM GTD/ITO电极上构建了一种新的标记型DNA生物传感器,通过Fc在DNA探针杂交前后的电化学信号变化可识别目标靶序列。采用循环伏安(CV)、示差脉冲(DPV)和交流阻抗(EIS)等方法对DNA探针在电极表面的固定和杂交进行表征。实验结果表明,该DNA生物传感器可以成功地识别乳腺癌基因靶序列,Fc的氧化还原电流与靶序列浓度在8.0×10-7～1.0×10-5 mol/L范围内呈线性关系,线性相关系数为0.9908,检测限为5.2×10-7 mol/L。     

温敏型铜银荧光纳米簇的绿色制备及细菌成像研究

在温和条件下以D-青霉胺为配体,通过一步法制备出水溶性的具有红色荧光的铜银纳米簇(CuAgNCs),并对其形貌、结构、荧光性能等进行了表征。结果表明,制备得到的纳米簇的量子产率可达9. 6%;在279~355 K温度范围内,该纳米簇的荧光强度与温度之间呈良好的线性关系,荧光强度随着温度的增加而减弱。此外,细胞毒性噻唑蓝(MTT)实验结果表明,合成的Cu-AgNCs显示出低毒性和较好的生物相容性,它们可以渗透大肠杆菌进行细胞成像。采用共聚焦荧光成像方法在293~313 K的生理温度范围内进行细菌体内温度测量,结果表明,制备的Cu-AgNCs有望作为光致发光温度计和生物传感器应用于荧光成像等领域。     

儿茶酚胺类神经递质微环境效应的研究进展

儿茶酚胺包括肾上腺素、去甲肾上腺素和多巴胺,是人体内一类重要的神经递质。因为含有邻苯二酚等多种活性基团,儿茶酚胺对电极表面附近环境的变化有着高度的敏感性,呈现出明显的微环境效应。本文从电化学实验和量子化学计算两个角度综述了儿茶酚胺类神经递质微环境效应的最新研究进展,重点介绍了电极表面的化学修饰情况和生理介质中的生物分子两种微环境因素对儿茶酚胺氧化能力的影响。大量的文献表明,化学修饰电极可改善儿茶酚胺在电极表面的分布与活性,对儿茶酚胺的电化学行为产生特有的催化效应。生理介质中的生物分子能够与儿茶酚胺及其氧化产物醌通过弱相互作用形成超分子,从而影响儿茶酚胺的电化学氧化能力。在此基础上,本文还对儿茶酚胺微环境效应的微观本质的研究前景进行了展望。     

《生物兼容性电极购置及应用》

具备生物兼容性的电极可改善生物分子在电极界面的有序分布与活性的保持，是研究生物分子电荷传递行为的有效场所。该书引人了一些新的途径和材料购置高生物兼容性的电极界面不仅有助于人们深人认识生物分子的结构与功能之间的关系，而且对于丰富化学修饰电极技术与理论、进一步开发仿生器件都具有重要意义。该书介绍了各类生物兼容性电极的制备新技术和应用实例，是作者近年来从事生物电化学领域研究工作的积累和总结。该书可供大专院校化学、生物等专业高年级本科生、研究生和科研人员参考阅读。     

电解煤浆制氢钛基阳极铂铁合金催化剂的制备及电催化活性研究

将预处理后的钛片作为电极基体, 采用恒电流法沉积Pt和Fe, 通过高温热处理得到Ti/Pt-Fe电极, 通过扫描电镜(SEM)、X射线衍射(XRD)、电子能谱(EDS)以及等离子发射光谱(ICP)等方法对所制备电极表面形貌、组分的合金化程度、催化层成分组成以及电极寿命等进行了表征; 在煤浆电解过程中, 采用两电极体系, 对所制备电极的电催化活性进行了测试. 结果表明: 所制备的电极表面呈层状结构, 且有大量峰形突起, 催化层形成了PtFe合金, 合金化程度较高, 与同面积的铂片电极、Ti/TiO₂Pt-Ru电极相比, 大大提高了电催化活性, 降低了电极成本.     

《生物兼容性电极购置及应用》

具备生物兼容性的电极可改善生物分子在电极界面的有序分布与活性的保持,是研究生物分子电荷传递行为的有效场所。该书引入了一些新的途径和材料购置高生物兼容性的电极界面不仅有助于人们深入认识生物分子的结构与功能之间的关系,而且对于丰富化学修饰电极技术与理论、进一步开发仿生器件都具有重要意义。该书介绍了各类生物兼容性电极的制备新技术和应用实例,是作者近年来从事生物电化学领域研究工作的积累和总结。该书可供大专院校化学、生物等专业高年级本科生、研究生和科研人员参考阅读。该书由清华大学罗国安、王宗花、王义明著,科学…     

用于细胞检测的微电极传感器设计及传感分析

本文针对肿瘤细胞的活性检测、神经细胞的神经递质检测与巨噬细胞等的氧化损伤检测等细胞检测中的核心问题,简要介绍电化学生化传感器和传感方法在细胞检测领域的应用和发展,重点对不同微电极结构的电化学传感器的设计制作、细胞检测方法及应用进展进行了综述。电化学生化传感器从单一检测电极向集成多功能和阵列式电极发展,从单个电极传感检测模式向芯片集成微电极式传感系统发展,而在其生物相容性、检测限和检测效率等方面尚需进一步提升和拓展。基于微机电系统(MEMS)技术制作的微电极研制,电极表面的多种化学和生物修饰的敏感膜研究,从硅基到聚合物柔性基底电极的材料拓展,小体积、植入式、可穿戴式的电化学生化传感器研制等是目前发展的方向,其在临床检验、精准医疗、运动健康监测、老年健康服务等诸多领域中显示出巨大的应用前景。     

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.     

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.