Search

We report new pyridine-based donor-acceptor (D-A) molecules that enable the direct reductive transformation of a variety of secondary and tertiary aliphatic bromides. A series of experimental and theoretical results suggested that the D-A molecules promote direct C-Br bond cleavage triggered by the excitation of the complex between the catalyst and the aliphatic bromide and that the alkyl groups significantly contribute to the stabilization of the complex, which improves the efficiency of its excitation.

The purpose of this study is to explore the potential application of photobiomodulation to irritable bowel syndrome. We established the following experimental groups: the Non-Stress + Sham group, which consisted of rats that were not restrained and were only subjected to sham irradiation; the Stress + Sham group, which underwent 1 hour of restraint stress followed by sham irradiation; and the Stress + Laser group, which was subjected to restraint stress and percutaneous laser irradiation bilaterally on the L6 dorsal root ganglia for 5 minutes each. The experiment was conducted twice, with three and two laser conditions examined. Following laser irradiation, a barostat catheter was inserted into the rat's colon. After a 30-minute acclimatization period, the catheter was inflated to a pressure of 60 mmHg, and the number of abdominal muscle contractions was measured over a 5-minute period. The results showed that photobiomodulation significantly suppressed the number of abdominal muscle contractions at average powers of 460, 70, and 18 mW. However, no significant suppression was observed at average powers of 1 W and 3.5 mW. This study suggests that photobiomodulation can alleviate visceral hyperalgesia induced by restraint stress, indicating its potential applicability to irritable bowel syndrome., (© 2024. The Author(s).)

The introduction of a chlorine atom could potentially endow peptide derivatives with notable bioactivity and applicability. However, despite considerable recent progress in C(sp 3 )-H functionalization chemistry, a general method for the site-selective chlorination of inert aliphatic C-H bonds in peptides still remains elusive. Herein, we report a site-selective C(sp 3 )-H chlorination of oligopeptides based on an N -chloropeptide strategy. N -chloropeptides, which are easily prepared from the corresponding native oligopeptides, are smoothly degraded in the presence of an appropriate copper catalyst, and a subsequent 1,5-hydrogen atom transfer affords γ- or δ-chlorinated peptides in excellent yield. A wide variety of amino acid residues can thus be site-selectively chlorinated in a predictable manner. This method hence enables the efficient synthesis of otherwise less accessible, chlorine-containing peptide fragments of natural peptides. We moreover demonstrate here the successful estimation of the stereochemistry of the chlorinated carbon atom in aquimarin A. Furthermore, we reveal that side-chain-chlorinated peptides can serve as highly useful substructures with a fine balance between stability and reactivity, which renders them promising targets for synthetic and medicinal applications.

With the aim of achieving the convergent elongation of peptide chains, an amide bond formation reaction that enables a peptide fragment coupling has long been pursued. The decarboxylative amidation recently reported by our group is a potential solution to this problem. In this article, a mechanistic analysis of the t-butyl hydroperoxide (TBHP) mediated-decarboxylative amidation of α-ketoacids that results in a significant advance in convergent peptide synthesis is described. Despite the observation of epimerization with low bulk substrates in preliminary studies, a systematic examination and understanding of the reaction mechanism enabled the development of a modified epimerization-free reaction whereby peptide fragment couplings using peptide α-ketoacids were successfully achieved.

In this article, an electron donor-acceptor (EDA) complex between a triarylamine and B(C 6 F 5 ) 3 that catalyzes the dehydrogenative cross-coupling of phenols is described. We demonstrate, for the first time, that the use of both components of the radical ion pairs generated by the photoexcitation of the EDA complex as co-catalysts, and the triarylaminium radical cation ( +· NAr 3 ) successfully promotes dehydrogenative cross-coupling between electron-rich phenols and 2-naphthols to provide electron-rich biphenol motifs using molecular oxygen as a terminal oxidant.

