聚集诱导发光天然产物:从发现到其多功能应用

来自于天然产物的聚集诱导发光(AIE)材料具有无需化学合成、生物兼容性好、天然可降解、药理活性等优点,正在逐渐成为环境监测、生物成像和疾病诊断等领域的有力工具.本文综述了目前从天然产物中发现的AIE材料,包括黄连素等生物碱、槲皮素等类黄酮多酚、丹宁酸等非类黄酮多酚以及其他皂苷、维生素等天然化合物.这些材料的发光机制主要有分子运动受限(RIM)、扭转分子内电荷转移(TICT)、激发态分子内质子转移(ESIPT)、J-聚集、簇发光(CTE)等.基于显著的AIE特性,这些天然产物表现出在pH、离子及生物标志物传感、细胞成像和生物诊疗等领域的巨大应用潜力.期望本文能够加深对聚集诱导发光现象的理解,启发对来源于天然产物的AIE分子的探索及新应用的开发.     

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...     

天然高分子细胞培养基质的研究进展

天然高分子材料如壳聚糖、丝素蛋白和胶原蛋白等具有异体抗原性弱、生物相容性好、可生物降解且能促进细胞粘附、生长和增殖等优点。同人工合成高分子材料相比,天然高分子几乎不含有机溶剂和引发剂等物质,生物安全性高,是细胞培养基质的首选原材料。近年来,随着生物科技的发展,其新功能也不断被发现并受到学术界的广泛重视。本文综述了天然多糖类和天然蛋白质类高分子材料的理化性质及在细胞培养基质领域中的应用,对目前所存在的一些问题进行了描述并预测其发展动向。     

核蛋白的生物功能及核肽的合成和应用

核蛋白或核肽是一类其侧链羟基通过磷酸二酯键连接到DNA 或RNA 的3′或5′端的天然生物大分子, 具有广泛的生物学效应, 包括DNA 及RNA 的复制、DNA 的转录、插入、缺失和重组等。核肽也指合成的核蛋白结合位点的片断, 作为一种新的工具既可用于研究核蛋白产生生物效应的机理, 又为开发新一类抗病毒、抗肿瘤药物开辟了道路。     

基于天然高分子的导电材料制备及其在柔性传感器件中的应用

天然高分子材料具有来源广泛、化学成分多样、生物相容性和生物降解性良好等优势,是一类绿色可持续再生资源.近年来,基于天然高分子的绿色柔性传感器件研究受到了国内外学者的广泛关注,并取得了长足的进展.本文以天然高分子导电材料为主线,总结了基于天然高分子制备导电材料的模板法和掺杂法.模板法直接以天然高分子材料的天然骨架结构作为基质,而掺杂法以天然高分子材料处理后的产物或衍生物作为基质.归纳了基于天然高分子的柔性导电材料在湿度、温度、应变、气流/气体、光、生物传感器件中应用的研究进展,最后展望了基于天然高分子的柔性导电材料在设计和组装柔性传感器方面的前景,为高效发展绿色柔性电子和天然高分子材料的高值化利用提供新思路.     

仿生矿化增强材料

近年来,随着材料科学领域的发展,机械性能优异且具有特定功能的有机-无机复合材料成为了研究热点。而天然的生物矿化过程产生了在自然界中分布广泛、结构特征多样性、机械性能优异的天然生物矿物,比如牙齿、骨骼、珍珠、贝壳、海胆刺、海洋红虫颚等。这些天然复合增强材料中的矿化组织结构特点和矿化机理为仿生设计与合成具有特定结构、特定功能和优异机械性能的材料提供了理论依据。通过模拟天然过程的仿生矿化方法,利用有机基质调控无机矿物成核生长为固态矿物,最终能够定向组装具有特定有序结构和先进功能的有机-无机复合材料。本文主要综述了自然界中通过生物矿化过程得到的高强度、高韧性的天然复合增强材料,以及受生物矿化增强现象的启发,在化学与材料仿生矿化合成中出现的一些有机-无机复合的增强材料。     

