In-situ dynamic catalysis electrode electrolyte interphase enabling Mg2+ insertion in 2D metal-organic polymer for high-capacity and long-lifespan magnesium batteries.

Rechargeable magnesium battery is regarded as the promising candidate for the next generation of high-specific-energy storage systems. Nevertheless, issues related to severe Mg-Cl dissociation at the electrolyte-electrode interface impede the insertion of Mg2+ into most materials, leading to severe polarization and low utilization of Mg-storage electrodes. In this study, a metal-organic polymer (MOP) Ni-TABQ (Ni-coordinated tetramino-benzoquinone) with superior surface catalytic activity is proposed to achieve the high-capacity Mg-MOP battery. The layered Ni-TABQ cathode, featuring a unique 2D π-d linear conjugated structure, effectively reduces the dissociation energy of MgxCly clusters at the Janus interface, thereby facilitating Mg2+ insertion. Due to the high utilization of active sites, Ni-TABQ achieves high capacities of 410 mAh/g at 200 mA g-1, attributable to a four-electron redox process involving two redox centers, benzoid carbonyls, and imines. This research highlights the importance of surface electrochemical processes in rechargeable magnesium batteries and paves the way for future development in multivalent metal-ion batteries.

An Unexpected Synthesis of 2-Sulfonylquinolines via Deoxygenative C2-Sulfonylation of Quinoline N-Oxides with Sulfonyl Chlorides.

A mild, efficient and practical protocol for the preparation of 2-sulfonylquinolines through CS2/Et2NH-induced deoxygenative C2-H sulfonylation of quinoline N-oxides with readily available RSO2Cl was developed. The reaction proceeded well under transition-metal-free conditions and exhibited a wide substrate scope and functional group tolerance. The preliminary studies suggested that the nucleophilic sulfonyl sources were generated in situ via the reaction of CS2, Et2NH and sulfonyl chlorides.

Nickel-Catalyzed Enantioselective Carbonyl Addition of Aryl Chlorides and Bromides to Aldehydes.

The Ni-catalyzed enantioselective addition reaction of aryl halides to aldehydes was studied with cyanobis(oxazoline) as chiral ligands and Mn as reductant. Aryl and heteroaryl bromides reacted with phenyl aldehyde at room temperature to produce dibenzyl alcohols in 16-99% yields with 53-92% ees. Moreover, the coupling of phenyl chloride with a variety of aryl, heteroaryl and alkyl aldehydes was demonstrated in the presence of cyanobis(oxazoline)/Ni(II) at 60 oC in generally high yields with moderate enantioselectivities.

Coupling of Aryl Chlorides with Lithium Nucleophiles Enabled by Molecularly Defined Alkynyllithium Palladium Catalysts.

Palladium-catalyzed cross-couplings of aryl chlorides usually call for bulky, electron-rich ligands such as phosphines or heterocyclic carbenes. We have now found that similarly powerful cross-coupling catalysts are obtained by the reaction of palladium salts with alkynyllithium reagents. The species initially formed in this process was characterized as a dilithium tetraalkinyl palladate complex. It catalyzes the coupling of aryl chlorides with the lithium salts of various terminal alkynes to give alkynyl arenes. The isolated Li-alkynyl-Pd complex also efficiently promotes the reaction of aryl, and allyl chlorides with (hetero)aryl-, alkyl-, and allyllithium compounds as well as lithium amines. None of these reactions proceeded in the presence of palladium salts alone. The preparative utility of this approach was demonstrated by the synthesis of 49 molecules, including pharmaceutically relevant compounds.

Breaking Boundaries: Giant Ultraviolet Birefringence in Dimension-Reduced Zn-Based Crystals.

Birefringent crystals have essential applications in optical communication areas. Low-dimensional structures with inherited structural anisotropy are potential systems for investigating birefringent materials with large birefringence. In this work, the zero-dimensional (0D) [(o-C5H5NO)2ZnCl2] (1) and [o-C5H6NO]2[ZnCl4] (2) were obtained by introducing the π-conjugated o-C5H5NO (4HP) into the three-dimensional (3D) ZnCl2. Remarkably, 1 exhibits a giant birefringence of 0.482@546 nm, which is the largest among Zn-based ultraviolet (UV) compounds and 160 times that of ZnCl2. According to structural and theoretical calculation analyses, the large optical polarizability, high spatial density, ideal distribution of the [(4HP)2ZnCl2]0 cluster, and the low dimension of 1 result in the dramatically increased birefringence compared to ZnCl2. This work will provide a valid route for accelerating the design and synthesis of compounds with excellent birefringence in low-dimensional systems.

