The Histone Variant H3.3 Is Required for Plant Growth and Fertility in Arabidopsis.

Histones are the core components of the eukaryote chromosome, and have been implicated in transcriptional gene regulation. There are three major isoforms of histone H3 in Arabidopsis. Studies have shown that the H3.3 variant is pivotal in modulating nucleosome structure and gene transcription. However, the function of H3.3 during development remains to be further investigated in plants. In this study, we disrupted all three H3.3 genes in Arabidopsis. Two triple mutants, h3.3cr-4 and h3.3cr-5, were created by the CRISPR/Cas9 system. The mutant plants displayed smaller rosettes and decreased fertility. The stunted growth of h3.3cr-4 may result from reduced expression of cell cycle regulators. The shorter stamen filaments, but not the fertile ability of the gametophytes, resulted in reduced fertility of h3.3cr-4. The transcriptome analysis suggested that the reduced filament elongation of h3.3cr-4 was probably caused by the ectopic expression of several JASMONATE-ZIM DOMAIN (JAZ) genes, which are the key repressors of the signaling pathway of the phytohormone jasmonic acid (JA). These observations suggest that the histone variant H3.3 promotes plant growth, including rosette growth and filament elongation.

A review on the transformation of birnessite in the environment: Implication for the stabilization of heavy metals.

Birnessite is ubiquitous in the natural environment where heavy metals are retained and easily transformed. The surface properties and structure of birnessite change with the changes in external environmental conditions, which also affects the fate of heavy metals. Clarifying the effect and mechanism of the birnessite phase transition process on heavy metals is the key to taking effective measures to prevent and control heavy metal pollution. Therefore, the four transformation pathways of birnessite are summarized first in this review. Second, the relationship between transformation pathways and environmental conditions is proposed. These relevant environmental conditions include abiotic (e.g., co-existing ions, pH, oxygen pressure, temperature, electric field, light, aging, pressure) and biotic factors (e.g., microorganisms, biomolecules). The phase transformation is achieved by the key intermediate of Mn(III) through interlayer-condensation, folding, neutralization-disproportionation, and dissolution-recrystallization mechanisms. The AOS (average oxidation state) of Mn and interlayer spacing are closely correlated with the phase transformation of birnessite. Last but not least, the mechanisms of heavy metals immobilization in the transformation process of birnessite are summed up. They involve isomorphous substitution, redox, complexation, hydration/dehydration, etc. The transformation of birnessite and its implication on heavy metals will be helpful for understanding and predicting the behavior of heavy metals and the crucial phase of manganese oxides/hydroxides in natural and engineered environments.

Base-Promoted Formal (3 + 2) Cycloaddition of α-Halohydroxamates with Electron-Deficient Alkenyl-iminoindolines To Synthesize Spiro-indolinepyrrolidinones.

Construction of pyrrolidinyl-spiroindoles with easily available starting materials has attracted considerable attention from the synthesis community and is in great demand. Here, we describe a base-promoted formal (3 + 2) cycloaddition of α-halohydroxamates with alkenyl-iminoindolines. The present methodology features mild reaction conditions and a broad substrate scope with up to 99% yield and excellent diastereoselectivity. The versatility of this approach is demonstrated through valuable synthetic transformations. Preliminary mechanistic studies shed light on the mechanism of this cycloaddition process.

Capture gaseous arsenic in flue gas by amorphous iron manganese oxides with high SO2 resistance.

In non-ferrous metal smelting, the problem of gaseous arsenic in high-sulfur flue gas is difficult to solve. Now we have developed oxygen-enriched amorphous iron manganese oxide (AFMBO) based on the unique superiority of iron-manganese oxide for arsenic capture to realize the effective control of gaseous arsenic in the non-ferrous smelting flue gas. The experimental results show that the arsenic adsorption capacity of AFMBO is up to 102.7 mg/g, which has surpassed most of the current adsorbents. In particular, AFMBO can effectively capture gaseous arsenic even at 12% v/v SO2 concentrations (88.45 mg/g). Moreover, the spent AFMBO possesses pronounced magnetic characteristics that make it easier to separate from dust, which is conducive to reducing the secondary environmental risk of arsenic. In terms of mechanism study, various characterization methods are used to explain the important role of lattice oxygen and adsorbed oxygen in the capture process of gaseous arsenic. Moreover, the reason for the efficient arsenic removal performance of AFMBO is also reasonably explained at the microscopic level. This study provides ideas and implications for gaseous arsenic pollution control research.