手性组装材料及其在对映体分离中的应用

手性组装材料作为一种新型功能复合材料,已经引起众多科学研究领域的广泛关注,尤其是其在对映体分离方面的潜在应用成为当前的研究热点。本文首先从手性来源角度对手性组装材料的构建机制进行了分类探讨,包括手性诱导、手性放大、手性传递和手性转录4个主要途径,其中具有手性的多孔金属有机骨架、纳米笼是基于手性诱导和手性传递机制构建的组装材料,手性凝胶的形成是基于手性放大机制,而手性转录机制主要用于手性多孔无机材料、螺旋纳米结构的构建。其次,介绍了手性组装材料的对映体识别功能,主要针对金属有机骨架化合物(MOFs)、手性凝胶和纳米笼三类手性组装材料在对映体分离中的应用进行了综述。阐述了天然生物大分子DNA的手性自组装特性及其对对映体的立体选择性识别功能,并介绍了DNA螺旋组装结构在手性等离子材料、非对称催化剂设计等方面的应用。最后,归纳了金属有机骨架化合物、手性凝胶、纳米笼和DNA等手性组装材料各自的优势,并对DNA在手性拆分领域的应用前景进行了展望。     

天然高分子材料水凝胶的制备及其应用进展

水凝胶是一种由高分子聚合物构成的三维网络材料,用自然界中天然存在的高聚物及其衍生物材料构建水凝胶,具有生物相容性、环境敏感性高、生物可降解性和对环境无污染等优势。本文介绍了近几年天然高分子水凝胶材料在医药卫生、食品、农业和环保等领域的应用情况;并按材料来源的不同,分类综述了蛋白质、多肽类水凝胶,海藻多糖水凝胶,动物多糖水凝胶,植物多糖水凝胶,其改性和制备复合水凝胶的最新技术、功能特性以及应用领域;最后对天然高分子水凝胶制备的改进方向和重点应用领域进行了展望。     

DNA原位自组装用于细胞荧光成像分析研究

DNA自组装由于其低毒性、高生物相容性和内置特性,在生物传感、药物递送和临床治疗中发挥着越来越重要的作用.与大多数天然聚合物或合成纤维相比,这些DNA分子相对坚固,可通过序列变异进行修饰.作为侧链连接到聚合物上形成的二级结构赋予DNA结构可设计的响应特性,如对金属离子、蛋白质、pH、DNA、RNA和其他一些小信号分子(...     

废弃天然高分子基功能材料

从废弃高分子角度对废弃生物质的高附加值再利用进行综述,阐述了废弃生物质中天然高分子的类型以及废弃生物质中包含的大量天然高分子具有官能团丰富、可降解、生物相容、无毒无害等优异的性能,归纳了废弃生物质的传统处理方法及作为材料使用的再利用途径,介绍了废弃天然高分子用作复合材料、吸附材料、载体材料、能源材料、医用高分子材料、智能高分子材料等的研究进展,并对废弃天然高分子的资源化利用进行了展望。     

4-硫脱氧胸苷及类似物在UVA光辅助治疗抗癌药物方面的研究

本文叙述了含硫碱基DNA的化学和医疗应用。硫碱基（Thio-base）有其独特的性质,比如,易烷基化,易氧化和强的紫外长波(400-315 nm,UVA)吸收。这些特定化学和物理性质存于含硫碱基、含硫核苷和含硫碱基DNA中,它们对制备修饰的DNA和对硫碱基的DNA与其它生物大分子之间进行光诱导的交联反应是非常有用的。功能化的含有硫碱基的DNA及其类似物可用于对DNA的修复的研究。本文也介绍和评述了利用紫外光/含硫脱氧胸（腺嘧啶脱氧核）苷（UVA/Thiothymidine）的抗癌疗法,同时,探讨了含硫核苷类似物和紫外线光之间的协同作用,为癌症和其它疾病治疗提供一种新的方法。     

