Stereodivergent Total Synthesis of Tacaman Alkaloids.

This paper describes a concise, asymmetric and stereodivergent total synthesis of tacaman alkaloids. A key step in this synthesis is the biocatalytic Baeyer-Villiger oxidation of cyclohexanone, which was developed to produce seven-membered lactones and establish the required stereochemistry at the C14 position (92 % yield, 99 % ee, 500 mg scale). Cis- and trans-tetracyclic indoloquinolizidine scaffolds were rapidly synthesized through an acid-triggered, tunable acyl-Pictet-Spengler type cyclization cascade, serving as the pivotal reaction for building the alkaloid skeleton. Computational results revealed that hydrogen bonding was crucial in stabilizing intermediates and inducing different addition reactions during the acyl-Pictet-Spengler cyclization cascade. By strategically using these two reactions and the late-stage diversification of the functionalized indoloquinolizidine core, the asymmetric total syntheses of eight tacaman alkaloids were achieved. This study may potentially advance research related to the medicinal chemistry of tacaman alkaloids.

Bond-Engineered MoSe2 Nanosheets with Expanded Layers and an Enriched 1T Phase for Highly Efficient Na+ Storage.

MoSe2 has attracted significant interest for Na+ storage due to its large interlayer distance, favorable band gap structure, and satisfying theoretical specific capacity. Nevertheless, the poor conductivity and large volume stress/strain always lead to poor cycle stability and limited rate capability. Herein, the P-Se bond and phase engineering strategies are proposed to enhance the stability of MoSe2 with the assistance of carbon compositing. Systematical characterizations confirm that the presence of a strong P-Se bond can ensure the good structural stability and enlarge the layer distance of the MoSe2 anode. 1T phase-enriched composition endows excellent conductivity and thus fast Na+ transport kinetics. Additionally, the combination of carbon contributes to the improvement of electron conductivity, further enhancing the reversible Na+ storage and cyclic stability. Consequently, an ultrastable reversible specific capacity of 347.8 mAh g-1 with a high retention ratio of 99.1% can be maintained after 1000 cycles at 1 A g-1, which is superior to the previous reports of MoSe2 nanosheets. The presented strategy is ingenious, offering an effective guidance to designing advanced electrodes to be applied in rechargeable batteries with a long lifespan.

Linear Codes Constructed from Two Weakly Regular Plateaued Functions with Index (p - 1)/2.

Linear codes are the most important family of codes in cryptography and coding theory. Some codes only have a few weights and are widely used in many areas, such as authentication codes, secret sharing schemes and strongly regular graphs. By setting p≡1(mod4), we constructed an infinite family of linear codes using two distinct weakly regular unbalanced (and balanced) plateaued functions with index (p-1)/2. Their weight distributions were completely determined by applying exponential sums and Walsh transform. As a result, most of our constructed codes have a few nonzero weights and are minimal.

The contribution of Ca and Mg to the accumulation of amino acids in maize: from the response of physiological and biochemical processes.

BACKGROUND: The quality of maize kernels is significantly enhanced by amino acids, which are the fundamental building blocks of proteins. Meanwhile, calcium (Ca) and magnesium (Mg), as important nutrients for maize growth, are vital in regulating the metabolic pathways and enzyme activities of amino acid synthesis. Therefore, our study analyzed the response process and changes of amino acid content, endogenous hormone content, and antioxidant enzyme activity in kernels to the coupling addition of sugar alcohol-chelated Ca and Mg fertilizers with spraying on maize. RESULT: (1) The coupled addition of Ca and Mg fertilizers increased the Ca and Mg content, endogenous hormone components (indole-3-acetic acid, IAA; gibberellin, GA; zeatin riboside, ZR) content, antioxidant enzyme activity, and amino acid content of maize kernels. The content of Ca and Mg in kernels increased with the increasing levels of Ca and Mg fertilizers within a certain range from the filling to the wax ripening stage, and significantly positively correlated with antioxidant enzyme activities. (2) The contents of IAA, GA, and ZR continued to rise, and the activities of superoxide dismutase (SOD) and catalase (CAT) were elevated, which effectively enhanced the ability of cells to resist oxidative damage, promoted cell elongation and division, and facilitated the growth and development of maize. However, the malondialdehyde (MDA) content increased consistently, which would attack the defense system of the cell membrane plasma to some extent. (3) Leucine (LEU) exhibited the highest percentage of essential amino acid components and a gradual decline from the filling to the wax ripening stage, with the most substantial beneficial effect on essential amino acids. (4) CAT and SOD favorably governed essential amino acids, while IAA and MDA negatively regulated them. The dominant physiological driving pathway for the synthesis of essential amino acids was "IAA-CAT-LEU", in which IAA first negatively drove CAT activity, and CAT then advantageously controlled LEU synthesis. CONCLUSION: These findings provide a potential approach to the physiological and biochemical metabolism of amino acid synthesis, and the nutritional quality enhancement of maize kernel.