A Study on the Removal of Impurity Elements Silicon and Zinc from Rubidium Chloride by Vacuum Distillation.

With the rapid development of high and new technology, rubidium and its compounds show broad application prospect and market demand with their unique characteristics. At present, the production of rubidium metal is mainly prepared by calcium thermal reduction of rubidium chloride. Rubidium metal obtained by reduction requires multi-step vacuum distillation to obtain high-purity rubidium metal. The purity of rubidium metal depends on the purity of the raw material rubidium chloride. Rubidium metal is relatively active and is easy to oxidize and explode in air. Therefore, a method combining vacuum decomposition and vacuum distillation to reduce impurity elements in rubidium chloride from raw materials is proposed in this paper. The experimental results show that under the conditions of pressure of 5-10 Pa, distillation temperature of 823 K and vacuum distillation time of 60 min, the contents of Si and Zn impurities are reduced from 1206 mg/kg and 310 mg/kg to less than 0.1 mg/kg, and the removal rates are 99.99% and 99.97%, respectively. Rubidium chloride has almost no loss, and through one-step vacuum distillation, the impurity elements silicon and zinc can be deeply removed, reducing the flammability and explosiveness, high cost, long process and other problems caused by the subsequent preparation of high-purity rubidium metal.

Evaluation of Pyrazolyl-Indolizine Derivatives as Antimicrobial Agents: Synthesis, In vitro, In silico ADMET and Molecular Docking Studies.

Herein, we report analogues of s-indacene by the synthesis of novel indolizine derivatives. Using chloroform as an appropriate solvent, sixteen derivatives of pyrazolyl-indolizine (4--19) were prepared by the reaction of 3-(dimethylamino)-1-(1H-pyrrol-2-yl)prop-2-en-1-one (1) with hydrazonoyl chloride derivatives (2) in the presence of triethylamine in good to excellent yields. We used NMR spectra, IR, mass spectrometry, as well as elemental analyses to prove the chemical structures and the purity of the synthesized compounds 4-19. Among all tested compounds 5, 9, 13 and 19 had a potent antimicrobial efficiency against Bacillus subtilis, Staphylococcus aureus, Pseudomonas aerginousea, Sallmonella typhemerium, and Candida albicans. Furthermore, a significant increase in lipid peroxidation (LPO) toward the Gram-negative bacteria, Pseudomonas aeruginosa when treated with compound 9 was observed, while compound 13 remarkably increased the cell membrane oxidation of Salmonella typhimurium. Additionally, we utilized docking studies and in silico methods to evaluate the drug-likeness, physicochemical properties, and ADMET profiles of the compounds. The results of the molecular docking simulation revealed that the synthesized compounds displayed decreased binding energy when interacting with the active sites of important enzymes, including Sterol 14-demethylase of C. albicans, Dihydropteroate synthase of S. aureus, LasR of P. aeruginosa, Glucosamine-6-phosphate synthase of S. typhimurium, and Gyrase B of B. subtilis.

Phosphonic Chloride Assisted Fabrication of Highly Emissive Mixed Halide Perovskite Films in Ambient Air for Blue Light-Emitting Diodes.

Blue perovskite light-emitting diodes (LEDs) have emerged as promising candidates for full-color display and lighting applications. However, the fabrication of blue-emitting perovskite films typically requires an inert environment, leading to increased complexity and cost in the manufacturing process, which is undesirable for applications of perovskite LEDs. Herein, we report a strategy to fabricate bright blue-emitting perovskite films in ambient air by incorporating phosphonic chlorides in a perovskite precursor solution. We used two different phosphonic chlorides, diphenylphosphonic chloride (DPPC) and phenylphosphonic dichloride (PPDC), and comparatively studied their effects on the properties of perovskite films and the blue LEDs. It is found that PPDC possesses a stronger chlorination ability due to higher hydrolysis reactivity; meanwhile, it has a stronger interaction with the perovskite compared to DPPC, resulting in an improved film quality and enhanced blue emission with a photoluminescence quantum yield of 45%, which represents the record value for the air-processed blue perovskite films. Blue perovskite LEDs are fabricated, and the emission wavelengths are effectively tuned by controlling the concentration of phosphonic chlorides. Benefiting from the optimized perovskite films with reduced nonradiative recombination and promoted charge injection and transport, the PPDC-derived blue perovskite LEDs exhibit improved performance with an external quantum efficiency of 3.3% and 1.2% for the 490 and 480 nm emission wavelength, respectively.

Study of the Corrosion Behavior of Stainless Steel in Food Industry.