Conventional methods for the construction of dehydroamino acids (ΔAAs), which are a unique class of non-proteinogenic amino acids, require the pre-installation of special amino acids. Herein, we report and demonstrate the practical utility of an N-chloropeptide strategy for the rapid construction of ΔAA-containing peptides. The electrophilic N-chlorination of peptide bonds is drastically accelerated by a catalytic amount of quinuclidine (ABCO), and the subsequent β-elimination of N-chloroamide efficiently provides ΔAA-containing peptides in high yield. The strategy enables, for the first time, the construction of a wide variety of ΔAA residues in peptides without any pre-functionalized side chains and facilitates the late-stage installation of ΔAA motifs into already-constructed oligopeptides, including a medicinally important macrocyclic peptide., (© 2022 Wiley-VCH GmbH.)

The homolytic cleavage of C-O bonds to afford alkyl radicals is an attractive yet challenging transformation in organic synthesis. Herein we describe a photocatalyzed deoxygenative C-C coupling reaction of xanthate salts, which can be easily prepared from the corresponding alcohols. The key to the success of this strategy is the low oxidation potential of the xanthate salt and the use of an appropriate phosphine to accelerate the desulfurative release of carbonyl sulfide.

A mild and chemoselective three-component thioesterification using olefins, α-ketoacids, and elemental sulfur has been developed. The photocatalytic activation of elemental sulfur, a cheap and abundant sulfur source, enables the rapid installation of a sulfur atom into molecules, reactions that ordinarily would require the use of reactive and malodorous sulfur-containing compounds such as thiols and thioacids. This novel reaction is characterized by high yields and a broad substrate scope, which enables the introduction of thioester moieties into complex molecules including a steroid, a peptide, and a nonprotected glycoside. Mechanistic studies indicated that the success of this transformation depends on the multiple roles played by the elemental sulfur, including those of a sulfurizing agent, a terminal oxidant, and a HAT mediator.

Purpose: Vadadustat is an oral hypoxia-inducible factor-prolyl hydroxylase inhibitor approved in Japan for the treatment of anemia in chronic kidney disease. This study investigated drug-drug interactions between vadadustat and oral iron supplements or iron-containing phosphate binders commonly used in Japanese clinical practice by conducting in vitro mechanistic and clinical pharmacokinetic studies., Methods: In the in vitro assessment, chelate formation of vadadustat with iron-containing agents was investigated in water and in a fed-state simulated intestinal fluid. Chelate formation was assessed by observation of a chelate-specific color, and the concentration of vadadustat was determined. In the single-dose, open-label, randomized, crossover clinical study, healthy male participants received 150 mg of vadadustat with or without oral iron-containing agents. Pharmacokinetic data were collected for up to 24 hours after vadadustat administration. Participants were monitored for adverse events during the study., Findings: Vadadustat formed a chelate precipitate with ferrous sulfate and ferric nitrate, as shown by development of a specific bright orange color in water. The proportions of vadadustat dissolved in the supernatant were 2% and 18%, respectively. Vadadustat did not form a chelate precipitate in a fed-state simulated intestinal fluid in the presence of sodium ferrous citrate, ferric citrate hydrate, or sucroferric oxyhydroxide; the proportion of vadadustat in supernatant ranged from 63% to 89%. In the clinical pharmacokinetic study, coadministration of vadadustat with sodium ferrous citrate, ferric citrate hydrate, sucroferric oxyhydroxide, or ferrous sulfate decreased the AUC 0-∞ by 54.0% to 89.7% and C max by 42.1% to 91.9%. No serious adverse events were reported., Implications: Chelate formation of vadadustat with iron-containing agents was confirmed by in vitro analysis and depended on the type of iron-containing agent. The AUC 0-∞ and C max of vadadustat decreased when coadministered with oral iron-containing agents. Our data suggest that the decreases in AUC 0-∞ and C max are a result of chelation in the gastrointestinal tract; therefore, coadministration of iron-containing agents with vadadustat should use a dosing interval. ClinicalTrials.gov Identifier: NCT03645863., (Copyright © 2021 The Author(s). Published by Elsevier Inc. All rights reserved.)

