Photoactive Nanostructures of Polypyrrole

The creation of nanostructures of the photoactive polymer polypyrrole (PPy) on glass substrates with the spin‐coating method is described. No additional post‐production treatment is necessary to obtain uniformly distributed photoactive nanostructures on macroscopically scaled substrates. Based on X‐ray reflectivity measurements, the critical solution concentration of PPy below which these nanostructures develop is determined. The PPy nanostructures are displayed with atomic force microscopy (AFM) measurements, which prove that the nanostructures form directly on the substrate. With UV/Vis spectroscopy the absorption behavior of the nanostructures is probed in comparison to PPy films and PPy solutions. A linear dependence of the absorption of the nanostructure on the surface coverage measured with AFM is detected. The influence of confinement on the conjugation length results in a modified absorption behavior of the nanostructures.     

Magnesium-Free Immobilization of DNA Origami Nanostructures at Mica Surfaces for Atomic Force Microscopy

DNA origami nanostructures (DONs) are promising substrates for the single-molecule investigation of biomolecular reactions and dynamics by in situ atomic force microscopy (AFM). For this, they are typically immobilized on mica substrates by adding millimolar concentrations of Mg²⁺ ions to the sample solution, which enable the adsorption of the negatively charged DONs at the like-charged mica surface. These non-physiological Mg²⁺ concentrations, however, present a serious limitation in such experiments as they may interfere with the reactions and processes under investigation. Therefore, we here evaluate three approaches to efficiently immobilize DONs at mica surfaces under essentially Mg²⁺-free conditions. These approaches rely on the pre-adsorption of different multivalent cations, i.e., Ni²⁺, poly-l-lysine (PLL), and spermidine (Spdn). DON adsorption is studied in phosphate-buffered saline (PBS) and pure water. In general, Ni²⁺ shows the worst performance with heavily deformed DONs. For 2D DON triangles, adsorption at PLL- and in particular Spdn-modified mica may outperform even Mg²⁺-mediated adsorption in terms of surface coverage, depending on the employed solution. For 3D six-helix bundles, less pronounced differences between the individual strategies are observed. Our results provide some general guidance for the immobilization of DONs at mica surfaces under Mg²⁺-free conditions and may aid future in situ AFM studies.     

On the Stability of DNA Origami Nanostructures in Low‐Magnesium Buffers

DNA origami structures have great potential as functional platforms in various biomedical applications. Many applications, however, are incompatible with the high Mg²⁺ concentrations commonly believed to be a prerequisite for maintaining DNA origami integrity. Herein, we investigate DNA origami stability in low‐Mg²⁺ buffers. DNA origami stability is found to crucially depend on the availability of residual Mg²⁺ ions for screening electrostatic repulsion. The presence of EDTA and phosphate ions may thus facilitate DNA origami denaturation by displacing Mg²⁺ ions from the DNA backbone and reducing the strength of the Mg²⁺–DNA interaction, respectively. Most remarkably, these buffer dependencies are affected by DNA origami superstructure. However, by rationally selecting buffer components and considering superstructure‐dependent effects, the structural integrity of a given DNA origami nanostructure can be maintained in conventional buffers even at Mg²⁺ concentrations in the low‐micromolar range.     

DNA Nanostructures for Targeted Antimicrobial Delivery

We report the use of DNA origami nanostructures, functionalized with aptamers, as a vehicle for delivering the antibacterial enzyme lysozyme in a specific and efficient manner. We test the system against Gram‐positive (Bacillus subtilis) and Gram‐negative (Escherichia coli) targets. We use direct stochastic optical reconstruction microscopy (dSTORM) and atomic force microscopy (AFM) to characterize the DNA origami nanostructures and structured illumination microscopy (SIM) to assess the binding of the origami to the bacteria. We show that treatment with lysozyme‐functionalized origami slows bacterial growth more effectively than treatment with free lysozyme. Our study introduces DNA origami as a tool in the fight against antibiotic resistance, and our results demonstrate the specificity and efficiency of the nanostructure as a drug delivery vehicle.     

Microscopic Visualization of Nanostructures of Cellulose Derivatives

Microscopy has proved to be a valuable tool for the investigation of supermolecular structures of cellulose derivatives. Thus, with AFM it was possible to show that statistically functionalized derivatives (degree of substitution below 3) form specific aggregates called fringed micelles. In contrast, derivatives with a non-statistic distribution exhibit a more network-like structure as known for galactomannans consisting of block-like structures. If samples are prepared by deposition of dilute solutions of polyelectrolytes on mica and drying at elevated temperature, the formation of nanorings is observed. In addition, AFM and REM were applied to investigate the morphology of membranes prepared of cellulose esters with unsaturated substituents. It was shown that cross-linking of the polymer chains in the membranes does not lead to a change in the nanostructure of the surface, i.g., the surface roughness and the pore sizes were not modified.     

