Reinforced Supramolecular Hydrogels from Attapulgite and Cyclodextrin Pseudopolyrotaxane for Sustained Intra‐Articular Drug Delivery

Injectable hydrogels for nonsteroidal anti‐inflammatory drugs’ (NSAIDs) delivery to minimize the side effects of NSAIDs and achieve long‐term sustained release at the targeted site of synovial joint are attractive for osteoarthritis therapy, but how to improve its mechanical strength remains a challenge. In this work, a kind of 1D natural clay mineral material, attapulgite (ATP), is introduced to a classical cyclodextrin pseudopolyrotaxane (PPR) system to form a reinforced supramolecular hydrogel for sustained release of diclofenac sodium (DS) due to its rigid, rod‐like morphology, and unique structure, which has great potential in tissue regeneration, repair, and engineering. Investigation on the interior morphology and rheological property of the obtained hydrogel points out that the ATP distributed in PPR hydrogel plays a role similar to the “reinforcement in concrete” and exhibits a positive effect on improving the mechanical properties of PPR hydrogel by regulating their interior morphology from a randomly distributed style to the well‐ordered porous frame structure. The hybrid hydrogels demonstrate good shear‐thinning and thixotropic properties, excellent biocompability, and sustained release behavior both in vitro and in vivo. Furthermore, preliminary in vivo treatment in an acute inflammatory rat model reveals that the ATP hybrid hydrogels present sustained anti‐inflammatory effect.     

Simultaneous determination of major components of Huangqi–Honghua extract in rat plasma using LC–MS/MS and application to a pharmacokinetic study

A sensitive and reliable LC–MS/MS method was developed and validated for simultaneous quantification of the major components of Huangqi–Honghua extact in rat plasma, including hydroxysafflor yellow A (HSYA), astragaloside IV (ASIV), calycosin‐7‐O‐β‐d ‐glucoside (CAG), calycosin, calycosin‐3′‐O‐glucuronide (C‐3′‐G) and calycosin‐3′‐O‐sulfate (C‐3′‐S). After extraction by protein precipitation with acetonitrile and methanol from plasma, the analytes were separated on a Hypersil BDS C₁₈ column by gradient elution with acetonitrile and 5 mM ammonium acetate. The detection was carried out on a triple quadrupole tandem mass spectrometer equipped with electrospray ionization source switched between negative and positive modes. HSYA was monitored in negative ionization mode from 0 to 4.9 min, and ASIV, CAG, calycosin, C‐3′‐G and C‐3′‐S were determined in positive ionization mode from 4.9 to 10 min. The lower limits of quantification of the analytes were 6.25 ng/mL for HSYA, 0.781 ng/mL for CAG and 1.56 ng/mL for ASIV and calycosin. The intra‐ and inter‐assay precision (RSD) values were within 13.43%, and accuracy (RE) ranged from ?8.75 to 9.92%. The validated method was then applied to the pharmacokinetic study of HSYA, ASIV, CAG, calycosin, C‐3′‐G and C‐3′‐S in rat after an oral administration of Huangqi–Honghua extract.     

Metabolomic analysis of raw Pinelliae Rhizoma and its alum‐processed products via UPLC–MS and their cytotoxicity

Alum‐processing is a traditional method to attenuate the toxicity of Pinelliae Rhizoma (tubers of Pinellia ternate, PT). The present study aimed at investigating the chemical and cytotoxic changes during alum processing. Metabolomic profiles of raw and alum‐processed PT were studied based on ultra‐performance liquid chromatography coupled with Orbitrap mass spectrometry. More than 80 chemicals in positive MS mode and 40 chemicals in negative MS mode, such as organic acids, amino acids, glucosides and nucleosides, were identified after multivariate statistical analysis, including principal component analysis and orthogonal partial least‐square discriminant analysis. Almost all of the identified chemical markers were significantly decreased ~10‐ to 100‐fold after alum processing. Meanwhile, the correlations between the chemical markers were assimilated to a positive coefficient from disorderly distribution during the processing. Raw PT extracts could inhibit the proliferation of human carcinoma cells (HCT‐116, HepG2, and A549) at the rate of 40.5, 24.8 and 31.6% more strongly than processed PT. It was concluded that the alum processing of PT could decrease the number of actively water‐soluble principles at the same time as decreasing toxicity. Given the water‐insoluble property of toxic calcium oxalate raphides in PT, we suggest that a more scientific processing method should be sought.     