This report describes the total synthesis of the complex, oxygenated tetracyclic alkaloid, lyconesidine B. The key synthetic challenge involves diastereoselective generation of a decahydroquinoline ring with a quaternary carbon at the angular position via domino cyclopropanation, ring-opening, and reduction. Another crucial step is the domino ene-yne metathesis involving a quaternary ammonium ion, leading to the construction of a decahydroazaazulen framework.

A mild and chemoselective method for the thioacylation of amines using α-keto acids and elemental sulfur has been developed. The key to the success of this transformation is the nucleophilic activation of elemental sulfur by thiols such as 1-dodecanethiol. A variety of functional groups, including unprotected hydroxyl, carboxyl, amide, sulfide, and tertiary amine moieties, are tolerated under the applied reaction conditions. To demonstrate the advantages of this method compared with conventional O-S exchange reactions using Lawesson's reagent or P 2 S 5 , thioamide moieties were introduced site-specifically into biologically active compounds.

Strategies for the formation of amide bonds, that is, one of the most basic and important transformations in organic synthesis, have so far focused predominantly on dehydration reactions. Herein, we report and demonstrate the practical utility of a novel decarboxylative amidation of α-ketoacids by using inexpensive tert-butyl hydroperoxide (TBHP), which is characterized by high yields, a broad substrate scope, mild reaction conditions, and a unique chemoselectivity. These features enable the synthesis of peptides from amino acid derived α-ketoacids under preservation of the stereochemical information., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

SiO2 film deposition and subsequent high‐temperature annealing resulted in the generation of a two‐dimensional electron gas (2DEG) at Al(Ga)N/GaN hetero‐interfaces, of which the 2DEG was originally fully depleted. The obtained mobilities and sheet carrier concentrations were over 1100 cm2/Vs and 3.0 × 1012 cm–2, respectively. Surface energy lowering, which is proof of the generated 2DEG, was observed by electron state analysis using hard X‐ray photoelectron spectroscopy. This damage‐less method that selectively generates a 2DEG can contribute not only toward improving some characteristics in existing devices but also toward creating entirely novel devices. [ABSTRACT FROM AUTHOR]

The inefficient endosomal escape of drugs or macromolecules is a major obstacle to achieving successful delivery to therapeutic targets. An efficient approach to circumvent this barrier is photochemical internalization (PCI), which uses light and photosensitizers for endosomal escape of the delivered macromolecules. The PCI mechanism is related to photogenerated singlet oxygen, but the mechanism is still unclear. In this study, we examined the relation of PCI to heat, pH and Ca 2+ ions using cell penetrating peptide (CPP)-cargo-photosensitizer (Alexa546 or Alexa633) conjugates. A cell temperature changing experiment demonstrated that heat (thermal mechanism) does not significantly contribute to the photoinduced endosomal escape. Inhibition of V-ATPase proton pump activity and endosomal pH upregulation indicated that PCI-mediated endosomal escape needs endosomal acidification prior to photoirradiation. Imaging of the CPP-cargo-photosensitizer and Ca 2+ ions during photostimulation showed that intracellular calcium increase is not the cause of the endosomal escape of the complex. The increment is mainly due to Ca 2+ influx. These findings show the importance of extra- and intracellular milieu conditions in the PCI mechanism and enrich our understanding of PCI-related changes in cell., (© 2019 American Society for Photobiology.)

Despite significant progress in the development of site-selective aliphatic C-H oxidations over the past decade, the ability to oxidize strong methylene C-H bonds in the presence of more oxidatively labile aromatic functionalities remains a major unsolved problem. Such chemoselective reactivity is highly desirable for enabling late-stage oxidative derivatizations of pharmaceuticals and medicinally important natural products that often contain such functionality. Here, we report a simple manganese small-molecule catalyst Mn(CF 3 -PDP) system that achieves such chemoselectivity via an unexpected synergy of catalyst design and acid additive. Preparative remote methylene oxidation is obtained in 50 aromatic compounds housing medicinally relevant halogen, oxygen, heterocyclic and biaryl moieties. Late-stage methylene oxidation is demonstrated on four drug scaffolds, including the ethinylestradiol scaffold where other non-directed C-H oxidants that tolerate aromatic groups effect oxidation at only activated tertiary benzylic sites. Rapid generation of a known metabolite (piragliatin) from an advanced intermediate is demonstrated.

