程序自组装DNA纳米花封装酶分子用于光热法检测循环肿瘤细胞

DNA纳米技术在生物传感领域引起人们广泛的研究兴趣,现已构建多种二维和三维DNA功能纳米结构.滚环扩增(RCA)作为一种等温扩增技术,为DNA纳米材料的设计和自组装提供了新途径.该文通过RCA一锅法合成封装有辣根过氧化物酶(HRP)的DNA纳米花(HRP@DNFs),进一步基于双核酸适体识别构建光热生物传感器,用于肝细...     

DNA纳米技术研究进展

DNA不只是遗传物质,还能通过折叠形成特定的二维、三维结构,作为一种天然纳米材料可参与各种功能结构和纳米器件的构造。DNA纳米技术从被提出到现在的三十多年间,得到了飞速发展,被应用于众多领域,对纳米科学产生了重大影响。本文将主要从三种典型的DNA纳米结构和DNA纳米技术的应用两个方面进行综述,并对DNA纳米技术的前景进行展望。     

基于DNA纳米结构的分子间相互作用研究

研究生物分子间的相互作用是研究生命本质过程中必不可少的环节.近年来,DNA纳米技术在分子间相互作用的研究中发挥了重要作用,取得了一系列进展. DNA纳米结构具有高度的可编程性和可寻址性,可以利用这些性质采取不同的方式将待测体系修饰在DNA纳米结构上,而且可以精确控制分子的排布、种类、数目等,因此可以作为研究分子间相互作用的模板.在此基础上结合单分子技术,如单分子荧光成像(SMF)、原子力显微术等(AFM),可以实现对单个分子的行为观测.本文首先简述了DNA纳米结构作为研究平台的构建,然后对DNA纳米结构在研究分子间相互作用中的应用进行了阐述,包括用作锚定平台、提供具有一定机械性能的支架以及提供纳米级的微环境,最后对DNA纳米技术的发展进行了总结与展望.     

基于核酸框架的分子机器

分子机器是一种由分子构建的微型设备,在受到适当的刺激如光、温度、pH或电磁场时,它能够在分子水平上执行类似宏观机器的机械运动.然而,分子机器的研究仍面临着许多技术挑战,包括如何精确控制分子机器的运动,如何构建大规模的分子机器系统等.作为有潜力的分子自组装技术,利用DNA纳米技术可以构建复杂的刺激响应纳米机器并精确调控其在分子水平的运动.本文中,我们简单介绍了DNA纳米技术的组装原理,综述了响应DNA链置换、光、热、pH和电场等不同类型刺激的核酸框架分子机器,并探讨了它们在药物递送、构建三维等离子体光学器件以及作为生物分子标尺等方面的应用.     

DNA纳米结构的生物安全性研究

DNA纳米结构的生物安全性研究对于其在生命科学领域的应用具有重要的意义.本文首先简单介绍了DNA纳米技术的发展以及DNA纳米结构的特点,重点分体外细胞和体内动物两个层次,综述了近年来DNA纳米结构的生物安全性研究进展,并对该领域未来的研究方向进行了展望.     

结构DNA纳米技术应用新进展

DNA具有非凡的分子识别性能和显著的结构特征,这使得它在材料的纳米级调控方面具有独特的优越性,在许多领域也展现出广阔的应用前景。本文从模块化DNA自组装和DNA折纸术两个方面综述了近些年DNA纳米技术,包括近年来DNA纳米技术中比较新型的组装方法;并从DNA纳米结构作为模板定位纳米粒子和蛋白以及用于生物医药等方面介绍了DNA纳米技术的应用;同时,对DNA纳米技术发展及应用进行了展望。     

DNA纳米机器

本文介绍了以DNA为基础的纳米机器的发展现状,强调了核酸作为一种材料在纳米科技领域的重要作用.着重阐述了利用链交换反应或环境因素变化可以驱动DNA二级结构的变化,从而可以构建出形式多样的纳米级核酸分子机器;评价了各类分子机器在效率、寿命和副产物方面的优缺点.在总结前人工作的基础上预测了核酸纳米技术在生命科学、材料科学以及计算科学等诸多方面可能的应用.     

DNA自组装结构在纳米诊疗中的应用

DNA分子具有良好的生物相容性和可编程性,被广泛用于构建新型纳米生物材料.研究者利用DNA纳米技术已构建了尺寸、形貌及对称性精确可控且可对环境条件做出特异性响应的DNA自组装结构,它们在生物成像及检测、药物的精准输送等纳米诊疗领域有着极大的应用潜力.然而, DNA纳米材料应用于活体系统存在稳定性不足、细胞摄取效率不高以及药物的包裹及可控释放程度不够等问题.本文简述了DNA自组装结构的构建方法以及将这些结构用于生物成像、生物检测和药物载带方面的进展,概括了提高DNA自组装结构体内稳定性及细胞摄取效率的方法,最后讨论了DNA自组装结构应用于纳米诊疗中所面临的机遇与尚待解决的问题.     

基于新型纳米传感材料的DNA生物传感器的应用

DNA是构建纳米技术和生物传感技术新设备的良好构建体。DNA生物传感器由于具有灵敏度高、选择性好等特点,近年来获得了飞速发展。研究发现,金属纳米粒子(MNPs)、碳基纳米材料等一系列纳米材料在传感器设计中提高了电化学DNA传感器的传感性能。本文侧重介绍了场效应晶体管、石墨烯、碳纳米管等新型纳米传感材料,以及基于这些材料的DNA生物传感器的最新进展,最后展望了DNA生物传感器的应用前景。     

DNA折纸术纳米反应器

基于DNA折纸技术,构建具有纳米尺度可寻址的新型DNA纳米反应器,是DNA纳米技术领域的一个最新研究思路和方向。它的优势首先在于其纳米定位能力,通过不同的化学或生物相互作用,已能够实现对包括化学小分子、生物大分子及人工纳米材料等的纳米级精确定位;其次,DNA折纸结构的丰富多样性,使构建纳米级仿生限域环境成为了可能;此外,DNA折纸结构本身的生物相容性及优良的产率,也保证了这一材料的可应用性。本文首先介绍了在DNA折纸结构上,对不同材料和分子进行纳米定位的一般方法和最新进展。然后,着重阐述了基于纳米定位技术,以DNA折纸结构作为纳米反应器,对一些化学、生化反应的成功调控。最后,基于现有的工作基础,我们提出了DNA折纸术纳米反应器概念在未来的发展方向及应用前景展望。     

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.