Cystathionine γ-lyase-derived H2S negatively regulates thymic egress via allosteric inhibition of sphingosine-1-phosphate lyase.

Thymic egress is a crucial process for thymocyte maturation, strictly regulated by sphingosine-1-phosphate lyase (S1PL). Recently, cystathionine γ-lyase (CSE), one of the enzymes producing hydrogen sulfide (H2S), has emerged as a vital immune process regulator. However, the molecular connection between CSE, H2S and thymic egress remains largely unexplored. In this study, we investigated the regulatory function of CSE in the thymic egress of immune cells. We showed that genetic knockout of CSE or pharmacological inhibition by CSE enzyme inhibitor NSC4056 or D,L-propargylglycine (PAG) significantly enhanced the migration of mature lymphocytes and monocytes from the thymus to the peripheral blood, and this redistribution effect could be reversed by treatment with NaHS, an exogenous donor of H2S. In addition, the CSE-generated H2S significantly increased the levels of S1P in the peripheral blood, thymus and spleen of mice, suppressed the production of proinflammatory cytokines and rescued pathogen-induced sepsis in cells and in vivo. Notably, H2S or polysulfide inhibited S1PL activity in cells and an in vitro purified enzyme assay. We found that this inhibition relied on a newly identified C203XC205 redox motif adjacent to the enzyme's active site, shedding light on the biochemical mechanism of S1PL regulation. In conclusion, this study uncovers a new function and mechanism for CSE-derived H2S in thymic egress and provides a potential drug target for treating S1P-related immune diseases.

Strain Self-Adaptive Iron Selenides Toward Stable Na+-Ion Batteries with Impressive Initial Coulombic Efficiency.

High tap density electrodes play a vital role in developing rechargeable batteries with high volumetric capacities, however, developing advanced electrodes with satisfied capacity, excellent structural stability, and achieving the resulted batteries with a high initial Coulombic efficiency (ICE) and good rate capability with long lifespan simultaneously, are still an intractable challenge. Herein, an ultrahigh ICE of 94.1% and stable cycling of carbon-free iron selenides anode is enabled with a high tap density of 2.57 g cm-3 up to 4000 cycles at 5 A g-1 through strain-modulating by constructing a homologous heterostructure. Systematical characterization and theoretical calculation show that the self-adaptive homologous heterointerface alleviates the stress of the iron selenide anodes during cycling processes and subsequently improves the stability of the assembled batteries. Additionally, the well-formed homologous heterostructure also contributes to the rapid Na+ diffusion kinetic, increased charge transfer, and good reversibility of the transformation reactions, endowing the appealing rate capability of carbon-free iron selenides. The proposed design strategy provides new insight and inspiration to aid in the ongoing quest for advanced electrode materials with high tap densities and excellent stability.

[Thinking from Horqin Grassland to Horqin Sandy Land]. / 从科尔沁草原到科尔沁沙地的思考.

We systematically elaborated and compared the spatial scope and landscape changes of Horqin Grassland and Horqin Sand Land from their definitions and ranges. Horqin Grassland is an area with geographical units named after Mongolian tribes, but the boundary is unclear. Horqin Sand Land is also an area that borrows tribal names, but has independent topographic and geomorphic units, and clear boundaries. Horqin Grassland and Horqin Sand Land belong to two spatial regions that are both cross and different. The area and range of Horqin Grassland are larger than that of Horqin Sand Land which has obvious regional characteristics, and is a typical and research object area to study the development and restoration of aeolian desertification. Based on those cognition, we summarized the technologies and example models of comprehensive land management and desertification controlling over the years, and finally sorted out what should be focused on in the future to serve the annihilation war against desertification for Horqin Sand Land.

Analysis of the clinical efficacy of visualization of percutaneous endoscopic lumbar discectomy combined with annulus fibrosus suture in lumbar disc herniation.

