Photobioelectronic studies with thylakoid membranes

The research described in this paper presents a method for chemically modifying the surface of plant photosynthetic membranes in such a way that electrical contact can be made. Colloidal platinum was prepared, precipitated directly onto thylakoid membranes from aqueous solution, and entrapped on fiberglass filter paper. This composition of matter was capable of sustained simultaneous photoevolution of hydrogen and oxygen when irradiated at any wavelength (400–700 nm) in the chlorophyll absorption spectrum. Experimental data support the interpretation that part of the platinum metal catalyst is precipitated adjacent to the photosystem-I reduction site of photosynthesis and that electron transfer occurs across the interface between photosystem I and the catalyst. When contacted with metal electrodes, the thylakoid-platinum combination was capable of generating a sustained flow of current through an external load resistor. Procedures for preparing this material and experimental data on its catalytic and electronic properties are presented. Also presented is an analysis of the flow of photocurrent in terms of the interfacial electron transfer reactions that occur at the interfaces of the components of the assembly.     

Recent Progress on Highly Selective and Sensitive Electrochemical Aptamer-based Sensors

Highly selective, sensitive, and stable biosensors are essential for the molecular level understanding of many physiological activities and diseases. Electrochemical aptamer-based (E-AB) sensor is an appealing platform for measurement in biological system, attributing to the combined advantages of high selectivity of the aptamer and high sensitivity of electrochemical analysis. This review summarizes the latest development of E-AB sensors, focuses on the modification strategies used in the fabrication of sensors and the sensing strategies for analytes of different sizes in biological system, and then looks forward to the challenges and prospects of the future development of electrochemical aptamer-based sensors.     

Spatiotemporal organization of coacervate microdroplets

Liquid–liquid phase separation (LLPS) has emerged as a new paradigm in the fields of soft matter, colloid chemistry, prebiotic chemistry, and cell biology. As phase separation is a dynamic assembly process, how to spatiotemporally regulate the assembly and disassembly of these micrometre-sized droplets, which are referred as biomolecular condensates in biology is essential for their diverse applications in various disciplines. Herein, we discuss recent advances in the spatiotemporal control of phase separation using different physical tools and external environmental stimuli in bulk solutions and living cells. Specifically, the exploration of phase transition in a compartmentalized protocellular system, which can bridge the gap between synthetic and intracellular LLPS systems, is summarized, and the challenges and future research directions are discussed.     

红外光谱法检测生物大分子损伤的研究进展

红外光谱技术由于其灵敏度高和对样品的非破坏性等优点已成为研究生物大分子损伤的重要工具。蛋白质、脂质和核酸等受到损伤时,其红外光谱特征吸收峰的峰位、峰型和峰强会发生变化,这为检测生物大分子损伤并进一步揭示相关疾病的发生、发展及早期预防提供了依据。还综述了近年来使用红外光谱法检测生物大分子损伤的研究进展,介绍了利用傅里叶变换红外光谱、衰减全反射傅里叶变换红外光谱和傅里叶红外显微等技术在蛋白质二级结构、膜脂流动性和离子通透性以及药物对DNA的作用机制等领域的应用,以及相关的定性和定量分析方法进行了评述,提出了目前红外光谱分析技术中存在的问题,并对今后红外光谱在生物医学领域中的应用前景作了展望,指出疾病早期诊断、红外光谱联用以及定量分析技术等将成为红外光谱领域未来的研究热点。     

组装阵列中耦联剂对表面增强拉曼光谱的影响

利用自组装技术,将不同浓度比例的对巯基苯胺和N,N'-二苯基硫脲为功能耦联分子,在光滑银基底表面组装不同表面密度的二维银纳米粒子阵列。通过对组装阵列和粗糙银表面耦联剂分子的表面增强拉曼光谱比较,阵列中对巯基苯胺分子拉曼信号得到了明显的增强,但只有微弱的N,N'-二苯基硫脲的拉曼增强信号,说明在这种组装阵列中得到的拉曼散射增强主要来自于银纳米粒子和光滑银表面之间。     

