Switchable Reversible Addition–Fragmentation Chain Transfer (RAFT) Polymerization with the Assistance of Azobenzenes

Modulating controlled radical polymerization is an interesting and important issue. Herein, modulating RAFT polymerization employing photosensitive azobenzenes is achieved. In the presence of azobenzenes and with visible light off, RAFT polymerization runs smoothly and follows a pseudo‐first‐order kinetics. In contrast, with light on, RAFT polymerization is greatly decelerated or quenched depending on the type and concentration of azobenzenes. Switchable RAFT polymerization of different (meth)acrylate monomers alternatively with light off and on is demonstrated. A mechanism of photoregulating RAFT polymerization involving radical quenching by azobenzenes is proposed.     

Noninvasive hemoglobin measurement based on optimizing Dynamic Spectrum method

An optimizing Dynamic Spectrum method based on short-time Fourier transform for noninvasive hemoglobin measurement was proposed. A total of 187 volunteers’ spectral data and blood samples were prepared for the calibration (167 samples) and prediction (20 samples) sets. Data processing with optimizing dynamic spectrum method was set as experimental group, while control group was with classical method based on fast Fourier transform. The model for hemoglobin prediction was established with partial least square regression. In the experimental group, the average prediction correlation coefficient was 0.8399, while that of the control group was 0.6686. The results demonstrate that the optimizing method has a good accuracy improvement for noninvasive hemoglobin measurement. The optimizing dynamic spectrum method combining statistical characteristics analysis as a modified analytical method has a promising application prospect of application in noninvasive blood component measurement field.     

Direct affinity screening chromatography–mass spectrometry assay for identification of antibacterial agents from natural product sources

A direct affinity screening – mass spectrometry assay, coupled to liquid chromatography, is presented as a tool for natural product drug discovery. Using the assay, fractionated extracts from a Caribbean gorgonian coral were shown to contain a new chemical entity (NCE) which binds to a mimic of the Gram positive bacterial cell wall (lysine–d-alanine–d-alanine). Conditions for observation of a specific noncovalent complex between the NCE and the target mimic using electrospray ionization-mass spectrometry were validated in a series of positive and negative control experiments, which featured flow injection analysis-based titrations. While the structural identity of the NCE could not be determined due to limited sample quantities, this work provides proof-of-principle for such an approach to potentially accelerate drug discovery from natural product sources.     

Thiol–Anhydride Dynamic Reversible Networks

The reaction of thiols and anhydrides to form ring opened thioester/acids is shown to be highly reversible and it is accordingly employed in the fabrication of covalent adaptable networks (CANs) that possess tunable dynamic covalent chemistry. Maleic, succinic, and phthalic anhydride derivatives were used as bifunctional reactants in systems with varied stoichiometries, catalyst, and loadings. Dynamic characteristics such as temperature-dependent stress relaxation, direct reprocessing and recycling abilities of a range of thiol–anhydride elastomers, glasses, composites and photopolymers are discussed. Depending on the catalyst strength, 100 % of externally imposed stresses were relaxed in the order of minutes to 2 hours at mild temperatures (80–120 °C). Pristine properties of the original materials were recovered following up to five cycles of a hot-press reprocessing technique (1 h/100 °C).     

Evaluation of the Fast Inverse Laplace Transform for Three-Dimensional NMR Distribution Functions

A fast inverse Laplace transform (ILT) for the three-dimensional (3-D) nuclear magnetic resonance distribution was proposed by the authors with a designed pulse sequence and an efficient data-processing algorithm in Zhang et al. (Appl Magn Reson 44:849–857, 2013). In this paper, evaluation method to the 3-D ILT algorithm is introduced and the simulation results using simulated data with three different signal-to-noise ratios demonstrate that the precision and speed are excellent.     

受限高分子薄膜界面动力学与缠结的关系

通过Monte Carlo模拟结合原始路径分析(PPA)的方法,阐述了缠结高分子薄膜的界面动力学与缠结程度的关系.研究发现,以吸附势能的临界值εwc≈-0.6 kBT附近为界,当墙壁-高分子作用势能从弱吸引到强排斥变化时,界面层中的链移动快于中心层,只有当墙壁的吸引作用增强到一定程度时,界面层中的链移动才会慢于中心层.界面动力学受到促进或阻碍可能与界面层和中心层的缠结程度直接相关:界面层的缠结程度保持在本体水平上基本不变;中心层的缠结程度在强吸引表面上低于界面层,而在弱吸引和排斥表面上高于界面层.此外,中心层和界面层中高分子链受限程度的变化对薄膜界面动力学行为的转变产生一定影响.对于薄膜中链密度分布情况随墙壁-高分子作用势能变化的分析为相关的物理化学机制提供了理论依据.     

