Electrochemistry is undergoing a resurgence in synthetic chemistry and has compelling advantages1. Repurposing natural enzymes through synthetic chemical strategies holds promise for exploring new chemical space2-6. Elegant strategies, including directed evolution7-10, artificial enzymes11 and photoenzymatic catalysis12,13, have demonstrated their capacities for expanding the applications of enzymes in both academia and industry. However, the integration of electrochemistry with enzymes has primarily been limited to replicating previously established enzyme functions14-16. Key challenges in achieving new enzyme reactivity with electricity include compatibility issues and difficulties in heterogeneous electron transfer. Here we report the reshaping of thiamine-dependent enzymes with ferrocene-mediated electrocatalysis to unlock an unnatural dynamic kinetic oxidation of α-branched aldehydes. This robust electroenzymatic approach yields various bioactive (S)-profens with up to 99% enantiomeric excess; it is applicable with whole cells overexpressing the enzyme and using down to 0.05 mol% enzyme loadings. Mechanistic investigations show multiple functions of the electroenzyme in precise substrate discrimination, accelerating racemization and facilitating kinetically matched electron transfer events.
Prenyl modification often improves the biological activities of compounds. Prenyltransferases have attracted attention as environmentally friendly biocatalysts for catalyzing prenyl modification of compounds. Compared to dimethylallyl modifications, research on geranyl modifications is relatively limited. To enrich biocatalytic toolboxes for generating potentially bioactive geranylated derivatives, this study developed methodologies to synthesize two types of geranylated compounds, i. e., geranylated tryptophan-containing cyclic dipeptides and geranylated naphthols, employing the F253G mutant of CdpC3PT, a cyclic dipeptide prenyltransferase from Neosartorya fischeri. The cyclic dipeptides (1-3) were transformed into C7-geranylated products (1G1-3G1), whereas 1-naphthol (4) and derivatives (5-6) yielded C4-geranylated products (4G1-6G1) and 2,7-dihydroxynaphthalene (7) generated a C3-geranylated product (7G1). All seven substrates and their geranylated products underwent antibacterial efficacy testing against Bacillus subtilis. Among them, five geranylated compounds (2G1 and 4G1-7G1) demonstrated antibacterial efficacies against Bacillus subtilis, with MIC values ranging from 4 to 32 μg/mL, surpassing their non-geranylated precursors. This research broadens the tools of geranyl-modifying biocatalysts, illustrates a case for developing highly efficient or function-altered biocatalysts and showcases the potential of prenyltransferases in the biosynthesis of bioactive small molecules.
共同富裕目标为乡村健康服务提供了新思路与新要求.从共同富裕的视角来看,发展乡村健康服务可以带动乡村经济可持续发展,促进健康公平,提升乡村健康治理水平.乡村健康服务长期面临着医疗资源配置不均衡、健康服务体制机制运行不畅、健康保障领域的城乡身份差别以及农民对基层医疗低度信任等问题.推动乡村健康服务发展要紧扣"富裕"和"共享"两个目标,从提升农民自身健康服务获取能力和乡村健康服务供给能力两个层次着手,通过发展乡村健康产业来赋能乡村经济,促进农民持续增收;通过优化城乡居民医保制度、优化健康服务供给体系、推动分级诊疗制度和医疗体制改革等增强乡村健康服务供给能力.
近年来积分制被广泛运用于乡村公共事务治理当中.为什么传统的积分制会在新时代乡村公共治理中重新焕发出生命力?其治理效能在新时代是如何发挥的?本文基于"动因-过程"的分析框架,通过湖南省D村的个案考察,分析了乡村公共治理中积分制的产生动因、运行机制以及实践效果.研究发现,积分制产生于行政与自治失衡引致的乡村公共治理自治组织基础动摇、村庄人情社会等非正式制度失灵导致的社会基础削弱.经由组织的整合、政府的推动以及社会的确认,最终形成了动力协调、组织调整、社会嵌入的运行机制.积分制通过激励农户参与在实践中既发挥了促进乡村治理关系的协调、社会治理的落实以及发展建设的共享等治理效能,同时也出现了引发组织创新惰性、降低干群之间的信任度以及目标替代等制度"异化"现象.
Prenylation usually improves structural diversity and bioactivity in natural products. Unlike the discovered enzymatic gem-diprenylation of mono- and tri-cyclic aromatic systems, the enzymatic approach for gem-diprenylation of bi-cyclic hydroxynaphthalenes is new to science. Here we report an enzymatic example for dearomative C4 gem-diprenylation of α-hydroxynaphthalenes, by the F253G mutant of a fungal prenyltransferase CdpC3PT. Experimental evidence suggests a sequential electrophilic substitution mechanism. We also explained the alteration of catalytic properties on CdpC3PT after mutation on F253 by modeling. This study provides a valuable addition to the synthetic toolkit for compound prenylation and it also contributes to the mechanistic study of prenylating enzymes.