Differential geometry based solvation model I: Eulerian formulation

This paper presents a differential geometry based model for the analysis and computation of the equilibrium property of solvation. Differential geometry theory of surfaces is utilized to define and construct smooth interfaces with good stability and differentiability for use in characterizing the solvent-solute boundaries and in generating continuous dielectric functions across the computational domain. A total free energy functional is constructed to couple polar and nonpolar contributions to the salvation process. Geometric measure theory is employed to rigorously convert a Lagrangian formulation of the surface energy into an Eulerian formulation so as to bring all energy terms into an equal footing. By minimizing the total free energy functional, we derive coupled generalized Poisson-Boltzmann equation (GPBE) and generalized geometric flow equation (GGFE) for the electrostatic potential and the construction of realistic solvent-solute boundaries, respectively. By solving the coupled GPBE and GGFE, we obtain the electrostatic potential, the solvent-solute boundary profile, and the smooth dielectric function, and thereby improve the accuracy and stability of implicit solvation calculations. We also design efficient second order numerical schemes for the solution of the GPBE and GGFE. Matrix resulted from the discretization of the GPBE is accelerated with appropriate preconditioners. An alternative direct implicit (ADI) scheme is designed to improve the stability of solving the GGFE. Two iterative approaches are designed to solve the coupled system of nonlinear partial differential equations. Extensive numerical experiments are designed to validate the present theoretical model, test computational methods, and optimize numerical algorithms. Example solvation analysis of both small compounds and proteins are carried out to further demonstrate the accuracy, stability, efficiency and robustness of the present new model and numerical approaches. Comparison is given to both experimental and theoretical results in the literature.     

Polymerizable C70 derivatives with acrylate functionality for efficient and stable solar cells

Fullerene-based organic solar cells are generally suffering from severe microstructure evolution occurring in their bulk heterojunction active layers and thus are extremely stable. To address it, four polymerizable C₇₀ fullerene derivatives, [6,6]-phenyl-C₇₁-ethyl acrylate (PC₇₁EA), [6,6]-phenyl-C₇₁-propyl acrylate (PC₇₁PrA), [6,6]-phenyl-C₇₁-butyl acrylate (PC₇₁BA), and [6,6]-phenyl-C₇₁-pentyl acrylate (PC₇₁PeA), have been designed, synthesized, and investigated. These fullerene compounds have a molecular structure, shape and size very like the conventional C₇₀ fullerene acceptor, [6,6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM), and have been found no different in their light absorption, redox potentials, and frontier orbital energy levels. Using these fullerene acrylates individually as acceptor and poly(3-hexylthiophene) as donor, organic solar cells have been fabricated and gave optimal efficiencies ranging from 3.32% to 4.16%, comparable to PC₇₁BM-based reference cells (4.06%). Owing to their acrylate functionality, these fullerene derivatives can turn into insoluble upon heating, and thus endow their solar cell devices much better thermostability than PC₇₁BM-based reference cells. The best one, coming from PC₇₁PeA devices, reported an optimal efficiency of 4.16%, and maintained 91.7% efficiency after heat treatment at 150 °C for 35 h. As a sharp contrast, the PC₇₁BM reference cell dropped its optimal efficiency from 4.06% to 0.48% only after 5 h heat treatment. X-ray diffraction, optical and atomic force microscopy, and space-charge-limited current method have been carried out to understand active layer structure, morphology, and charge mobility change during heat treatment.     

Hierarchical Integration of Organic Core/Shell Microwires for Advanced Photonics

The combination of multiple components or structures into integrated micro/nanostructures for practical application has been pursued for many years. Herein, a series of hierarchical organic microwires with branch, core/shell (C/S), and branch C/S structures are successfully constructed based on organic charge transfer (CT) cocrystals with structural similarity and physicochemical tunability. By regulating the intermolecular CT interaction, single microwires and branch microstructures can be integrated into the C/S and branch C/S structures, respectively. Significantly, the integrated branch C/S microwires, with multicolor waveguide behavior and branch structure multichannel waveguide output characteristics, can function as an optical logic gate with multiple encoding features. This work provides useful insights for creating completely new types of organic microstructures for integrated optoelectronics.     

Genetic Fusion of Thermoresponsive Polypeptides with UCST-type Behavior Mediates 1D Assembly of Coiled-Coil Bundlemers

Thermoresponsive resilin-like polypeptides (RLPs) of various lengths were genetically fused to two different computationally designed coiled coil-forming peptides with distinct thermal stability, to develop new strategies to assemble coiled coil peptides via temperature-triggered phase separation of the RLP units. Their successful production in bacterial expression hosts was verified via gel electrophoresis, mass spectrometry, and amino acid analysis. Circular dichroism (CD) spectroscopy, ultraviolet-visible (UV/Vis) turbidimetry, and dynamic light scattering (DLS) measurements confirmed the stability of the coiled coils and showed that the thermosensitive phase behavior of the RLPs was preserved in the genetically fused hybrid polypeptides. Cryogenic-transmission electron microscopy and coarse-grained modeling revealed that functionalizing the coiled coils with thermoresponsive RLPs leads to their thermally triggered noncovalent assembly into nanofibrillar assemblies.