Plant WRKY transcription factors are responsible for biotic and abiotic stresses and play an important role in enhancing their adaptability. The AtWRKY33 is a gene that functions in response to abiotic stresses such as low temperature, drought, salinity, etc. In this study, a recombinant vector YG8198-ZmWRKY53 carrying the ZmWRKY53, an interspecific homolog of the dicotyledonous AtWRKY33, was transferred to rice plants by Agrobacterium mediated transformation. The ectopic expression of the ZmWRKY53 in transgenic rice plants conferred cold tolerance with a higher accumulation of free proline and water-soluble sugars, an increase in chlorophyll content, a decrease in electrolyte leakage rate and MDA levels compared to control plants. This result suggests that ZmWRKY53 may confer cold tolerance in rice., (© 2024. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

The high‐frequency characteristics of high electron mobility transistors applying AlGaN for a channel layer (AlGaN channel HEMTs) with greater impacts of alloy disorder scattering than those in conventional HEMTs with a GaN channel layer (GaN channel HEMTs) are investigated. The obtained electron saturation velocity was 4.7 × 106 cm/s and the cutoff frequency was 7 GHz in the AlGaN channel HEMTs with a gate length of 1 μm. These results are promising for several gigahertz band operations of AlGaN channel HEMTs. [ABSTRACT FROM AUTHOR]

An α-ketoacid could be converted into a reactive acylating agent by treatment with hypervalent iodine(III) species, and in so doing, we discovered a novel decarboxylative acylation of alcohols that affords a variety of esters in excellent yields. The esterification has been applied to a sterol bearing a free carboxylic acid and shows unique chemoselectivity. The procedure is racemization-free and operates under mild conditions.

Cost-effective and feasible methods for early diagnosis of Alzheimer's disease (AD) are needed. We present two methods to measure AD-related biomarkers simultaneously from one nasal smear for the purpose of diagnosing AD. Japanese men and women aged 63-85 years old were recruited in 2015-2016 for this case-control study. A total of 25 AD cases and 25 controls (22 men and 28 women) participated in this research. Nasal smears were collected from the common nasal meatus, inferior concha, middle nasal meatus, and olfactory cleft, and the proteins in the samples were analyzed by two methods, which we named PGD (Pre-treatment with guanidine- n-Dodecyl-beta-D-maltoside solution) method 1 (PGD-I) and 2 (PGD-II). The PGD-I method measured total tau and amyloid-β (Aβ)42, but no differences in median levels of total tau and Aβ42 between AD cases and controls were found in any of the nasal locations. The PGD-II method measured Aβ42, total tau, and phosphorylated tau, but levels of Aβ40 in all nasal locations of both groups were near zero. Median levels of phosphorylated tau to total tau (p-tau/t-tau) ratios in the middle nasal meatus and in the olfactory cleft were significantly higher in AD cases than in controls, and could significantly predict AD. To assess diagnostic reliability, areas under the ROC curve were 0.74 (95% CL = 0.52-0.95, p = 0.030) for the middle nasal meatus and 0.72 (95% CL = 0.52-0.92, p = 0.029) for the olfactory cleft. Thus, PGD-I and PGD-II can detect AD-related biomarkers in nasal smears and PGD-II may be a useful tool for diagnosing AD.