Self-Healable Polyelectrolytes with Mechanical Enhancement for Flexible and Durable Supercapacitors

The practical application of advanced personalized electronics is inseparable from flexible, durable, and even self-healable energy storage devices. However, the mechanical and self-healing performance of supercapacitors is still limited at present. Herein, highly transparent, stretchable, and self-healable poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPSA)/poly(vinyl alcohol) (PVA)/LiCl polyelectrolytes were facilely prepared by one-step radical polymerization. The cooperation of PAMPSA and PVA significantly increased the mechanical and self-healing capacity of the polyelectrolyte, which exhibited superior stretchability of 938 %, stress of 112.68 kPa, good electrical performance (ionic conductivity up to 20.6 mS cm⁻¹), and high healing efficiency of 92.68 % after 24 h. After assembly with polypyrrole-coated single-walled carbon nanotubes, the resulting as-prepared supercapacitor had excellent electrochemical properties with high areal capacitance of 297 mF cm⁻² at 0.5 mA cm⁻² and good rate capability (218 mF cm⁻² at 5 mA cm⁻²). Besides, after cutting in two the supercapacitor recovered 99.2 % of its original specific capacitance after healing for 24 h at room temperature. The results also showed negligible change in the interior contact resistance of the supercapacitor after ten cutting/healing cycles. The present work provides a possible solution for the development of smart and durable energy storage devices with low cost for next-generation intelligent electronics.     

Hitherto-Unexplored Photodynamic Therapy of Ag2S and Enhanced Regulation Based on Polydopamine In Vitro and Vivo

Given their superior penetration depths, photosensitizers with longer absorption wavelengths present broader application prospects in photodynamic therapy (PDT). Herein, Ag₂S quantum dots were discovered, for the first time, to be capable of killing tumor cells through the photodynamic route by near-infrared light irradiation, which means relatively less excitation of the probe compared with traditional photosensitizers absorbing short wavelengths. On modification with polydopamine (PDA), PDA-Ag₂S was obtained, which showed outstanding capacity for inducing reactive oxygen species (increased by 1.69 times). With the addition of PDA, Ag₂S had more opportunities to react with surrounding O₂, which was demonstrated by typical triplet electron spin resonance (ESR) analysis. Furthermore, the PDT effects of Ag₂S and PDA-Ag₂S achieved at longer wavelengths were almost identical to the effects produced at 660 nm, which was proved by studies in vitro. PDA-Ag₂S showed distinctly better therapeutic effects than Ag₂S in experiments in vivo, which further validated the enhanced regulatory effect of PDA. Altogether, a new photosensitizer with longer absorption wavelength was developed by using the hitherto-unexplored photodynamic function of Ag₂S quantum dots, which extended and enhanced the regulatory effect originating from PDA.     

Recent progress on the frontiers of polyoxometalates structures and applications

<正>Polyoxometalates (POMs), a class of discrete anionic metal oxides in groups Ⅴ and Ⅵ, are constructed via the condensation of metal oxide polyhedral (MO_x, M=W~(Ⅵ), Mo~(Ⅵ),V~Ⅴ, Nb, Ta, etc. and x=4–7) with each other in a corner-,edge-, or rarely in a face-sharing manner [1–3]. Up to now,the broadening family of POM derivatives ranges from small     

Tertiary Amines Differentiated from Primary and Secondary Amines by Active Ester‐Functionalized Hexabenzoperylene in Field Effect Transistors

Herein, we report two novel derivatives of hexabenzoperylene (HBP) that are functionalized with ester groups. Methyl acetate functionalized HBP ( 1 ) in single crystals self‐assembles into a supramolecular nanosheet, which has a two‐dimensional π‐stack of HBP sandwiched between two layers of ester groups. With the same self‐assembly motif, active ester‐functionalized HBP ( 2 ) in field effect transistors has enabled differentiation of tertiary amines from primary and secondary amines, in agreement with the fact that active ester reacts with primary and secondary amines but not with tertiary amines to form amides.     

