Degradation of parathion methyl by reactive sorption on the cerium oxide surface: The effect of solvent on the degradation efficiency

A simple and easily scalable “wet” procedure was used to prepare nanocrystalline cerium oxide capable of destroying the toxic organophosphate pesticide parathion methyl. The synthetic procedure consists of the direct precipitation of cerous salt with aqueous ammonia in the absence of CO₂. The prepared cerium oxide was able to decompose the organophosphate compounds both in nonpolar (e.g., heptane) and polar aprotic (e.g., acetonitrile) solvents. However, in solvents with hydrogen-bond donating ability, the –OH groups on the cerium oxide surface were solvated and inactivated. The preferential solvation model was used to express the experimental dependencies of the cerium oxide degradation efficiency on the composition of the water-acetonitrile mixture. In certain solvent systems, some empirical polarity scales, such as the alpha-scale or the Dimrodth-Richardt parameter ET(30), may be correlated with the degradation efficiency of cerium oxide.     

Experimental and mechanistic study of mudstone volumetric swelling at the bottom of salt cavern gas storage

Salt cavern gas storage is one of the vital strategic natural gas reserves and emergency peak shaving facilities all over the world. However, rock salt in China is primarily bedded salt, usually composed of many thin salt layers and interlayers (e.g., anhydrite, mudstone, and glauberite). During the water solution mining process of the cavern, the insoluble mudstones fall to the bottom and account for 1/3 up to 2/3 of the storage capacity. The bulk volume of the insoluble mudstones is almost twice its in-suit volume. It is of great urgency to investigate the swelling mechanisms of the bottom insoluble mudstones. Given this, we first analyzed the mineral composition of salt rock and insoluble mudstones by using XRD and SEM methods. Then, experimental studies were carried out considering both clay swelling and physical packing. At last, the zeta potential tests were conducted to reveal the swelling mechanisms of the bottom mudstones. Results show that the volumetric expansion of mudstones is made up of three parts: clay swelling, particle surface bound water volume, and pore space free water volume increase. Because the content of expansive clay in the bottom mudstones is less than 2%, and the high salinity brine in the cavern has excellent clay stability performance, clay swelling is not the main contributor to the volumetric expansion of the bottom mudstones. Measurement results show that the surface of the mudstones is negatively charged after hydration. Electrostatic repulsion can increase the spacing between small rock particles and creates approximately 47.6% of the pore space, which is the main factor in the volumetric expansion of mudstones. This study provides a theoretical basis for the mining solution and capacity enlargement during the construction of bedded salt cavern gas storage in China.     

Systematic Modulation of Thiol Functionalities in Inexpensive Porous Polymers for Effective Mercury Removal

Through accumulation, mercury contamination in aquatic systems still poses serious health risks despite the strict regulations on drinking water and industrial discharge. One effective strategy against this is adsorptive removal, in which a suitably functionalized porous material is added to water treatment protocols. Thiol (SH) group-grafted structures perform commendably; however, insufficient attention is paid to the cost, scalability, and reusability or how the arrangement of sulfur atoms could affect the Hg^II binding strength. We used an inexpensive and scalable porous covalent organic polymer (COP-130) to systematically introduce thiol functional groups with precise chain lengths and sulfur content. Thiol-functionalized COP-130 demonstrates enhanced wettability and excellent Hg^II uptake of up to 936 mg g⁻¹, with fast kinetics and exceptionally high selectivity. These Hg adsorbents are easily regenerated with HCl and can be used at least six times without loss of capacity even after treatment with strong acid, a rare performance in the domain of Hg-removal research.     

化妆品中的肽化学*

随着科技进步和产业提升,人们不断从本源上追求美、从长效上保持美、从机制上激发美。众多肽类化合物,已被证实在人体内具有独特的生物学促进或抑制作用,也因此被广泛应用于美妆产品。以化妆品中生物活性肽的不同功效为主线,对其化学结构进行分析并阐述其中的生理作用机制。     

Single-Step Hydrothermal Synthesis of Biochar from H3PO4-Activated Lettuce Waste for Efficient Adsorption of Cd(II) in Aqueous Solution

Developing an ideal and cheap adsorbent for adsorbing heavy metals from aqueous solution has been urgently need. In this study, a novel, effective and low-cost method was developed to prepare the biochar from lettuce waste with H₃PO₄ as an acidic activation agent at a low-temperature (circa 200 °C) hydrothermal carbonization process. A batch adsorption experiment demonstrated that the biochar reaches the adsorption equilibrium within 30 min, and the optimal adsorption capacity of Cd(II) is 195.8 mg∙g⁻¹ at solution pH 6.0, which is significantly improved from circa 20.5 mg∙g⁻¹ of the original biochar without activator. The fitting results of the prepared biochar adsorption data conform to the pseudo-second-order kinetic model (PSO) and the Sips isotherm model, and the Cd(II) adsorption is a spontaneous and exothermic process. The hypothetical adsorption mechanism is mainly composed of ion exchange, electrostatic attraction, and surface complexation. This work offers a novel and low-temperature strategy to produce cheap and promising carbon-based adsorbents from organic vegetation wastes for removing heavy metals in aquatic environment efficiently.     