The buffer layer in AlGaN channel HEMTs to suppress the off-state drain leakage current is investigated. By employing an AlN for the buffer layer in Al0.39Ga0.61N/Al0.16Ga0.84N HEMTs, the off-state drain leakage current was sufficiently suppressed and the breakdown voltage was enhanced. It was considered that employing the AlN for the buffer layer is important for extracting the superior material properties of the AlGaN in the channel layer. [ABSTRACT FROM AUTHOR]

The fundamental device characteristics of AlGaN channel high electron mobility transistors formed on 4H-SiC and sapphire substrates are compared, and it is found that the drivability is apparently better for the SiC substrate. Judging from the simultaneous enhancement in mobility and the carrier concentration of the two-dimensional electron gases for the SiC substrate, the advantages of the SiC substrate originate from the excellent crystal quality of the AlGaN channel layer including the interface with the AlGaN barrier layer, which should be due to less lattice mismatch with the substrate. [ABSTRACT FROM AUTHOR]

Amide-containing molecules are ubiquitous in natural products, pharmaceuticals, and materials science. Due to their intermediate electron-richness, they are not amenable to any of the previously developed N-protection strategies known to enable remote aliphatic C-H oxidations. Using information gleaned from a systematic study of the main features that makes remote oxidations of amides in peptide settings possible, we developed an imidate salt protecting strategy that employs methyl trifluoromethanesulfonate as a reversible alkylating agent. The imidate salt strategy enables, for the first time, remote, nondirected, site-selective C(sp 3 )-H oxidation with Fe(PDP) and Fe(CF 3 PDP) catalysis in the presence of a broad scope of tertiary amides, anilide, 2-pyridone, and carbamate functionality. Secondary and primary amides can be masked as N-Ns amides to undergo remote oxidation. This novel imidate strategy facilitates late-stage oxidations in a broader scope of medicinally important molecules and may find use in other C-H oxidations and metal-mediated reactions that do not tolerate amide functionality.

LHY/CCA1 genes play a key role in the plant circadian clock system and are highly conserved among plant species. However, the evolutionary process of the LHY/CCA1 gene family remains unclear in angiosperms. To obtain details of the phylogeny of these genes, this study characterized LHY/CCA1 genes in a model woody plant,Populus tree.The evolutionary process of angiosperm LHY/CCA1 genes was elucidated using three approaches: comparison of exon–intron structures, reconstruction of phylogenetic trees and examination of syntenic relationships. In addition, the molecular evolutionary rates and the expression patterns of Populus LHYs were analyzed.Gene duplication events of Populus LHYs and Arabidopsis LHY/CCA1 had occurred independently by different chromosomal duplication events arising in each evolutionary lineage. Populus LHYs were under purifying selection by estimating substitution rates of these genes. Further, Populus LHYs conserved diurnal expressions in leaves and stems but the transcripts of LHY2 were more abundant than those of LHY1 in Populus plants.This study uncovered phylogenetic relationships of the LHY/CCA1 gene family in angiosperms. In addition, the transcript abundance and the evolutionary differences between Populus LHY1 and LHY2 imply that Populus LHY2, rather than LHY1, may have a major role in the Populus clock system.

The synthesis of benzocyclobutenes from simple arenes bearing a directing group was investigated via the palladium-catalyzed cyclization of norbornene derivatives. This approach allowed for the facile construction of benzocyclobutenes along with the double functionalization of the C-H bonds at the positions ortho and meta to the directing group. This result shows that the key palladacyclopentene intermediate in the Catellani reaction can be prepared by the directed double ortho C-H activation of the substrate. The results of this study also revealed that the combination of an N-protected amino acid with benzoquinone (BQ) was effective for this transformation.

To characterize the genes for enzymes involved in the biosynthesis of polyamines (PAs), their expression profiles were investigated and the levels of PAs in Arabidopsis thaliana quantified. In the Arabidopsis genome, eight genes involved in PAs biosynthesis were identified and the expression profiles of these genes were analysed, not only under abiotic stress to determine whether they were stress-inducible, constitutive, or stress-repressible, but also in various organs to show their tissue specificity. AtADC2 and AtSPMS mRNAs, encoding arginine decarboxylase and spermine synthase, clearly increased in response to NaCl and dehydration and abscisic acid treatments. Stress-inducible accumulation of AtADC2 mRNA correlated with putrescine (Put) accumulation under NaCl and dehydration treatments. In a cold condition, AtSAMDC2 mRNA increased significantly. AtADC2 and AtSAMDC2 mRNA were expressed in sexual organs such as flowers, buds and immature siliques. PAs also accumulated in sexual organs. These results suggest that the transcripts of eight genes involved in PA biosynthesis show different profiles of expression not only in response to environmental stress but also during plant development. [ABSTRACT FROM AUTHOR]