One‐electron redox properties of DNA nucleobases and common tautomers

The redox properties of DNA play an influential role in several important processes such as DNA mutation and the interaction of DNA with drugs. Structural changes in DNA nucleobases from its canonical form to its tautomeric forms can alter these properties and may lead to DNA mutation due to altered base‐pairing properties. Experimental results for the standard value of DNA redox properties vary due to choice of methodology and solvent. Theoretical determination of these properties is helpful in pinpointing standard values but still vary depending on methodology and chosen experimental benchmark. However, it is of importance to identify the overall trend of electron mobility within DNA while providing reliable standard values for redox reactions. In this work, we present the results of theoretical calculations for redox properties. Using the thermodynamic cycle, we can approximate reliable values. We report the electron affinities, ionization potentials, and redox potential for the canonical DNA nucleobases and their rare tautomers. For each of these properties, we evaluate its overall trend to gain a greater understanding of the role that electron attachment and electron mobility have within the DNA strand. All calculations are computed at the M06‐2X/6–31++G(d,p) level of theory. © 2014 Wiley Periodicals, Inc.     

Direct Sensing of 5‐Methylcytosine by Polymerase Chain Reaction

The epigenetic control of genes by the methylation of cytosine resulting in 5‐methylcytosine (5mC) has fundamental implications for human development and disease. Analysis of alterations in DNA methylation patterns is an emerging tool for cancer diagnostics and prognostics. Here we report that two thermostable DNA polymerases, namely the DNA polymerase KlenTaq derived from Thermus aquaticus and the KOD DNA polymerase from Thermococcus kodakaraensis, are able to extend 3′‐mismatched primer strands more efficiently from 5 mC than from unmethylated C. This feature was advanced by generating a DNA polymerase mutant with further improved 5mC/C discrimination properties and its successful application in a novel methylation‐specific PCR approach directly from untreated human genomic DNA.     

Adsorption of DNA onto gold nanoparticles and graphene oxide: surface science and applications

The interaction between DNA and inorganic surfaces has attracted intense research interest, as a detailed understanding of adsorption and desorption is required for DNA microarray optimization, biosensor development, and nanoparticle functionalization. One of the most commonly studied surfaces is gold due to its unique optical and electric properties. Through various surface science tools, it was found that thiolated DNA can interact with gold not only via the thiol group but also through the DNA bases. Most of the previous work has been performed with planar gold surfaces. However, knowledge gained from planar gold may not be directly applicable to gold nanoparticles (AuNPs) for several reasons. First, DNA adsorption affinity is a function of AuNP size. Second, DNA may interact with AuNPs differently due to the high curvature. Finally, the colloidal stability of AuNPs confines salt concentration, whereas there is no such limit for planar gold. In addition to gold, graphene oxide (GO) has emerged as a new material for interfacing with DNA. GO and AuNPs share many similar properties for DNA adsorption; both have negatively charged surfaces but can still strongly adsorb DNA, and both are excellent fluorescence quenchers. Similar analytical and biomedical applications have been demonstrated with these two surfaces. The nature of the attractive force however, is different for each of these. DNA adsorption on AuNPs occurs via specific chemical interactions but adsorption on GO occurs via aromatic stacking and hydrophobic interactions. Herein, we summarize the recent developments in studying non-thiolated DNA adsorption and desorption as a function of salt, pH, temperature and DNA secondary structures. Potential future directions and applications are also discussed.     

DNA Nanotechnology-based Biocomputing

With silicon-based microelectronic technology pushed to its limit,scientists hunt to exploit biomolecules to power the bio-computer as substitutes.As a typical biomolecule,DNA now has been employed as a tool to create computing systems because of its superior parallel computing ability and outstanding data storage capability.However,the key challenges in this area lie in the human intervention during the computation process and the lack of platforms for central processor.DNA nanotechnology has created hundreds of complex and hierarchical DNA nanostructures with highly controllable motions by exploiting the unparalleled self-recognition properties of DNA molecule.These DNA nanostructures can provide platforms for central processor and reduce the human intervention during the computation process,which can offer unprecedented opportunities for biocomputing.In this review,recent advances in DNA nanotechnology are briefly summarized and the newly emerging concept of biocomputing with DNA nanostructures is introduced.     

