双极制界面电位法测定鲱鱼精dsDNA与联苯胺的结合参

将鲱鱼精dsDNA通过自吸附方式固定在铅笔芯电极(CP)表面制备出DNA/CP.在pH7.38磷酸缓冲溶液(PBS)中,考察联苯胺(BZ)与铅笔芯电极表面鲱鱼精dsDNA相互作用后所导致的DNA/CP零流电位Ezcp变化.结果显示,随着BZ浓度或结合时间的增加,DNA/CP的Ezcp均正移;且当BZ浓度在8.0×10-7～1.0 × 10-5 mol·L-1或结合时间在2～18min内,Ezcp与BZ浓度对数lg[BZ]或结合时间呈正比关系.由此计算出dsDNA与BZ结合反应呈现一级动力学反应方程,其结合比为1∶1,表观结合常数为3.98×106L·mol-1,表观速率常数为2.06×104 s-,半衰期为3.36×10-5s.本方法简单灵敏安全,对拓宽致癌或致毒小分子与DNA作用的研究方法有参考价值.     

Virus crystallography and structural virology: a personal perspective

My first experiences with crystallography were as a graduate student at the University of Glasgow determining the structure of aromatic hydrocarbons using only primitive hand calculation techniques. I had my first experience using electronic computers as a post-doc in the lab of William Lipscomb in Minnesota. That gave me a good preparation for the structure determination of haemoglobin with Max Perutz in Cambridge. The discovery of the conserved globin fold had a major impact on my subsequent activities. It also provided the foundation for the development of the molecular replacement method and non-crystallographic symmetry electron density averaging that was essential for the structure determination of simple icosahedral viruses. The structure determination of a common cold virus was also a major stimulus for the study of more complex viruses and the development of the use of cryo-electron microscopy. This provided the basis for the investigation of lipid-enveloped viruses such as Sindbis virus and dengue virus. It also provided the technology for the study of bacteriophage DNA packaging motors and the mechanisms of infection by tailed and untailed phages.     

Tracing dsDNA Virus–Host Coevolution through Correlation of Their G-Quadruplex-Forming Sequences

The importance of gene expression regulation in viruses based upon G-quadruplex may point to its potential utilization in therapeutic targeting. Here, we present analyses as to the occurrence of putative G-quadruplex-forming sequences (PQS) in all reference viral dsDNA genomes and evaluate their dependence on PQS occurrence in host organisms using the G4Hunter tool. PQS frequencies differ across host taxa without regard to GC content. The overlay of PQS with annotated regions reveals the localization of PQS in specific regions. While abundance in some, such as repeat regions, is shared by all groups, others are unique. There is abundance within introns of Eukaryota-infecting viruses, but depletion of PQS in introns of bacteria-infecting viruses. We reveal a significant positive correlation between PQS frequencies in dsDNA viruses and corresponding hosts from archaea, bacteria, and eukaryotes. A strong relationship between PQS in a virus and its host indicates their close coevolution and evolutionarily reciprocal mimicking of genome organization.     

Model‐Free Rheo‐AFM Probes the Viscoelasticity of Tunable DNA Soft Colloids

Atomic force microscopy rheological measurements (Rheo‐AFM) of the linear viscoelastic properties of single, charged colloids having a star‐like architecture with a hard core and an extended, deformable double‐stranded DNA (dsDNA) corona dispersed in aqueous saline solutions are reported. This is achieved by analyzing indentation and relaxation experiments performed on individual colloidal particles by means of a novel model‐free Fourier transform method that allows a direct evaluation of the frequency‐dependent linear viscoelastic moduli of the system under investigation. The method provides results that are consistent with those obtained via a conventional fitting procedure of the force‐relaxation curves based on a modified Maxwell model. The outcomes show a pronounced softening of the dsDNA colloids, which is described by an exponential decay of both the Young's and the storage modulus as a function of the salt concentration within the dispersing medium. The strong softening is related to a critical reduction of the size of the dsDNA corona, down to ≈70% of its size in a salt‐free solution. This can be correlated to significant topological changes of the dense star‐like polyelectrolyte forming the corona, which are induced by variations in the density profile of the counterions. Similarly, a significant reduction of the stiffness is obtained by increasing the length of the dsDNA chains, which we attribute to a reduction of the DNA density in the outer region of the corona.     