Background: The Japanese cedar (Cryptomeria japonica D. Don) is one of the most important Japanese forest trees, occupying approximately 44% of artificial forests and planted in East Asia, the Azores Archipelago, and certain islands in the Indian Ocean. Although the huge genome of the species (ca. 9 Gbp) with abundant repeat elements may have represented an obstacle for genetic analysis, this species is easily propagated by cutting, flowered by gibberellic acid, transformed by Agrobacterium, and edited by CRISPR/Cas9. These characteristics of C. japonica recommend it as a model conifer species for which reference genome sequences are necessary. Results: Herein, we report the first chromosome-level assembly of C. japonica (2n = 22) using third-generation selfed progeny (estimated homozygosity rate = 0.96). Young leaf tissue was used to extract high molecular weight DNA (> 50 kb) for HiFi PacBio long-read sequencing and to construct an Hi-C/Omni-C library for Illumina short-read sequencing. The 29× and 26× genome coverage of HiFi and Illumina reads, respectively, for de novo assembly yielded 2,651 contigs (9.1 Gbp, N50 contig size 12.0 Mbp). Hi-C analysis mapped 97% of the nucleotides on 11 chromosomes. The assembly was verified through comparison with a consensus linkage map comprising 7,781 markers. BUSCO analysis identified ∼ 91% conserved genes. Conclusions: Annotations of genes and comparisons of repeat elements with other Cupressaceae and Pinaceae species provide a fundamental resource for conifer research. [ABSTRACT FROM AUTHOR]

In the South China Sea, a significant amount of methane hydrate exists in the sediment containing fine-grained soil. Increasing temperature and/or decreasing pore pressure can remarkably degrade the mechanical characteristics of this methane hydrate–bearing fine-grained sediment (HBFS). In this study, several compression tests under triaxial stress condition on HBFS are performed with changing temperature and pore pressure. The experimental results reveal that the HBFS specimen has an enhanced stiffness and failure strength characteristic under lower temperature and/or higher pore pressure conditions. An improved phase state parameter H is presented as a characterization for the temperature and pore pressure condition, which considers the capillary effect for HBFS with wide pore size distribution. The secant modulus and failure strength tend to linearly increase with the rising improved phase state parameter H. The internal friction angle is independent of the temperature and pore pressure, while the cohesion exhibits a significantly linear increase with the rising improved phase state parameter H. In addition, the shear–dilatancy curve shifts to the right with the rising improved state parameter H owing to the enhanced cementing strength of hydrate–soil cluster. These research findings are beneficial for grasping the mechanical behavior of HBFS. Furthermore, this research also provides data support for building the constitutive model of HBFS during methane hydrate recovery. [ABSTRACT FROM AUTHOR]

Background: Dirigent (DIR) genes play a key role in the development of organic products in plants. They confer conformational influence on processes that lack stereoselectivity and regioselectivity through processes that are mostly understood. They are required to produce lignans, which are a unique and widely distributed family of plant secondary metabolites with intriguing pharmacological characteristics and potential role in plant development. DIR genes are implicated in the process of lignification and protect plants from environmental stresses, including biotic and abiotic stresses. Nevertheless, no research has been performed on the DIR gene family in Solanum lycopersicum. This study provides detailed information on the DIR gene family in S. lycopersicum. Methods and results: The conserved domain analysis, phylogenetic analysis, evolutionary adaptation, cis-acting elements, proteomic analysis, signal peptide detection, transmembrane potential analysis, sequence identity and similarity analysis, gene assembly, genomic localization, duplication of gene analysis, and evolutionary linkage of 31 potential DIR genes were studied. All these analyses provide a deep understanding of DIR genes in the S. lycopersicum genome that will provide a useful reference for further functional analysis of the DIR genes in S. lycopersicum. Conclusion: This research provides an in-depth and comprehensive explanation of the detailed process and structural characterization of DIR genes in the genome of S. lycopersicum, laying the groundwork for future plant genetic engineering and crop development exploration. This work will provide valuable information for identifying DIR genes in higher plants and support future research on the DIR gene family. [ABSTRACT FROM AUTHOR]