Rapid Synthesis of Propargyl-γ-Modified Peptide Nucleic Acid Monomers for Late-Stage Functionalization of Oligomers

The exceptional hybridization properties of peptide nucleic acids (PNAs) coupled with the ease of their synthesis has made this artificial nucleic acid mimetic a desirable platform for diagnostics, therapeutics and supramolecular engineering. PNA backbone modifications have been extensively explored to finetune physicochemical properties and for conjugation of functional molecules. Here, we detail the synthesis of a universal γ-propargyl-PNA backbone from serine, and its acylation with the four DNA canonical nucleobases. The availability of serine as d or l enantiomer provide simple accesses to PNA oligomers for hybridization with natural oligonucleotides or for orthogonal hybridization circuitry. We show that late-stage conjugation enables optimization of the physicochemical properties. This approach is appealing due to its orthogonality to Fmoc-SPPS, its flexibility and ease for introducing diversity by on-resin copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC). We exemplified the utility of these novel monomers with PNA based hybridization chain reactions (HCRs).     

Chemical synthesis of cross-link lesions found in nitrous acid treated DNA: a general method for the preparation of N2-substituted 2'-deoxyguanosines

Treatment of DNA with nitrous acid results in the formation of DNA-DNA cross-links. Two cross-link lesions have previously been isolated and their structures assigned based on spectroscopic data. The major lesion has been proposed to consist of two deoxyguanosine (dG) nucleosides sharing a common N2 atom (1), while the structure of the minor lesion has been proposed to consist of a common nitrogen atom linking C2 of a dG nucleoside to C6 of deoxyadenosine (2). The chemical synthesis of 1 and 2, utilizing a palladium-catalyzed coupling, is described herein. It is demonstrated that the spectroscopic properties of synthetic 1 are identical to that of lesion 1 obtained from nitrous acid cross-linked DNA, thus providing a proof of its structure. Comparison of the limited spectroscopic data available for lesion 2 originating from nitrous acid cross-linked DNA to synthetic 2 supports its structural assignment. The synthetic approach used for synthesis of 1 and 2 is shown to be a general method for the preparation of a variety of N2-substituted dG nucleosides in good yields.     

DNA nanostructure-based nucleic acid probes: construction and biological applications

In recent years, DNA has been widely noted as a kind of material that can be used to construct building blocks for biosensing, in vivo imaging, drug development, and disease therapy because of its advantages of good biocompatibility and programmable properties. However, traditional DNA-based sensing processes are mostly achieved by random diffusion of free DNA probes, which were restricted by limited dynamics and relatively low efficiency. Moreover, in the application of biosystems, single-stranded DNA probes face challenges such as being difficult to internalize into cells and being easily decomposed in the cellular microenvironment. To overcome the above limitations, DNA nanostructure-based probes have attracted intense attention. This kind of probe showed a series of advantages compared to the conventional ones, including increased biostability, enhanced cell internalization efficiency, accelerated reaction rate, and amplified signal output, and thus improved in vitro and in vivo applications. Therefore, reviewing and summarizing the important roles of DNA nanostructures in improving biosensor design is very necessary for the development of DNA nanotechnology and its applications in biology and pharmacology. In this perspective, DNA nanostructure-based probes are reviewed and summarized from several aspects: probe classification according to the dimensions of DNA nanostructures (one, two, and three-dimensional nanostructures), the common connection modes between nucleic acid probes and DNA nanostructures, and the most important advantages of DNA self-assembled nanostructures in the applications of biosensing, imaging analysis, cell assembly, cell capture, and theranostics. Finally, the challenges and prospects for the future development of DNA nanostructure-based nucleic acid probes are also discussed.

In recent years, DNA has been widely noted as a kind of material that can be used to construct building blocks for biosensing, in vivo imaging, drug development, and disease therapy because of its advantages of good biocompatibility and programmable properties.     

Synthesis, characterization, DNA binding and cleavage properties and anticancer studies of ruthenium(III) Schiff base complexes

A Schiff base (HL) has been synthesized and characterized by physico-chemical, spectroscopic and X-ray crystallography studies. Three of its Ru(III) complexes were synthesized and characterized by analytical and spectroscopic studies. The DNA binding properties of HL and its Ru(III) complexes have been investigated by electronic absorption spectroscopy. Also, HL and its Ru(III) complex [RuCl₂(AsPh₃)L] were tested for DNA cleavage properties. The results showed that the complex cleaves DNA more rapidly than the free ligand. Further, an in vitro study of the cytotoxicity of HL and the complex [RuCl₂(AsPh₃)L] was carried out.