g-C3N4表面改性及其光催化制H2与CO2还原研究进展

Solar energy is the largest renewable energy source in the world and the primary energy source of wind energy, tidal energy, biomass energy, and fossil fuel. Photocatalysis technology is a sunlight-driven chemical reaction process on the surface of photocatalysts that can generate H₂ from water, decompose organic contaminants, and reduce CO₂ into organic fuels. As a metal-free polymeric material, graphite-like carbon nitride (g-C₃N₄) has attracted significant attention because of its special band structure, easy fabrication, and low costs. However, some bottlenecks still limit its photocatalytic performance. To date, numerous strategies have been employed to optimize the photoelectric properties of g-C₃N₄, such as element doping, functional group modification, and construction of heterojunctions. Remarkably, these modification strategies are strongly associated with the surface behavior of g-C₃N₄, which plays a key role in efficient photocatalytic performance. In this review, we endeavor to provide a comprehensive summary of g-C₃N₄-based photocatalysts prepared through typical surface modification strategies (surface functionalization and construction of heterojunctions) and elaborate their special light-excitation and response mechanism, photo-generated carrier transfer route, and surface catalytic reaction in detail under visible-light irradiation. Moreover, the potential applications of the surface-modified g-C₃N₄-based photocatalysts for photocatalytic H₂ generation and reduction of CO₂ into fuels are summarized. Finally, based on the current research, the key challenges that should be further studied and overcome are highlighted. The following are the objectives that future studies need to focus on: (1) Although considerable effort has been made to develop a surface modification strategy for g-C₃N₄, its photocatalytic efficiency is still too low to meet industrial application standards. The currently obtained solar-to‑hydrogen (STH) conversion efficiency of g-C₃N₄ for H₂ generation is approximately 2%, which is considerably lower than the commercial standards of 10%. Thus, the regulation of the surface/textural properties and electronic band structure of g-C₃N₄ should be further elucidated to improve its photocatalytic performance. (2) Significant challenges remain in the design and construction of g-C₃N₄-based S-scheme heterojunction photocatalysts by facile, low-cost, and reliable methods. To overcome the limitations of conventional heterojunctions thoroughly, a promising S-scheme heterojunction photocatalytic system was recently reported. The study further clarifies the charge transfer route and mechanism during the catalytic process. Thus, the rational design and synthesis of g-C₃N₄-based S-scheme heterojunctions will attract extensive scientific interest in the next few years in this field. (3) First-principle calculation is an effective strategy to study the optical, electrical, magnetic, and other physicochemical properties of surface strategy modified g-C₃N₄, providing important information to reveal the charge transfer path and intrinsic catalytic mechanism. As a result, density functional theory (DFT) computation will be paid increasing attention and widely applied in surface-modified g-C₃N₄-based photocatalysts.     

商用聚丙烯酸类高吸水树脂粒子尺寸及分布与其凝胶浓度的关系

研究了6种商用聚丙烯酸类高吸水树脂(SAP)粒子尺寸大小及分布对其形成凝胶的临界浓度的影响,通过傅里叶变换红外光谱、X射线光电子能谱对样品的成分进行了分析,使用光学显微镜和ImageJ软件统计了样品未吸水时粒子的尺寸及分布,通过测定样品吸水后的膨胀比,估算得到了样品吸水后的粒子的尺寸及分布,用流变学方法和倒置实验法测定了高吸水树脂形成凝胶的临界浓度(凝胶点)。 结果表明,这6种商用聚丙烯酸类高吸水树脂吸水后的粒子的尺寸大小对其形成凝胶的临界浓度的影响不符合理论预测,这是由于粒子尺寸分布宽度不均一造成的。 在选择粒子大小分布占优的均一范围内,样品的凝胶浓度随着粒子尺寸的增大而降低。     

N-取代苄基-3,5-双苄叉基-哌啶-4-酮的合成及其抗癌活性的测定

以取代苄胺或伯胺为原料,依次经过Michael加成、Dieckmann缩合、水解脱羧和羟醛缩合反应,合成了10种新化合物(8a～8j),目标化合物的结构经1H NMR、IR、MS和元素分析确证。 初步的MTT法生物活性测试表明,目标化合物在100 mg/L浓度下能有效抑制白血病K562细胞、乳腺癌HO8910PM细胞和卵巢癌MDR-MB-231细胞的增殖,具有潜在的抗癌活性。