The objective of this study is to compare the clinical effectiveness of visualization of percutaneous endoscopic lumbar discectomy (VPELD) combined with annulus fibrosus suture technique and simple percutaneous endoscopic lumbar discectomy (PELD) technique in the treatment of lumbar disc herniation. A retrospective analysis was conducted on 106 cases of lumbar disc herniation treated with foraminoscopic technique at our hospital from January 2020 to February 2022. Among them, 33 cases were treated with VPELD combined with annulus fibrosus suture in group A, and 73 cases were treated with PELD in group B. The preoperative and postoperative visual analogue scale (VAS), functional index (Oswestry Disability Index, ODI), healing of the annulus fibrosus, intervertebral space height, and postoperative recurrence were recorded and compared between the two groups. All patients underwent preoperative and postoperative MRI examinations, and the average follow-up period was 12 ± 2 months. Both groups showed significant improvements in postoperative VAS and ODI scores compared to the preoperative scores (P < 0.05), with no statistically significant difference between the groups during the same period (P > 0.05). There was no significant decrease in intervertebral space between the two groups after surgery (P > 0.05). Group A showed significantly lower postoperative recurrence rate and better annulus fibrosus healing compared to group B (P < 0.05). The VPELD combined with annulus fibrosus suture technique is a safe, feasible, and effective procedure for the treatment of lumbar disc herniation. When the indications are strictly adhered to, this technique can effectively reduce the postoperative recurrence rate and reoperation rate. It offers satisfactory clinical efficacy and can be considered as an alternative treatment option for eligible patients.

Ca and Mg stimulate protein synthesis in maize kernel through the action of endogenous hormones and defense enzymes.

Soil calcium (Ca) and magnesium (Mg) mineral states in rain-fed arid regions of Northwest China are inefficient, and their levels of substitution and water-soluble states are far below the lowest threshold required for maize growth, resulting in frequent physiological diseases, restricting synthesis of kernel protein (CRP). Our study set up different levels of foliar spraying of Ca and Mg fertilizers before maize pollination to examine the response characteristics of physiological and biochemical indicators in kernel, and the driving process of CRP synthesis. The main findings were: (1) Ca and Mg significantly increased the levels of CRP and endogenous hormones, and the activities of defense enzymes and CRP synthesis enzymes, which decreased significantly and stabilized at the maturity stage of maize. (2) The synthesis and accumulation of CRP were synergistically regulated by endogenous hormones, defense enzymes, and CRP synthase enzymes, with the degree of regulation varying with the level of Ca and Mg supplementation. Indole-3-acetic acid (IAA), gibberellin (GA), zeatin riboside (ZR), catalase (CAT), malondialdehyde (MDA), and glutamate dehydrogenase (GDH) were the primary physiological driving indicators of CRP synthesis, with CRP having a significant synergistic relationship with CAT and a remarkable trade-off with other driving indicators. (3) The dominant driving pathway of CRP synthesis was "Ca, Mg-IAA or GA or ZR-CAT-GDH-CRP". Ca and Mg positively affected IAA and GA levels, and IAA and GA positively regulated CAT activity. However, CAT negatively regulated GDH levels, causing GDH to negatively influence the synthesis and accumulation of CRP and its components. The findings provide theoretical support for further study of inter-root endogenous hormones and soil microbe-driven processes in the regulation of maize quality by Ca and Mg.

Asymmetric pre-growing season warming may jeopardize seed reproduction of the sand-stabilizing shrub Caragana microphylla.

Our current understanding of the processes and mechanisms by which seasonal asymmetric warming affects seed reproduction in semiarid regions, which are essential in preserving the stability of both vegetation ecosystem structure and function, remains poorly understood. Here, we conducted a field warming experiment, including pre-growing season warming (W1), in-growing season warming (W2), and combined pre- and in-growing season warming (W3) treatments, to investigate the seed reproductive strategy of Caragana microphylla, an important sand-stabilizing shrub, from the perspective of reproductive phenology, reproductive effort, and reproductive success. Results show that the warming treatments advanced the initial stages of reproductive phenology, prolonged its duration, and decreased its synchrony (magnitude = W3 > W2 > W1). Additionally, flowering phenology was more sensitive to warming than podding phenology. The W1 treatment inclined seed reproduction towards the conservative strategy with low reproductive effort and success. The W3 treatment tended to increase seed reproductive effort and success. While the W2 treatment did not affect reproductive success, it did increase reproductive effort. Changes in reproductive phenology explained 20 % of the variation in reproductive effort and 38 % of the variation in reproductive success. However, these changes also directly hindered reproductive success (direct effect = -0.57) while indirectly promoting reproductive success (indirect effect = 0.27) by increasing reproductive efforts. Our results reveal that the seasonal asymmetry of warming altered the seed reproduction strategy of sand-stabilizing shrubs, with warmer winters and springs before the growing season decreasing seed fecundity.