AISI 304L stainless steel is widely used in the processing equipment and food and beverage handling industries due to its corrosion resistance, hygienic properties, and cost-effectiveness. However, it is prone to pitting and crevice corrosion phenomena, the development of which can be influenced by factors such as chloride concentration, temperature, humidity, and bacterial presence. Surface treatments, including roughness levels and residual tensile stress, can significantly affect the corrosion behavior and resistance of the material. This study aims to evaluate the impact of three different surface treatments on the durability of AISI 304L steel. The correlation between surface roughness resulting from pre-treatment and pitting potential values will be examined. Additionally, the influence of different concentrations of biocide additives on surface durability will be assessed to determine the maximum effective concentration for preventing pitting phenomena. Passivation processes will also be evaluated as a potential solution for improving the pitting potential and overall durability of the components. By optimizing surface treatments and biocide concentrations, improved corrosion resistance and durability can be achieved, ensuring the long-term performance and reliability of AISI 304L steel components in critical applications such as food processing and beverage handling.

Advancements in hydrochlorination of alkenes.

The hydrochlorination of alkenes has been extensively studied in research and is commonly featured in organic chemistry textbooks as an exemplification of the Markovnikov rule. However, the application of this reaction is typically limited to specific alkenes, such as highly substituted ones, styrenes, or strained systems. Conversely, monosubstituted or 1,2-disubstituted alkenes do not readily react with HCl gas or solutions of HCl gas at practical rates. The challenges associated with hydrochlorination reactions for these "non-activated" alkenes have spurred considerable research efforts over the past 30 years, which constitute the primary focus of this review. The discussion begins with classical polar hydrochlorinations, followed by metal-promoted radical hydrochlorinations, and concludes with a brief overview of recent anti-Markovnikov hydrochlorinations.

Photocatalytic Synthesis of ß-Keto Primary Chlorides by Selective Chlorocarbonylation of Olefins.

Functionalized primary alkyl chlorides are precursors to a plethora of scaffolds but their access from chemical feedstocks remains challenging. Herein, we report a concise dual Ni/photoredox catalytic protocol for regioselective chlorocarbonylation of unactivated alkenes that enables rapid access to ß-keto primary chlorides. The catalytic process features an extensive substrate scope, scalability and functional group tolerance. The Ni/photocatalytic Cl⋅ generation and subsequent cross-coupling is implicated for the process based on the control experiments and DFT study. The synthetic utility of the protocol has been further corroborated through functionalization of complex substrates and modifications of the product.

Elimination of inhibitory effects of dodecyl dimethyl benzyl ammonium chloride on microalgae in wastewater by cocultivation with a newly screened microbial consortium.

As one of the most commonly used biocidal cationic surfactants, benzalkonium chlorides (BACs) have been an increasing concern as emerging contaminants. Wastewater has been claimed the main point for BACs to enter into the environment, but to date, it is still largely unknown how the BACs affect the microbes (especially microalgae) in the practical wastewater and how to cost-effectively remove them. In this study, the inhibitory effects of a typical BACs, dodecyl dimethyl benzyl ammonium chloride (DDBAC), on a green microalga Chlorella sp. in oxidation pond wastewater were investigated. The results showed that though a hermetic effect at the first 2 days was observed with the DDBAC at low concentration (<6 mg/L), the algal growth and photosynthesis were significantly inhibited by the DDBAC at all the tested concentrations (3 to 48 mg/L). Fortunately, a new microbial consortium (MC) capable of degrading DDBAC was screened through a gradient domestication method. The MC mainly composed of Wickerhamomyces sp., Purpureocillium sp., and Achromobacter sp., and its maximum removal efficiency and removal rate of DDBAC (48 mg/L) respectively reached 98.1 % and 46.32 mg/L/d. Interestingly, a microbial-microalgal system (MMS) was constructed using the MC and Chlorella sp., and a synergetic effect between the two kinds of microorganisms was proposed: microalga provided oxygen and extracellular polysaccharides as co-metabolic substrates to help the MC to degrade DDBAC, while the MC helped to eliminate the DDBAC-induced inhibition on the alga. Further, by observing the seven kinds of degradation products (mainly including CH5O3P, C6H5CH2-, and C8H11N), two possible chemical pathways of the DDBAC degradation were proposed. In addition, the metagenomic sequencing results showed that the main functional genes of the MMS included antibiotic-resistant genes, ABC transporter genes, quorum sensing genes, two-component regulatory system genes, etc. This study provided some theoretical and application findings for the cost-effective pollution prevention of BACs in wastewater.

Palladium N-Heterocyclic Carbene-Catalyzed Aminations: An Outline.