Configurational Lability at Tetrahedral Phosphorus: syn/anti-Isomerization of a P-Stereogenic Phosphiranium Cation by Intramolecular Epimerization at Phosphorus

Tetrahedral main-group compounds are normally configurationally stable, but P-epimerization of the chiral phosphiranium cations syn- or anti-[Mes*P(Me)CH₂CHPh][OTf] (Mes*=2,4,6-(t-Bu)₃C₆H₂) occurred under mild conditions at 60 °C in CD₂Cl₂, resulting in isomerization to give a syn-enriched equilibrium mixture. Ion exchange with excess [NBu₄][Δ-TRISPHAT] (Δ-TRISPHAT=Δ-P(o-C₆Cl₄O₂)₃) followed by chromatography on silica removed [NBu₄][OTf] and gave mixtures of syn- and anti-[Mes*P(Me)CH₂CHPh][Δ-TRISPHAT]?x[NBu₄][Δ-TRISPHAT]. NMR spectroscopy showed that isomerization proceeded with epimerization at P and retention at C. DFT calculations are consistent with a mechanism involving P-C cleavage to yield a hyperconjugation-stabilized carbocation, pyramidal inversion promoted by σ-interaction of the P lone pair with the neighboring β-carbocation, and ring closure with inversion of configuration at P.     

Visible-Light-Induced C4-Selective Functionalization of Pyridinium Salts with Cyclopropanols

The site-selective C?H functionalization of heteroarenes is of considerable importance for streamlining the rapid modification of bioactive molecules. Herein, we report a general strategy for visible-light-induced β-carbonyl alkylation at the C4 position of pyridines with high site selectivity using various cyclopropanols and N-amidopyridinium salts. In this process, hydrogen-atom transfer between the generated sulfonamidyl radicals and O?H bonds of cyclopropanols generates β-carbonyl radicals, providing efficient access to synthetically valuable β-pyridylated (aryl)ketones, aldehydes, and esters with broad functional-group tolerance. In addition, the mild method serves as an effective tool for the site-selective late-stage functionalization of complex and medicinally relevant molecules.     

A thermochemical analysis of inhalational anesthetics

The mechanism of the anesthetic process is of interest both to the clinician and to the pharmacologist. However, this is still an unsettled issue and a multitude of models have been proposed for the process. Noticing that most models propose either a molecular perturbation by the agents or an effect on some colligative property, we explore in this article the thermodynamical consequences of these postulations. Comparison of these with experimental findings is then made. The comparison shows the inconsistency of many of the models with the facts: (i) it refutes the long accepted conviction, culminated in the unitary hypothesis, that general anesthetics act not at a particular receptor site but invariably on all. Some consequences of this finding are demonstrated. (ii) it implies that a simple phospholipid medium is not feasible as an anesthetic site. (iii) it infers that proteins do have the properties required from anesthetic sites.Dedicated to Prof. Menachem Steinberg on the occasion of his 65th birthday     

On the plastic deformation of bulk syndiotactic polypropylene

 The plastic deformation of syndiotactic polypropylene (sPP) bulk samples has been investigated. A structural comparison of the initial states before and after plastic deformation by necking is carried out by X-ray diffraction observations. Independent of the initial states (amorphous, semi-crystalline with different crystal phases), only the planar all-trans crystal form of sPP is present in the deformed samples after necking. Form these results, molecular mechanisms of the plastic deformation in the neck zone of semi-crystalline polymers will be discussed. Received: 11 February 1997 Accepted: 15 August 1997     

Cathodes for Aqueous Zn-Ion Batteries: Materials,Mechanisms, and Kinetics

As concerns about the safety of lithium-ions batteries (LIBs) increases, aqueous zinc-ion batteries (ZIBs) with a lower cost, higher safety, and higher co-efficiency have attracted more and more interest. However, finding suitable cathode materials is still an urgent problem in ZIBs. In recent years, a lot of significant works have been reported, including manganese-based cathodes, vanadium-based cathodes, Prussian blue analog-based materials, and sustainable quinone cathodes. In this review, some typical cathode materials are introduced. The detailed storage mechanisms and methods for improving the reaction kinetics of the zinc ions are summarized. Finally, the issues, challenges, and the research directions are provided.