Influence of Educational Background on Untreated Dental Caries and Gingival Bleeding.

Objective: This study aims to investigate the impact of educational background on the occurrence of untreated dental caries and gingival bleeding, shedding light on the potential implications for public health policy and dental care. Methods: The study was conducted among 160 80 Shenggong Technology Company employees. An online questionnaire survey was administered to collect relevant data, focusing on the participants' educational backgrounds, income levels, and oral hygiene practices. Educational achievements were categorized into two groups: MSDB: middle school degree or below, and CDA: college degree or above. A team of three experienced dentists conducted comprehensive oral health assessments, evaluating untreated dental caries and the presence of gingival bleeding. Dental caries results were categorized as follows: less than 2 untreated dental caries, 2-4 untreated dental caries, or more than 4 untreated dental caries. Gingival bleeding results were classified as 0, slight, or severe. Statistical analysis was performed using SPSS software (IBM, Armonk, NY, USA), employing Fisher's exact test to compare untreated dental caries and gingival bleeding prevalence between the two educational background groups. Significance was determined at P < .05. Results: The analysis included 40 participants with an MSDB and 40 with a CDA. The findings revealed no significant differences in age or gender distribution between these groups. However, participants with an MSDB exhibited a significantly higher incidence of untreated dental caries (P = .0008) and were more likely to experience gingival bleeding (P = .0397) compared to their counterparts with a college degree or above. Conclusions: This study underscores that individuals with an educational background of a middle school degree or below are more prone to both untreated dental caries and gingival bleeding compared to those with a higher educational background.

SWATH-MS-Based Proteomics Reveals the Regulatory Metabolism of Amaryllidaceae Alkaloids in Three Lycoris Species.

Alkaloids are a class of nitrogen-containing alkaline organic compounds found in nature, with significant biological activity, and are also important active ingredients in Chinese herbal medicine. Amaryllidaceae plants are rich in alkaloids, among which galanthamine, lycorine, and lycoramine are representative. Since the difficulty and high cost of synthesizing alkaloids have been the major obstacles in industrial production, particularly the molecular mechanism underlying alkaloid biosynthesis is largely unknown. Here, we determined the alkaloid content in Lycoris longituba, Lycoris incarnata, and Lycoris sprengeri, and performed a SWATH-MS (sequential window acquisition of all theoretical mass spectra)-based quantitative approach to detect proteome changes in the three Lycoris. A total of 2193 proteins were quantified, of which 720 proteins showed a difference in abundance between Ll and Ls, and 463 proteins showed a difference in abundance between Li and Ls. KEGG enrichment analysis revealed that differentially expressed proteins are distributed in specific biological processes including amino acid metabolism, starch, and sucrose metabolism, implicating a supportive role for Amaryllidaceae alkaloids metabolism in Lycoris. Furthermore, several key genes collectively known as OMT and NMT were identified, which are probably responsible for galanthamine biosynthesis. Interestingly, RNA processing-related proteins were also abundantly detected in alkaloid-rich Ll, suggesting that posttranscriptional regulation such as alternative splicing may contribute to the biosynthesis of Amaryllidaceae alkaloids. Taken together, our SWATH-MS-based proteomic investigation may reveal the differences in alkaloid contents at the protein levels, providing a comprehensive proteome reference for the regulatory metabolism of Amaryllidaceae alkaloids.

The determinants of effective defluorination by the LiAl-LDHs.

Millions of people in poor areas are still under the threat of fluoride contamination. How to effectively separate fluorine in water is an important step to reduce the ecological risk. In this paper, we performed a systematic DFT calculation focused on the defluorination behavior between the LiAl- and MgAl-LDHs. The results indicated that the LiAl-LDHs exhibited high chemical activity before the defluorination, because of the better electronic structure. After the defluorination, the LiAl-LDHs with adsorbed-F- were also more stable than the MgAl-LDHs. In addition, the existence of coordination covalent bond for the adsorbed-F- attached to the LiAl-LDHs was confirmed. This is an important reason for the high defluorination efficiency by the LiAl-LDHs. In addition, a series of weak interaction, including hydrogen bond and van der Waals interaction were also observed. Finally, a LiAl-LDHs with excellent fluoride removal properties were synthesized well by simple hydrothermal method. The results showed that our synthesized LiAl-LDHs with the capacity of 156.09 mg/g, could be effectively defluorinated in water. Notably, it surpasses most materials and has potential applications.