A Case Study of the Likes and Dislikes of DNA and RNA in Self‐Assembly

Programmed self‐assembly of nucleic acids (DNA and RNA) is an active research area as it promises a general approach for nanoconstruction. Whereas DNA self‐assembly has been extensively studied, RNA self‐assembly lags much behind. One strategy to boost RNA self‐assembly is to adapt the methods of DNA self‐assembly for RNA self‐assembly because of the chemical and structural similarities of DNA and RNA. However, these two types of molecules are still significantly different. To enable the rational design of RNA self‐assembly, a thorough examination of their likes and dislikes in programmed self‐assembly is needed. The current work begins to address this task. It was found that similar, two‐stranded motifs of RNA and DNA lead to similar, but clearly different nanostructures.     

Chemically Modified Carbon Nanotubes for Use in Electroanalysis

The discovery of carbon nanotubes has had a profound impact on many areas of science and technology, not least that of electroanalysis. The properties and applications of carbon nanotubes themselves have been well reviewed in the literature and a number of reviews with an electrochemical emphasis have been published. However, the modification of carbon nanotubes has recently been the focus of much research, primarily to improve their solubility in various solvents. Yet modified carbon nanotube electrodes also allow the electrochemist to tailor the properties of the carbon nanotubes, or the electrode surface to impart desired properties such as enhanced sensing capabilities. In this review we attempt to comprehensively cover the different chemical and electrochemical modification strategies and research carried out using modified carbon nanotubes for electroanalytical and bioanalytical applications. Furthermore we also discuss the use of modified carbon nanotubes in electrocatalysis and biocatalysis from an analytical aspect, as well as seeking to dispel some of the myths surrounding the “electrocatalytic” properties of carbon nanotubes.     

化学改性环氧树脂水基涂料的研究-涂膜性能

化学改性环氧树脂水基涂料的研究-涂膜性能     

Characterization of chemical heterogeneity in polymer systems using hydrolysis and tapping‐mode atomic force microscopy

Characterization of polymer coatings microstructure is critical to the fundamental understanding of the corrosion of coated metals. An approach for mapping the chemical heterogeneity of a polymer system using chemical modification and tapping‐mode atomic force microscopy (TMAFM) is demonstrated. This approach is based on the selective degradation of one of the phases in a multiphase polymer blend system and the ability of TMAFM to provide nanoscale lateral information about the different phases in the polymer system. Films made of a 70:30 polyethyl acrylate/polystyrene (PEA/PS) blend were exposed to a hydrolytic acidic environment and analyzed using TMAFM. Pits were observed to form in the PEA/PS blend films, and this degradation behavior was similar to that of the PEA material. Using these results, the domains in the 70:30 blend were identified as the PS‐rich regions and the matrix as the PEA‐rich region. This conclusion was confirmed by Fourier transform infrared‐attenuated total reflection analyses that revealed the hydrolysis of the PEA material. TMAFM phase imaging was also used to follow pit growth of the blend as a function of exposure time. The usefulness of the chemical modification/AFM imaging approach in understanding the degradation process of a coating film is discussed. © 2001 John Wiley & Sons, Inc. J Polym Sci B Part B: Polym Phys 39: 1460–1470, 2001     

Helical DNA Origami Tubular Structures with Various Sizes and Arrangements

We developed a novel method to design various helical tubular structures using the DNA origami method. The size‐controlled tubular structures which have 192, 256, and 320 base pairs for one turn of the tube were designed and prepared. We observed the formation of the expected short tubes and unexpected long ones. Detailed analyses of the surface patterns of the tubes showed that the short tubes had mainly a left‐handed helical structure. The long tubes mainly formed a right‐handed helical structure and extended to the directions of the double helical axes as structural isomers of the short tubes. The folding pathways of the tubes were estimated by analyzing the proportions of short and long tubes obtained at different annealing conditions. Depending on the number of base pairs involved in one turn of the tube, the population of left‐/right‐handed and short/long tubes changed. The bending stress caused by the stiffness of the bundled double helices and the non‐natural helical pitch determine the structural variety of the tubes.     

