Activity

We present an experimentally parametrized molecular dynamics study of single-molecule and collective orientational relaxation in neat benzonitrile through the analysis of the reorientational anisotropy and polarizability anisotropy time correlation function (PA-TCF). The simulations show that the PA-TCF is dominated by collective reorientation after 20 ps. Collective reorientation is found to be slower than single-molecule reorientation by a factor of 1.67, consistent with recent experiments. The simulations provide direct evidence of local antiparallel benzonitrile configurations. These structures, which have been the center of some debate, are responsible for the slower rate of collective versus single-molecule reorientation in the liquid. Further structural analysis indicates that significant Coulombic interactions between the nitrile group and hydrogen atoms on adjacent molecules play a role in the formation of the antiparallel structures. The single-molecule dynamics reflected in the anisotropy are complex and consist of a ballistic regime, restricted angular diffusion, and spatially anisotropic free diffusion. The principal components of the rotational diffusion tensor are independently obtained and shown to reproduce the free diffusion regime of the anisotropy for each principal axis according to the predictions of a previous theory.The aspiration of the multi-attribute method (MAM) is to utilize a single mass spectrometry-based method that can measure multiple attributes simultaneously, thus enabling data-driven decisions more quickly and efficiently. However, challenges associated with identifying and quantitating critical quality attributes such as asparagine deamidation and isoaspartic acid using conventional ultrahigh-pressure liquid chromatography (UHPLC) coupled to mass spectrometry have necessitated long gradients to ensure sufficient separation for quantitation. Microfluidic chip-based capillary zone electrophoresis mass spectrometry (CZE-MS) shows potential to enable rapid charge-based separation of peptide mixtures, and this approach was evaluated using multipeptide mixtures of synthetic peptides as well as digested protein therapeutics. In these experiments, repeatability, linearity, and peak-to-peak resolution of several peptide families containing asparagine deamidation and/or isoaspartic acid were demonstrated. In addition, a comparison of peptide map results acquired with both UHPLC-MS and CZE-MS for two enzymatically digested biological therapeutics showed comparable sequence coverage and quantitation results between the two approaches. As MAM becomes increasingly utilized for analysis of biological therapeutics, MS instrument demand will rapidly increase, resulting in a bottleneck. A CZE-based separation shows potential to alleviate this bottleneck by drastically increasing MAM throughput while providing results comparable to those acquired using conventional UHPLC separations.Functionalized oligonucleotides (ONs) are widely applied as target binding molecules for biosensing and regulators for gene expression. Numerous efforts have been focused on developing facile methods for preparing these useful ONs carrying diverse modifications. Herein, we present a general method for postsynthetic modification of ONs via oxidative amination of 4-thio-2′-deoxyuridine (4SdU). 4SdU-containing ON can be derived by both alkyl and aromatic amines. Using this approach, ONs are successfully attached with alkyne/azide, biotin and dansylamide moieties, and these as-prepared ONs possess the expected biorthogonal reactivity, streptavidin affinity and fluorescent property, respectively. Furthermore, we also directly install fluorophores to the ON nucleobase based on oxidative amination of 4SdU, and these fluorophores exhibit distinct luminescence behaviors before and after conjugation. We believe our method will be a versatile strategy for constructing various functionalized ONs used in a wide range of nucleic acid applications.Research on advanced electrode materials (AEMs) has been explosive for the past decades and constantly promotes the development of batteries, supercapacitors, electrocatalysis, and photovoltaic applications. However, traditional preparation and modification methods can no longer meet the increasing requirements of some AEMs because some of the special reactions are thermodynamically and/or kinetically unfavorable and thus need harsh conditions. Among various recently developed advanced materials synthesis and modification routes, the plasma-assisted (PA) method has received increasing attention because of its unique and different “species reactivity” nature, as well as its wider and adjustable operating conditions. In this Spotlight on Applications, we highlight some recent developments and describe our recent progress by applying PA systems in the synthesis and modification of AEMs, including direct processing, PA deposition, and plasma milling (P-milling). The mechanisms of how plasma works for specific reactions are reviewed and discussed. It is shown that the PA technique has become a powerful and efficient tool in the following areas, including but not limited to materials synthesis, doping, surface modification, and functionalization. find more Finally, the prospect and challenges are also proposed for AEM preparation and modification using PA systems. This article aims to provide up-to-date information about the progress of PA technology in the fields of chemistry and materials science.Reduced graphene oxide and molybdenum disulfide (rGOMoS2) are the most representative two-dimensional materials, which are promising for a humidity sensor owing to its high surface area, a large number of active sites, and excellent mechanical flexibility. Herein, we introduced a highly sensitive and stable rGOMoS2-based humidity sensor integrated with a low-power in-plane microheater and a temperature sensor, directly insertable to transformer insulating oil, and analyzed by a newly developed customized sensor interface electronics to monitor the sensor’s output variations in terms of relative humidity (RH) concentration. rGOMoS2 sensing materials were synthesized by simple ultrasonication without using any additives or additional heating and selectively deposited on titanium/platinum (Ti/Pt) interdigitated electrodes on a SiO2 substrate using the drop-casting method. The significant sensing capability of p-n heterojunction formation between rGO and MoS2 was observed both in the air and transformer insulating oil environment.