Systematic control technologies for gaseous pollutants from non-ferrous metallurgy.

Air pollutant emissions represent a critical challenge in the green development of the non-ferrous metallurgy industry. This work studied the emission characteristics, formation mechanisms, phase transformation and separation of typical air pollutants, such as heavy metal particles, mercury, sulfur oxides and fluoride, during non-ferrous smelting. A series of purification technologies, including optimization of the furnace throat and high-temperature discharge, were developed to collaboratively control and recover fine particles from the flue gas of heavy metal smelting processes, including copper, lead and zinc. Significant improvements have been realized in wet scrubbing technology for removing mercury, fluoride and SO2 from flue gas. Gas-liquid sulfidation technology by applying H2S was invented to recycle the acid scrubbing wastewater more efficiently and in an eco-friendly manner. Based on digital technology, a source reduction method was designed for sulfur and fluoride control during the whole aluminum electrolysis process. New desulfurization technologies were developed for catalytic reduction of the sulfur content in petroleum coke at low temperature and catalytic reduction of SO2 to elemental sulfur. This work has established the technology for coupling multi-pollutant control and resource recovery from the flue gas from non-ferrous metallurgy, which provides the scientific theoretical basis and application technology for the treatment of air pollutants in the non-ferrous metallurgy industry.

Direct Acylation of Unactivated Alkyl Halides with Aldehydes through N-Heterocyclic Carbene Organocatalysis.

Catalytic acylation of organohalides with aldehydes is an ideal strategy for the direct synthesis of ketones. However, the utilization of unactivated alkyl halides in such a transformation remains a formidable challenge. In this study, we developed a cross-coupling reaction of aldehydes with unactivated alkyl halides through N-heterocyclic carbene catalysis. With this protocol, various ketones could be rapidly synthesized from readily available starting materials under mild conditions. This organocatalytic system was successfully applied in the late-stage functionalization of pharmaceutical derivatives. Mechanistic investigations suggest a closed-shell nucleophilic substitution mechanism for this reaction.

Radical Acylalkylation of 1,3-Enynes To Access Allenic Ketones via N-Heterocyclic Carbene Organocatalysis.

An N-heterocyclic carbene organocatalytic 1,4-difunctionalization of 1,3-enynes was developed. This organocatalytic strategy was suitable for a broad spectrum of substrates to efficiently synthesize allenic ketones bearing diverse substituents. Preliminary mechanistic studies suggest a radical reaction pathway for this organocatalytic acylalkylation process.

Sulphur ylide-mediated cyclopropanation and subsequent spirocyclopropane rearrangement reactions.

The efficient construction of cyclopropyl spiroindoline skeletons and the exploration of related follow-up synthetic transformations have elicited considerable interest amongst members of the chemistry community. Here, we describe a formal (2 + 1) annulation and three-component (1 + 1 + 1) cascade cyclisation via sulphur ylide cyclopropanation under mild conditions. The spiro-cyclopropyl iminoindoline moiety can be readily transformed into another medicinally interesting pyrrolo[3,4-c]quinoline framework through a novel rearrangement process.

Deep eutectic solvent for spent lithium-ion battery recycling: comparison with inorganic acid leaching.

Deep eutectic solvents (DESs) as novel green solvents are potential options to replace inorganic acids for hydrometallurgy. Compared with inorganic acids, the physicochemical properties of DESs and their applications in recycling of spent lithium-ion batteries were summarized. The viscosity, metal solubility, toxicological properties and biodegradation of DESs depend on the hydrogen bond donor (HBD) and acceptor (HBA). The viscosity of ChCl-based DESs increased according to the HBD in the following order: alcohols < carboxylic acids < sugars < inorganic salts. The strongly coordinating HBDs increased the solubility of metal oxide via surface complexation reactions followed by ligand exchange for chloride in the bulk solvent. Interestingly, the safety and degradability of DESs reported in the literature are superior to those of inorganic acids. Both DESs and inorganic acids have excellent metal leaching efficiencies (>99%). However, the reaction kinetics of DESs are 2-3 orders of magnitude slower than those of inorganic acids. A significant advantage of DESs is that they can be regenerated and recycled multiple times after recovering metals by electrochemical deposition or precipitation. In the future, the development of efficient and selective DESs still requires a lot of attention.