目前市场和社会组织等多元主体被纳入养老服务的供给体系中,养老服务在供给主体上初步呈现出多元化.然而在长者用餐服务的实证研究中,依据组织整合的视角,同时从体制、结构、运行三个层面对养老服务中多元主体的整合情况进行分析,发现目前的养老服务供给体系虽然在供给主体上呈现出多元化,但不同主体之间欠缺整合.优化养老服务的多元合作供给,必须从服务规划者、多元主体供给架构、信息沟通机制方面着手,建构多元供给主体的整合框架.
乡村文化振兴战略背景下,新乡贤为破解当前农村公共文化服务供给严重不足的困境提供了新的思路.基于“双层认同与行动模型”,以湖南省石羊塘镇为对象研究新乡贤在公共文化服务供给中的作用.研究发现,新乡贤扮演了政府、社会、市场与村民之间的沟通者角色,发挥了反馈村民公共文化需求、协助政府履行文化服务职能、整合社会公益文化资源、促进市场力量参与的作用,并从三个维度阐述了新乡贤参与的作用机理:乡土认同是基础,组织认同是保障,身份认同是核心.政府应该充分发挥新乡贤的作用,有效提升农村公共文化服务水平.
以CNKI数据库中的311篇CSSCI来源期刊论文以及Web Of Science平台中的716篇核心合集库文献作为研究样本,运用CiteSpace5.6.R2软件进行可视化计量分析,发现既有健康乡村研究文献的主要议题有乡村居民个体健康影响因素、乡村中的特殊群体健康、乡村健康风险与健康保障三个方面,国内研究与国外研究在议题设置阶段上有些许差别.进一步分析可知,国内研究将集中于乡村振兴战略和乡村治理现代化,相关重点议题有:"大健康"理念下的健康乡村研究、健康乡村政策研究、健康乡村韧性度提升研究、数字化健康乡村研究.
<span id="ChDivSummary" name="ChDivSummary" class="abstract-text">2020年之后,相对贫困将成为中国贫困的主要形式。相对贫困受到哪些因素的影响,城市人口中的本地居民与流动人口的贫困致因是否存在差异?本文基于制度视角构建了"制度结构-个体行动-贫困形成"的分析框架,运用二元Logistic回归模型和中国综合社会调查2015年度的数据,分析了公共服务供给、生计资本(物质资本、人力资本和社会资本)以及生计策略对相对贫困的影响。研究结果显示,相对贫困的发生是一个包含制度结构和个体行动因素的缺失集;城市相对贫困的形成存在空间分异,物质资本、人力资本对流动人口发挥了更为显著的致贫效应,城镇人口则在公共服务供给和生计策略对相对贫困的影响上呈现出显著性。相对贫困治理应该统筹城乡扶贫、深化配套制度改革,以及充分利用互联网等现代信息技术。本文深化了贫困致因的制度分析,凸显了基本公共服务的减贫作用,进一步强化了主观能动性在脱贫中的作用。未来应该结合农村相对贫困开展研究,比较城镇贫困与农村贫困致因的差异并统筹治理城乡相对贫困。</span>
Biflavonoids are pharmaceutically important compounds. Prenylation usually improves bioactivity; however, prenylated biflavonoids are rare in nature. Here, we report successful prenylation or geranylation of biflavonoids using fungal prenyltransferase CdpC3PT and its mutants. F253 was identified as a key residue related to donor selectivity, which enables the switching from utilizing DMAPP to GPP precisely at the same C-3''' site of biflavonoids. Furthermore, another residue W181 was discovered to generally increase prenylation activity toward biflavonoids.
地方治理是国家治理体系的重要组成部分.通过CiteSpace软件对CSSCI期刊论文进行计量分析,发现我国地方治理研究的主题有地方公民参与、地方治理现代化、地方政府与社会关系、地方治理变革实践四类.未来地方治理的研究应该聚焦于地方部门治理的精准化、地方同协作治理的常态化和中国地方治理经验的国际化.
Prenylation increases the bioactivity of flavonoids. Herein, we report the first examples of regioselective enzymatic geranylation of biflavonoids using Aspergillus terreus aromatic prenyltransferase (AtaPT). For biflavonoids 1-3 dimerized through a diphenyl linkage, geranylation occurs at the hydrogen bond involving C5 "-OH group, which is less chemically accessible than other OH groups in the molecule. This study would be referential for developing green synthetic solutions for prenylated biflavonoids.
任何组织都有其使命追求.有些社会组织并不具备扶贫的使命,却在履行扶贫的责任.不符合使命要求的责任承担会降低扶贫绩效.农村扶贫中的社会组织的根本使命是在保证组织发展的前提下,满足贫困农民的现实需求而非政府的需求.其责任主要是动员扶贫资源、参与扶贫规划、开展公民教育;承接政府职能、呈现农民需求并监督政府.责任的履行要坚持使命限度、能力限度和优势限度.