化学修饰铋膜电极的制备和应用研究进展

本文综述了近年来化学修饰铋膜电极的制备和应用的研究进展。首先介绍了铋膜电极的制备方法,然后介绍铋膜电极的应用和研究进展,包括铋膜电极在检测重金属离子、硝基酚类化合物、药物、杀虫剂及一些生物活性物质等方面的应用。     

Single‐Molecule Mechanochemical Sensing Using DNA Origami Nanostructures

While single‐molecule sensing offers the ultimate detection limit, its throughput is often restricted as sensing events are carried out one at a time in most cases. 2D and 3D DNA origami nanostructures are used as expanded single‐molecule platforms in a new mechanochemical sensing strategy. As a proof of concept, six sensing probes are incorporated in a 7‐tile DNA origami nanoassembly, wherein binding of a target molecule to any of these probes leads to mechanochemical rearrangement of the origami nanostructure, which is monitored in real time by optical tweezers. Using these platforms, 10 pM platelet‐derived growth factor (PDGF) are detected within 10 minutes, while demonstrating multiplex sensing of the PDGF and a target DNA in the same solution. By tapping into the rapid development of versatile DNA origami nanostructures, this mechanochemical platform is anticipated to offer a long sought solution for single‐molecule sensing with improved throughput.     

利用化学修饰的细菌视紫红质薄膜进行光学信息存储的研究

细菌视紫红质(bacteriorhodopsin,bR)具有独特的光、化学和热稳定性.bR光循环中间态M态的最大吸收峰相对于始态明显地发生蓝移,所以基于bR(→)M的光致变色模型可以为光学应用尤其是信息存储提供一个机制.但是野生型bR 中M态的寿命很短,不适合用来进行信息存储.本文采用化学添加剂的方法,将bR/聚乙烯醇(PVA)薄膜的中间态M态的寿命显著延长.用此化学修饰的bR薄膜作为记录介质进行缩微图像存储,所得到的图像具有较高的对比度和较长的保存时间.此实验首次实现了在化学修饰的bR薄膜上基于bR始态和中间态M态的双稳态模型在光学信息存储上的应用.     

Study on Antibacterial Activity and Structure of Chemically Modified Lysozyme

Lysozyme is a natural protein with a good bacteriostatic effect, but its poor inhibition of Gram-negative bacteria limits its development potential as a natural preservative. Therefore, the modification of natural lysozyme to expand the antimicrobial spectrum become the focus of lysozyme study. Egg white lysozyme has low cost, rich content in nature, is easy to obtain, strong stability, and high enzyme activity, so it can be applied in the modification of lysozyme. Egg white lysozyme was modified by chemical methods using organic acids. Caffeic acid and p-coumaric acid in organic acids were used as modifiers, and 1-Ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxy succinimide were used as dehydration condensation agents during modification. A certain degree of modified lysozyme was obtained through appropriate modification conditions. The antibacterial properties and structure of the obtained two organic acid-modified lysozymes were compared with natural enzymes. The results showed that compared with the native enzyme, the activity of modified lysozyme decreased, but the inhibitory effect on Gram-negative bacteria was enhanced. The minimum inhibitory concentrations of caffeic acid-modified enzyme and p-coumaric acid-modified enzyme on Escherichia coli and Pseudomonas aeruginosa were 0.5 mg/mL and 0.75 mg/mL, respectively. However, the antibacterial ability of modified lysozyme to Gram-positive bacteria was lower than that of the natural enzyme. The minimum inhibitory concentration of caffeic acid-modified enzyme and p-coumaric acid-modified enzyme to Staphylococcus aureus and Bacillus subtilis was 1.25 mg/mL. The peak fitting results of the amide-I band absorption peak in the infrared spectroscopy showed that the content of the secondary structure of the two modified enzymes obtained after modification was different from that of natural enzymes. In the study, two organic acids were used to modify egg white lysozyme, which enhanced the enzyme’s inhibition of Gram-negative bacteria, and analyzed the mechanisms for the change in the enzyme’s antibacterial ability from the perspective of the structural change of the modified enzyme, providing a new idea for lysozyme modification.     

Computer‐Aided Production of Scaffolded DNA Nanostructures from Flat Sheet Meshes

The use of DNA as a nanoscale construction material has been a rapidly developing field since the 1980s, in particular since the introduction of scaffolded DNA origami in 2006. Although software is available for DNA origami design, the user is generally limited to architectures where finding the scaffold path through the object is trivial. Herein, we demonstrate the automated conversion of arbitrary two‐dimensional sheets in the form of digital meshes into scaffolded DNA nanostructures. We investigate the properties of DNA meshes based on three different internal frameworks in standard folding buffer and physiological salt buffers. We then employ the triangulated internal framework and produce four 2D structures with complex outlines and internal features. We demonstrate that this highly automated technique is capable of producing complex DNA nanostructures that fold with high yield to their programmed configurations, covering around 70 % more surface area than classic origami flat sheets.