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.     

Elucidating Molecule–Plasmon Interactions in Nanocavities with 2 nm Spatial Resolution and at the Single‐Molecule Level

The fundamental understanding of the subtle interactions between molecules and plasmons is of great significance for the development of plasmon‐enhanced spectroscopy (PES) techniques with ultrahigh sensitivity. However, this information has been elusive due to the complex mechanisms and difficulty in reliably constructing and precisely controlling interactions in well‐defined plasmonic systems. Herein, the interactions in plasmonic nanocavities of film‐coupled metallic nanocubes (NCs) are investigated. Through engineering the spacer layer, molecule–plasmon interactions were precisely controlled and resolved within 2 nm. Efficient energy exchange interactions between the NCs and the surface within the 1–2 nm range are demonstrated. Additionally, optical dressed molecular excited states with a huge Lamb shift of ≈7 meV at the single‐molecule (SM) level were observed. This work provides a basis for understanding the underlying molecule–plasmon interaction, paving the way for fully manipulating light–matter interactions at the nanoscale.