信任关系是政府与社会组织交往中不可避免的主题.传统研究多认为信任关系只包含信任,并赋予其绝对正面的意义.然而此种单一视角无法解释当代中国政府与社会组织间互动的复杂性与矛盾性.基于对《中国NGO口述史》的分析发现,在政府与社会组织的交往中,信任与不信任共生共存、利害兼施,都具备积极的正向功能和消极的负向功能.要合理发挥信任的正外部性,重视信任的非对称性和强迫性,同时妥善处理不信任的激励性,高度重视不信任的消耗性,构建政府与社会组织间理性适度的良性信任关系.
深度贫困地区的贫困主要表现为物质资本、人力资本和社会资本等“三维资本”的短缺.政府治理工具、市场治理工具和社会治理工具在该地区发挥了重要作用,但是其选择不当也造成深度贫困地区难以脱贫,表现为:过于强势的政府治理工具影响扶贫绩效、强调盈利的市场治理工具排斥真正的贫困者、尚显稚嫩的社会治理工具缺乏持续的扶贫能力.要实现可持续脱贫,必须结合贫困农民需求,既要有差异化个性化,又要立足长远地优化配置治理工具.
新中国成立以来,乡村内生秩序先后经历了建国初期的行政渗透、人民公社时期的双重挤压、改革开放初期的重获新生以及后税费时期的转型生长四个阶段.随着国家政权建设、社会改造运动以及市场化改革进程的加快,利益分化的组织形态、契约主导的市场秩序、组织化的社会关联正在重塑内生秩序的社会基础和组织基础.透过“制度—过程—能力”的三维分析框架,可见村庄场域中内生秩序的逻辑演进路线.在权威主体自觉性的制度安排、利益主体策略性的调适行动以及人际能量场赋予的行动能力的运行机制下,制度嵌入与内生秩序达致适配能够降低制度的嵌入成本,避免乡村治理的内卷化,实现乡村治理体系的动态平衡.
Relocation aimed at poverty alleviation is one of the main ways to eliminate poverty accurately.With more than thirty years of practice of relocation aimed at poverty alleviation,a large number of related research re-sults have emerged.Through reviewing and sorting out,we can find that the existing researches mainly focus on four aspects:the policy process,the implementation and resettlement,the follow-up development of immigrants and benefit evaluation.These documents have laid foundation for the current research,but there are also some problems.Follow-up research should be expanded in developing and innovating mechanisms and policies of reloca-tion aimed at alleviate poverty,improving and enhancing the grassroots governance structure and governance capac-ity in poverty alleviation,formulating targeted follow-up poverty alleviation measures and exploring effective com-bination of relocation aimed at poverty alleviation and long-term regional development planning.
Based on the theoretical analysis of the literature, this paper compares the indexes of GDP, fiscal revenue, import and export volume, foreign trade dependency and utilization of foreign capital in the four cities of the middle reaches of the Yangtze River and Hunan Province, and compares the horizontal and vertical multi-analysis, selection of Yueyang City case study. The study argues that opening is the general trend of development. Yueyang open and development both the advantages of superior location, good industry, the platform has a complete foundation and advantages, but also the industry level is not high, the project pull weak, poor development environment and short board, must be more open vision and mind, take the initiative to deal with, grab Grasp the opportunity, learn from experience, momentum and on. On this basis, from the ideological emancipation, the introduction of large projects, do a strong platform to encourage large "sea", optimize the environment and other five aspects, targeted to open the rise of the specific path and strategy.
政策议程是公共政策研究的重要领域.现有研究着重分析政策议程的动力、类型及过程,较少阐述政策议程的心理基础.本文从心理视角来分析政策议程、传播与注意力的心理基础及机制.分析结果显示,政策议程有个体和社会两种心理机制.非理性因素的风险条件认知和时间距离影响个体的心理机制,社会偏见和社会服从影响了社会的心理机制.政策议程传播有人际传播、媒介传播和公共传播三种方式,且都受到信任、情感、直觉及信任等心理要素的影响.注意力是政策议程与传播的心理反应机制,可通过聚焦机制、情景机制与配置机制影响政策议程与传播的形式及过程.
地方病是贫困地区致贫的一大根源,有效治理地方病型贫困是实现精准脱贫目标过程中不可回避的责任.在贫困恶性循环理论的基础上,通过构建地方病型贫困的双向恶性循环模型,深入分析地方病型贫困生成的供给与需求逻辑.在贫困地区的自我脱贫与发展能力欠缺的现实背景下,对地方病型贫困治理提出了供给与需求两方面的制度要求.供给性制度障碍与需求性制度障碍都严重制约着地方病型贫困的有效治理.前者包括不完善的地方病型贫困脱贫制度和较弱的政府治理能力,后者表现为居民守旧的生活习惯和落后的思想观念.应通过加大地方病型贫困治理制度的供给力度,提升地方病型贫困治理能力的供给水平,重塑地方病型贫困群体的脱贫需求,优化地方病型贫困的治理效果,助力农村贫困人口实现脱贫,进一步促进全面小康社会的建成.