Fyn Signaling in Ischemia-Reperfusion Injury: Potential and Therapeutic Implications.

Ischemic stroke caused by arterial occlusion is the most common type of stroke and is one of the leading causes of disability and death, with the incidence increasing each year. Fyn is a nonreceptor tyrosine kinase belonging to the Src family of kinases (SFKs), which is related to many normal and pathological processes of the nervous system, including neurodevelopment and disease progression. In recent years, more and more evidence suggests that Fyn may be closely related to cerebral ischemia-reperfusion, including energy metabolism disorders, excitatory neurotoxicity, intracellular calcium homeostasis, free radical production, and the activation of apoptotic genes. This paper reviews the role of Fyn in the pathological process of cerebral ischemia-reperfusion, including neuroexcitotoxicity and neuroinflammation, to explore how Fyn affects specific signal cascades and leads to cerebral ischemia-reperfusion injury. In addition, Fyn also promotes the production of superoxide and endogenous NO, so as to quickly react to produce peroxynitrite, which may also mediate cerebral ischemia-reperfusion injury, which is discussed in this paper. Finally, we revealed the treatment methods related to Fyn inhibitors and discussed its potential as a clinical treatment for ischemic stroke.

The role of doped-Mn on enhancing arsenic removal by MgAl-LDHs.

To meet the challenges posed by global arsenic water contamination, the MgAlMn-LDHs with extraordinary efficiency of arsenate removal was developed. In order to clarify the enhancement effect of the doped-Mn on the arsenate removal performance of the LDHs, the cluster models of the MgAlMn-LDHs and MgAl-LDHs were established and calculated by using density functional theory (DFT). The results shown that the doped-Mn can significantly change the electronic structure of the LDHs and improve its chemical activity. Compared with the MgAl-LDHs that without the doped-Mn, the HOMO-LUMO gap was smaller after doping. In addition, the -OH and Al on the laminates were also activated to improve the adsorption property of the LDHs. Besides, the doped-Mn existed as a novel active site. On the other hand, the MgAlMn-LDHs with the doped-Mn, the increased of the binding energy, as well as the decreased of the ion exchange energy of interlayer Cl-, making the ability to arsenate removal had been considerably elevated than the MgAl-LDHs. Furthermore, there is an obvious coordination covalent bond between arsenate and the laminates of the MgAlMn-LDHs that with the doped-Mn.

Remote C(sp3 )-H Acylation of Amides and Cascade Cyclization via N-Heterocyclic Carbene Organocatalysis.

The direct functionalization of inert C(sp3 )-H bonds under environmentally benign catalytic conditions remains a challenging task in synthetic chemistry. Here, we report an organocatalytic remote C(sp3 )-H acylation of amides and cascade cyclization through a radical-mediated 1,5-hydrogen atom transfer mechanism using N-heterocyclic carbene as the catalyst. Notably, a diversity of nitrogen-containing substrates, including simple linear aliphatic carbamates and ortho-alkyl benzamides, can be successfully applied to this organocatalytic system. With the established protocol, over 120 examples of functionalized δ-amino ketones and isoquinolinones with diverse substituents were easily synthesized in up to 99 % yield under mild conditions. The robustness and generality of the organocatalytic strategy were further highlighted by the successful acylation of unactivated C(sp3 )-H bonds and late-stage modification of pharmaceutical molecules. Then, the asymmetric control of the radical reaction was attempted and proven feasible by using a newly designed chiral thiazolium catalyst, and moderate enantioselectivity was obtained at the current stage. Preliminary mechanistic investigations including several control reactions, KIE experiments, and computational studies shed light on the organocatalytic radical reaction mechanism.

Oxidative Radical NHC Catalysis: Divergent Difunctionalization of Olefins through Intermolecular Hydrogen Atom Transfer.

Oxidative N-heterocyclic carbene (NHC) organocatalysis, typically leading to the formation of acyl azolium reactive intermediates, constitutes one of the most important activation strategies for the NHC-catalyzed chemical transformations. Here, we report an unprecedented oxidative radical NHC catalysis by using peroxyester as the external single-electron oxidant to realize divergent difunctionalization of olefins. The key to success of this chemistry is the catalytic generation of oxygen radicals that could trigger an intermolecular hydrogen atom transfer to activate the inert C-H bonds, thereby enabling the productive radical relay process. With this protocol, commonly used general chemicals could serve as radical precursors to allow efficient synthesis of value-added products in a straightforward and cost-effective manner. Preliminary mechanistic investigations, including control experiments and DFT calculations, shed light on the NHC organocatalytic radical reaction mechanism.