Amination reactions play a pivotal role in synthetic organic chemistry, facilitating the generation of nitrogen-containing scaffolds with broad applications in drug synthesis, material production, polymer formation, and the generation of amino acids and peptides. Amination offers the potential to fine tune the properties of natural products and produce functional materials for various applications. Palladium N-heterocyclic carbene (Pd-NHC) emerges as an innovative and highly effective catalyst in this context. Under favorable reaction conditions, this robust and simple catalyst efficiently facilitates the synthesis of a diverse range of compounds with varying complexity and utility. Pd-NHC complexes exhibit significant σ-electron donating potential, enhancing the ease of the oxidative addition process in their mechanistic pathway. Their steric topography further contributes to a rapid reductive elimination. These complexes demonstrate remarkable stability, a result of the strong Pd-ligand bond. The wide variety of Pd-NHC complexes has proven highly efficient in catalyzing reactions across a spectrum of complexities, from simple to intricate. The domain of aminations catalyzed by Pd-NHC has undergone significant diversification, presenting new opportunities, particularly in the realms of material chemistry and natural product synthesis. This review outlines the advancements in Pd-NHC-catalyzed amination reactions, covering literature up to date.

Ligand Relay for Nickel-Catalyzed Decarbonylative Alkylation of Aroyl Chlorides.

Transition metal-catalyzed direct decarboxylative transformations of aromatic carboxylic acids usually require high temperatures, which limit the substrate's scope, especially for late-stage applications. The development of the selective decarbonylative of carboxylic acid derivatives, especially the most fundamental aroyl chlorides, with stable and cheap electrophiles under mild conditions is highly desirable and meaningful, but remains challenging. Herein, a strategy of nickel-catalyzed decarbonylative alkylation of aroyl chlorides via phosphine/nitrogen ligand relay is reported. The simple phosphine ligand is found essential for the decarbonylation step, while the nitrogen ligand promotes the cross-electrophile coupling. Such a ligand relay system can effectively and orderly carry out the catalytic process at room temperature, utilizing easily available aroyl chlorides as an aryl electrophile for reductive alkylation. This discovery provides a new strategy for direct decarbonylative coupling, features operationally simple, mild conditions, and excellent functional group tolerance. The mild approach is applied to the late-stage methylation of various pharmaceuticals. Extensive experiments are carried out to provide insights into the reaction pathway and support the ligand relay process.

Cobalt-Catalyzed Electroreductive Alkylation of Unactivated Alkyl Chlorides with Conjugated Olefins.

Reactions of unactivated alkyl chlorides under mild and sustainable conditions are rare compared to those of alkyl bromides or iodides. As a result, synthetic methods capable of modifying the vast chemical space of chloroalkane reagents, wastes, and materials are limited. We report the cobalt-catalyzed reductive addition of unactivated alkyl chlorides to conjugated alkenes. Co-catalyzed activation of alkyl chlorides is performed under electroreductive conditions, and the resulting reactions constitute formal alkyl-alkyl bond formation. In addition to developing an operationally simple methodology, detailed mechanistic studies provide insights into the elementary steps of a proposed catalytic cycle. In particular, we propose a switch in the mechanism of C-Cl bond activation from nucleophilic substitution to halogen atom abstraction, which is critical for efficiently generating alkyl radicals. These mechanistic insights were leveraged in designing ligands that enable couplings of primary, secondary, and tertiary alkyl chlorides.

Werner Salt as Nickel and Ammonia Source for Photochemical Synthesis of Primary Aryl Amines.

Cheap, stable and easy-to-handle Werner ammine salts have been known for more than a century; but they have been rarely used in organic synthesis. Herein, we report that the Werner hexammine complex [Ni(NH3 )6 ]Cl2 can be used as both a nitrogen and a catalytic nickel source that allow for the efficient amination of aryl chlorides in the presence of a catalytic amount of bipyridine ligand under the irradiation of 390-395 nm light without the need of any additional catalysts. More than 80 aryl chlorides, including more than 20 drug molecules, were aminated, demonstrating the practicality and generality of this method in synthetic chemistry. A slow NH3 release mechanism is in operation, obviating the problem of catalyst poisoning. Still interestingly, we show that the Werner salt can be easily recovered and reused, solving the problem of difficult recovery of transition metal nickel catalysts. The protocol thus provides an efficient new strategy for the synthesis of primary aryl amines.

Bismuth and Chlorine Dual-Doped Perovskite Chloride as a Phase-Structure-Stable and Moisture-Resistant Solid Electrolyte for Chloride Ion Batteries.