Amino acids are essential building blocks in biology and chemistry. Whereas nature relies on a small number of amino acid structures, chemists desire access to a vast range of structurally diverse analogues1–3. The selective modification of amino acid side-chain residues represents an efficient strategy to access non-canonical derivatives of value in chemistry and biology. While semisynthetic methods leveraging the functional groups found in polar and aromatic amino acids have been extensively explored, highly selective and general approaches to transform unactivated C–H bonds in aliphatic amino acids remain less developed4,5. Here we disclose a stepwise dehydrogenative method to convert aliphatic amino acids into structurally diverse analogues. The key to the success of this approach lies in the development of a selective catalytic acceptorless dehydrogenation method driven by photochemical irradiation, which provides access to terminal alkene intermediates for downstream functionalization. Overall, this strategy enables the rapid synthesis of new amino acid building blocks and suggests possibilities for the late-stage modification of more complex oligopeptides.Effective dehydrogenation of amino acids and short peptides using cobalt and photocatalysis is used to make a range of unnatural products of value in chemistry and biology. [ABSTRACT FROM AUTHOR]

Jiuqu (starter) makes an important contribution to the formation of the flavor characteristics of Hongqu rice wine (HQW). Gutian Qu (GTQ) and Wuyi Qu (WYQ) are two kinds of Jiuqu commonly used in HQW brewing, but the comparison of the two kinds of HQW is still insufficient at present. The objective of this study was to compare the dynamic changes of amino acids (AAs), higher alcohols (HAs), bioamines (BAs), volatile flavor compounds (VFCs), and microbial communities in HQW fermentation, with GTQ and WYQ as starter. This study used an automatic amino acid analyzer, GC, HPLC, and GC-MS to detect AAs, HAs, Bas, and VFCs during fermentation; metagenomic sequencing technology was used to elucidate the microbial community and its functional characteristics. The results showed that the contents of AAs and HAs in HQW brewed with WYQ (WYW) were significantly higher than those in HQW brewed with GTQ (GTW). On the contrary, the majority of BAs in GTW were significantly higher than those in WYW. The composition of VFCs in WYW and GTW were obviously different, as most of the VFCs were notably enriched in WYW, while ethyl caproate, isoamyl acetate, ethyl heptanoate, ethyl nonanoate, 1-decanol, citronellol, phenethyl acetate, and hexanoic acid were more abundant in GTW. Burkholderia gladioli, Pantoea dispersa, Weissella cibaria, Monascus purpureus, and Saccharomyces cerevisiae were the predominant microbial populations in GTW brewing at the species level, while Sphingomonas sp., Kosakonia cowanii, Enterobacter asburiae, Leuconostoc lactis, Aspergillus niger, and Saccharomyces cerevisiae were the dominant microbial species in WYW brewing. The abundance of functional genes involved in BAs biosynthesis were much higher in GTW brewing, while the abundance of functional genes related to the metabolism of characteristic VFCs were much higher in WYW brewing. Collectively, these findings provided evidence for elucidating the effects of Jiuqu and microbial communities on HQW flavor quality, and laid a solid foundation for the improvement of HQW flavor quality. [ABSTRACT FROM AUTHOR]

To improve the efficiency of coalbed methane and recoverability of reservoirs, enhanced fracturing technology is usually required to improve the low porosity and permeability status of coal reservoirs. As a feasible method for strengthening permeability, microwave–LN2 freeze–thaw (MLFT) cycles modify the microscopic pore structure of coal through the coupled effect of temperature stress changes, phase change expansion, and fatigue damage. 1H nuclear magnetic resonance combined with fractal dimension theory was used to characterize quantitatively the pore system and geometric features of coal. The geometric fractal model constructed using the T2 spectrum indicates that the fractal dimensions Dp and De have high fitting accuracy, demonstrating that percolation and effective pores exhibit good fractal characteristics. Dp and De are correlated negatively and positively, respectively, with the cyclic parameters. The relevance analysis shows that the NMR fractal method can reflect the pore–fracture heterogeneity of coal, which has a significant effect on the percentage of fluid migration space. This study reveals that MLFT cycles have significant enhancement effects on promoting the extension of multi-type pores structures within the coal matrix, as well as the connectivity and permeability of cracks. [ABSTRACT FROM AUTHOR]