焦炉上升管内壁结焦炭层的光谱学分析及结焦机理研究

以焦炉上升管内壁结焦炭层块为研究对象，采用X射线荧光光谱仪（XRF）、X射线衍射仪（XRD）、傅里叶红外光谱仪（FTIR）和激光共聚焦拉曼光谱仪（Raman）对结焦炭层的元素组成，以及各结焦炭层的矿物组成、组成结构和分子结构进行测试。分析从结焦炭层块外表面向内表面过渡的各结焦炭层的差异性，揭示焦炉上升管内壁结焦机理。结果表明焦炉上升管内粉尘中Fe，S和Cr极易催化荒煤气中蒽、萘等稠环芳烃化合物成炭，在焦炉上升管内壁形成炭颗粒沉积，为焦油凝结挂壁提供载体，在荒煤气温度降至结焦温度时易结焦积碳。结焦炭层均含有芳香层结构，随着结焦炭层从外表面向内表面过渡，各结焦炭层的面层间距(d₀₀₂)逐渐降低、层片直径(L_a)先降低后增加、层片堆砌高度(Lc)和芳香层数(N)先稳定后增加。结焦炭层石墨化过程是由结焦炭层内表面向外表面进行，主要包括其片层外缘的羧基和部分C-O结构的降解剥离，从而形成高度规整的共轭结构。结焦炭层块中C元素是以结晶碳与无定型碳的混合物形式存在。以上研究为解决焦炉上升管内壁结焦及腐蚀问题，提高换热器换热效率，有效回收焦炉荒煤气显热，降低焦化企业能耗提供实验基础和理论依据。     

Quantum Dots Microstructural Metrology: From Time-Resolved Spectroscopy to Spatially Resolved Electron Microscopy

Colloidal quantum dots (QDs) have unique optical and electrical properties with promising applications in next-generation semiconductor technologies, including displays, lighting, solar cells, photodetectors, and image sensors. Advanced analytical tools to probe the optical, morphological, structural, compositional, and electrical properties of QDs and their ensemble solid films are of paramount importance for the understanding of their device performance. In this review, comprehensive studies on the state-of-the-art metrology approaches used in QD research are introduced, with particular focus on time-resolved (TR) and spatially resolved (SR) spectroscopy and microscopy. Through discussing these analysis techniques in different QD system, such as various compositions, sizes, and shell structures, the critical roles of these TR-spectroscopic and SR-microscopic techniques are highlighted, which provide the structural, morphological, compositional, optical, and electrical information to precisely design QDs and QD solid films. The employment of TR and SR analysis in integrated QD device systems is also discussed, which can offer detailed microstructural information for achieving high performance in specific applications. In the end, the current limitations of these analytical tools are discussed, and the future development of the possibility of interdisciplinary research in both QD fundamental and applied fields is prospected.     

A Shell-by-Shell Approach for Synthesis of Mesoporous Multi-Shelled Hollow MOFs for Catalytic Applications

Over the past two decades, advanced materials with hollow interiors have received significant attention in materials research owing to their great application potential across a vast number of technological fields. Though with great difficulty, multi-shelled hollow metal–organic frameworks (MSHMs) have also been successfully synthesized in recent years. Herein, a rational shell-by-shell soft-templating protocol has been devised to fabricate highly uniform multi-shelled hollow cobalt-imidazole-based MOF (ZIF-67). For the first time, it has become possible to endow mesoporosity to this new type of functional material (i.e., mesoporous MOFs). When used as carrier materials in catalytic reactions, in principle, these mesoporous MSHMs with high surface area not only improve the dispersity of metal nanoparticles (NPs), but also efficiently facilitate the mass diffusion of the reactions, resulting in enhanced catalyst activity. Moreover, the obtained MSHMs/M nanocomposites serve as base-metal bifunctional catalysts for one-pot oxidation-Knoevenagel condensation cascade reaction, in which the MSHMs itself serves as a pristine active catalyst in addition to its role of catalyst support. The results demonstrate that excellent multifunctional catalysts can be achieved via preparing intrinsically microporous bulk MOFs into extrinsically mesoporous MSHMs which possess many structural merits that conventional bulk MOFs do not have.