Perovskite chloride, an anion conductor, is a promising candidate to be a solid electrolyte for high-energy and sustainable chloride ion batteries (CIB). However, it suffers from poor structural stability at low temperature and in ambient conditions, which leads to its transformation from an ionic conductor to an insulator. Herein, a bismuth and chlorine dual doping strategy is developed to stabilize the cubic structure of CsSnCl3 in harsh environments. The as-prepared dual-doped CsSn0.9 Bi0.1 Cl3.1 material with an optimized composition maintains its cubic structure at the extremely low temperature of 213 K for 10 days and at 40% relative humidity for 50 days, while the undoped cubic material deteriorates and transforms to a monoclinic phase under these conditions in less than 1 day. Consequently, the dual doping achieves efficient chloride ion conduction that is superior to single bismuth doping due to the introduction of interstitial chlorine facilitating chloride ion transport. Importantly, the practicality of the as-prepared solid electrolyte is demonstrated in different symmetric solid cells and by various CIBs using the organic electrode couple, a multivalent metal chloride cathode, or a new high-voltage metal oxychloride cathode.

Facile Synthesis of Anhydrous Rare-Earth Trichlorides from their Oxides in Chloridoaluminate Ionic Liquids.

Wide applications of anhydrous rare-earth (RE) trichlorides RECl3 in organometallic chemistry, for the synthesis of optical and magnetic materials, and as catalysts require a facile approach for their synthesis. The known methods use or produce toxic substances, are complicated and have limited reliability and upscaling. It has been shown that task-specific ionic liquids (ILs) can dissolve many metal oxides without special reaction conditions at moderate temperature, making the metals accessible to downstream chemistry. Using imidazolium chloridoaluminate ILs, pure crystalline anhydrous RECl3 (RE=La-Nd, Sm-Dy) can be synthesized in one step from RE oxides in high yield. The Lewis acidic IL acts as solvent and reaction partner. The by-product [Al4 O2 Cl10 ]2- , which was detected spectroscopically, remains in solution. The reacted IL can be removed quantitatively by washing. ILs with various imidazolium cations and AlCl3 content and the effect of temperature and reaction time were tested.

Synthesis of Ketonylated Carbocycles via Excited-State Copper-Catalyzed Radical Carbo-Aroylation of Unactivated Alkenes.

Carbocycles are core skeletons in natural and synthetic organic compounds possessing a wide diversity of important biological activities. Herein, we report the development of an excited-state copper-catalyzed radical carbo-aroylation of unactivated alkenes to synthesize ketonylated tetralins, di- and tetrahydrophenanthrenes, and cyclopentane derivatives. The reaction is operationally simple and features mild reaction conditions that tolerate a broad range of functional groups. Preliminary mechanistic studies suggest a reaction pathway beginning with photoexcitation of [CuI-BINAP]2 and followed by a single electron transfer (SET), radical aroylation of unactivated alkenes, radical cyclization, and re-aromatization, affording the desired ketonylated carbocycles.

Risks of benzalkonium chlorides as emerging contaminants in the environment and possible control strategies from the perspective of ecopharmacovigilance.

An unprecedented increase in the use of disinfection products triggered by the coronavirus disease 2019 (COVID-19) pandemic is resulting in aggravating environmental loads of disinfectants as emerging contaminants, which has been considered a cause for worldwide secondary disasters. This review analyzed the literature published in the last decade about occurrence, bioaccumulation, and possible environmental risks of benzalkonium chlorides (BKCs) as emerging contaminants. Results indicated that BKCs globally occurred in municipal wastewater, surface water, groundwater, reclaimed water, sludge, sediment, soil, roof runoff, and residential dust samples across 13 countries. The maximum residual levels of 30 mg/L and 421 µg/g were reported in water and solid environmental samples, respectively. Emerging evidences suggested possible bioaccumulation of BKCs in plants, even perhaps humans. Environmentally relevant concentrations of BKCs exert potential adverse impacts on aquatic and terrestrial species, including genotoxicity, respiratory toxicity, behavioural effects and neurotoxicity, endocrine disruption and reproductive impairment, phytotoxicity, etc. Given the intrinsic biocidal and preservative properties of disinfectants, the inductive effects of residual BKCs in environment in terms of resistance and imbalance of microorganisms have been paid special attention. Considering the similarities of disinfectants to pharmaceuticals, from the perspective of ecopharmacovigilance (EPV), a well-established strategy for pharmaceutical emerging contaminants, we use the control of BKC pollution as a case, and provide some recommendations for employing the EPV measures to manage environmental risks posed by disinfectant emerging contaminants.