Graphene-DNA hybrid materials: Assembly, applications, and prospects

Among the carbon-based nanomaterials such as carbon nanotubes, fullerenes, graphene and nanodiamonds, graphene received recently widespread attention owing to its exceptional structural, electronic and mechanical properties and potential applications in various domains. However, all currently known forms of graphene materials are not well dispersible or soluble in most common solvents. This limitation deters to explore the chemistry of graphene at the molecular level and its nanobio device applications. One well known solution to this problem is the use of dispersing agents such as polymers, biopolymers, or surfactants in conjunction with the appropriate experimental conditions. Among the various biomolecules, deoxyribonucleic acid (DNA) has emerged as an appealing biomacromolecule for functional materials due to its biocompatibility and renewability in addition to its very interesting double helix structure, which guarantees a range of unique properties that are difficult to detect in other molecules and polymers. Hence, the combination of graphene (a carbon-based nanomaterial), showing exceptional electronic properties, and DNA (a nanostructured biomolecule), having extraordinary recognition properties, demonstrates a new type of nanobio hybrid material. This, in turn, leads to a successful incorporation of the properties of the two different components in new hybrid materials that present important features for potential applications that range from advanced biomedical systems by means of very sensitive electrochemical sensors and biosensors to highly efficient electronics- and optics-based biochips. This article will focus on the recent advancement of the methods available for the chemical functionalization of graphene using DNA by different interactions (covalent or non-covalent and insertion of DNA through graphene nanopore or nanogap), various types of assemblies, and future prospects. Furthermore, the various potential applications of the resulting new nanobio hybrid materials are also highlighted.     

Diallyl sulfides: Selective inhibitors of family X DNA polymerases from garlic (Allium sativum L.)

Diallyl sulfides, organosulfur compounds isolated from garlic (Allium sativum L.), selectively inhibit the activities of mammalian family X DNA polymerases (pols), such as pol β, pol λ and terminal deoxynucleotidyl transferase (TdT), in vitro. The purified fraction (i.e., Sample-A) consisted of diallyl trisulfide, diallyl tetrasulfide and diallyl pentasulfide (molecular ratio: 5.3:3:1). Commercially purchased diallyl sulfides also inhibited the activities of family X pols, and the order of their effect was as follows: Sample-A > diallyl trisulfide > diallyl disulfide > diallyl monosulfide, suggesting that the number of sulfur atoms in the compounds might play an important structural role in enzyme inhibition. The suppression of human cancer cell (promyelocytic leukaemia cell line, HL-60) growth had the same tendency as the inhibition of pol X family among the compounds. Diallyl sulfides were suggested to bind to the pol β-like region of family X pols.     

Size matters: Challenges in imprinting macromolecules

A large number of molecularly imprinted polymers (MIPs) have been investigated and reported over the last decade. Various templates have been successfully exploited and used, leading to significant advances in separation, adsorption, catalysis, sensing, and drug delivery. Among all the templates, small molecules have dominated in the synthesis of MIPs. In contrast, progress made in imprinting macromolecules has been slow, mainly due to the challenges presented by the size, structure and conformational fragility of biological macromolecules. In this review, we focus on discussing some key issues involved in the imprinting of macromolecules from recent publications. The similarity and difference between imprinting small molecules and macromolecules are highlighted. Other aspects relating to polymer design and function are also discussed.     

Electrochemical determination of anticancer drug fulvestrant at dsDNA modified pencil graphite electrode

The interaction of fulvestrant with double-stranded DNA (dsDNA) was studied by means of differential pulse voltammetry (DPV) at dsDNA modified pencil graphite electrode (PGE). The decrease in intensity of the guanine oxidation signals was used as an indicator for the interaction mechanism and sensitive determination of fulvestrant in pH 4.80 acetate buffer (30% ethanol). A linear dependence of the guanine oxidation signals was observed within the range of 1.00–20.00 μg/mL fulvestrant, with a detection limit of 0.41 μg/mL. The determination method was validated according to the standard validation procedure. The proposed method was applied to fulvestrant pharmaceutical dosage form.     

Functionalization of carbon nanomaterials for advanced polymer nanocomposites: A comparison study between CNT and graphene

The allotropes of carbon nanomaterials (carbon nanotubes, graphene) are the most unique and promising substances of the last decade. Due to their nanoscale diameter and high aspect ratio, a small amount of these nanomaterials can produce a dramatic improvement in the properties of their composite materials. Although carbon nanotubes (CNTs) and graphene exhibit numerous extraordinary properties, their reported commercialization is still limited due to their bundle and layer forming behavior. Functionalization of CNTs and graphene is essential for achieving their outstanding mechanical, electrical and biological functions and enhancing their dispersion in polymer matrices. A considerable portion of the recent publications on CNTs and graphene have focused on enhancing their dispersion and solubilization using covalent and non-covalent functionalization methods. This review article collectively introduces a variety of reactions (e.g. click chemistry, radical polymerization, electrochemical polymerization, dendritic polymers, block copolymers, etc.) for functionalization of CNTs and graphene and fabrication of their polymer nanocomposites. A critical comparison between CNTs and graphene has focused on the significance of different functionalization approaches on their composite properties. In particular, the mechanical, electrical, and thermal behaviors of functionalized nanomaterials as well as their importance in the preparation of advanced hybrid materials for structures, solar cells, fuel cells, supercapacitors, drug delivery, etc. have been discussed thoroughly.