Single-Electron Transfer Reactions Enabled by N-Heterocyclic Carbene Organocatalysis.

Over the past decades, N-heterocyclic carbene (NHC) organocatalysis has undergone a flourish of development on the basis of closed-shell reaction paths. By contrast, the emerging area of single-electron transfer (SET) reactions enabled by NHC catalysis still remain underdeveloped, but offer plenty of opportunities to develop new catalytic modes and useful synthetic methods. A number of interesting transformations were triggered by the SET process from the electron-rich Breslow intermediates to various single-electron acceptors. In additions, recent studies revealed that the Breslow radical cations could also be generated by single-electron reduction of the electron-deficient acyl azolium intermediates. These discoveries open a new avenue for NHC organocatalysis to harness radical reactions. The present review will focus on the exciting advancements in the dynamic area of radical NHC organocatalysis.

Changes in carbohydrate metabolism and endogenous hormone regulation during bulblet initiation and development in Lycoris radiata.

BACKGROUND: Lycoris species have great ornamental and medicinal values; however, their low regeneration efficiency seriously restricts their commercial production. Understanding the mechanism of bulblet propagation in this genus, which has remained underexplored to date, could provide a theoretical basis for improving the reproductive efficiency. Therefore, we studied the bulblet initiation and developmental processes in Lycoris radiata. RESULTS: We found that bulblets are formed on the junctions of the innermost layers of scales and the basal plate, and initially present as an axillary bud and gradually develop into a bulblet. We also determined the changes in carbohydrate and endogenous hormone contents during bulblet initiation and development, as well as the expression patterns of genes involved in carbohydrate metabolism and hormone biosynthesis and signaling through transcriptome analysis. Soluble sugars derived from starch degradation in the outer scales are transported to and promote bulblet initiation and development through starch synthesis in the inner scales. This process is mediated by several genes involved in carbohydrate metabolism, especially genes encoding ADP glucose pyrophosphorylase, a crucial starch synthesis enzyme. As for hormones, endogenous IAA, GA, and ABA content showed an increase and decrease during bulblet initiation and development, respectively, which were consistent with the expression patterns of genes involved in IAA, GA, and ABA synthesis and signal transduction. In addition, a decrease in ZR content may be down- and up-regulated by CK biosynthesis and degradation related genes, respectively, with increasing auxin content. Furthermore, expression levels of genes related to BR, JA, and SA biosynthesis were increased, while that of ethylene biosynthesis genes was decreased, which was also consistent with the expression patterns of their signal transduction genes. CONCLUSIONS: The present study provides insights into the effect of carbohydrate metabolism and endogenous hormone regulation on control of L. radiata bulblet initiation and development. Based on the results, we propose several suggestions to improve L. radiata propagation efficiency in production, which will provide directions for future research.

Bifunctional Brønsted Base Catalyzed [3 + 3] Annulations of Indolin-2-imines and α,ß-Unsaturated Imides: An Enantioselective Approach to α-Carbolinones.

Asymmetric construction of α-carbolinones with easily available starting materials has recently attracted considerable attention from the synthesis community, and the development of effective catalysis for this target is in great demand. Here, a bifunctional Brønsted base catalyzed asymmetric [3 + 3] cyclization of indolin-2-imines and α,ß-unsaturated N-acylated succinimides was developed by using the strategy of noncovalent bonding catalysis. With this organocatalytic protocol, a variety of tetrahydro-α-carbolinones bearing different substituents were synthesized with up to 99% yield and up to 96:4 er.

Palladium-catalysed decarboxylative annulations of vinylethylene carbonates leading to diverse functionalised heterocycles.

Heterocycles are the fundamental structural motifs found in natural products and biologically active compounds. The construction of these structures is therefore an important task in organic chemistry. Vinylethylene carbonates (VECs) are versatile building blocks that can undergo transition metal catalysed decarboxylation to enable various kinds of interesting transformations. This review provides an overview of the significant achievements of VECs in palladium-catalysed annulations over the past five years. The flexible reactivity of VECs is demonstrated by various [3 + 2], [5 + n] and other types of annulations, which could offer powerful protocols for accessing diverse functionalised heterocycles.