This review highlights the use of DACH as a versatile ligand in catalytic asymmetric transformations providing mechanistic rationales and relevant comments presented in chronological order for each of the 21 reaction types with references up to December 25, 2023. Intended to be as practically comprehensive as possible, this review assembles useful examples of using DACH as a ligand in organocatalytic or as metal complexes in asymmetric transformations. The resulting enantiomerically enriched, if not pure, chiral non-racemic small molecules are of great utility as value added intermediates in the total synthesis of natural products, in the design and synthesis of medicinally important compounds, and in other areas in organic and bioorganic chemistry where chirality plays a role. The graphic image depicts Spartacus with his arms folded in the same sense of chirality as (R , R)-DACH. 1 Introduction 2 DACH: A Brief Historical Narrative 3 Catalytic Asymmetric Hydrogenation of Alkenes 4 Catalytic Asymmetric Dihydroxylation of Alkenes 5 Catalytic Asymmetric Sulfoxidation and Sulfimidation 6 Catalytic Asymmetric 1,4-Conjugate Addition 6.1 Using Jacobsen's DACH Metal–salen Complexes as Catalysts 6.2 Using Takemoto's Bifunctional H-Bonding DACH Thiourea Organocatalyst 6.3 Using DACH Ni(II) Complexes as Catalysts 6.4 Using DACH H-Bonding Catalysis 7 Catalytic Asymmetric Epoxidation of Alkenes 8 Catalytic Asymmetric Claisen Rearrangement 9 Catalytic Asymmetric 1,2-Nucleophilic Addition to Carbonyl Compounds 9.1 Catalytic Asymmetric Addition of Dialkylzinc to Aldehydes and Ketones 9.2 Catalytic Asymmetric Alkynylation of Aldehydes and Ketones 9.3 Catalytic Asymmetric Addition of Cyanide to Aldehydes and Ketones 10 Catalytic Asymmetric Allylic Alkylation 11 Catalytic Asymmetric Cyclopropanation of Alkenes 12 Catalytic Asymmetric Cycloaddition Reactions 13 Catalytic Asymmetric Aziridination of Alkenes 14 Catalytic Asymmetric Hydrogenation of Prochiral Ketones and Imines 15 Catalytic Asymmetric Aldol Reactions 16 Catalytic Asymmetric Opening of Small Ring Systems 16.1 Desymmetrization of meso -Epoxides and meso -Aziridines 16.2 Kinetic Resolution of Racemic Epoxides 16.3 Enantioselective Addition of CO2 to Epoxides 16.4 Enantioselective Ring Opening of Oxetanes 17 Catalytic Asymmetric Strecker Reactions 18 Catalytic Asymmetric Mannich Reactions 19 Catalytic Asymmetric Henry and Aza-Henry Reactions 20 Catalytic Asymmetric Morita–Baylis–Hillman and Rauhut–Currier Reactions 21 Catalytic Asymmetric Petasis Reactions 22 Organocatalytic Asymmetric Cascade Reactions 23 Miscellaneous Catalytic Reactions 24 Conclusion and Outlook 25 DACH Catalysts and Ligands List [ABSTRACT FROM AUTHOR]

A photooxidation approach to the conversion of phosphines into the corresponding phosphine oxides is reported. By taking advantage of O2 in the air as an oxidant and oxygen source, phosphine oxides were obtained efficiently in moderate to excellent yields. A four-coordinated organoboron compound was used as the photocatalyst to activate O2 to its singlet state. This photooxidation method features mild reaction conditions, broad functional-group tolerance, and a wide substrate scope. [ABSTRACT FROM AUTHOR]