亜鉛結合タンパク質のモデルとしてのメタロチオネイン-3におけるサルフェン硫黄の役割

筑波大学 (University of Tsukuba)201

Chiral BINAP-based hierarchical porous polymers as platforms for efficient heterogeneous asymmetric catalysis

手性多孔有机聚合物具有较高的稳定性和催化活性,广泛用于多相不对称催化中.目前研究多集中在合成具有微孔结构的聚合物,而少有具有多种孔道结构(包含介; 孔和微孔)的聚合物的报道.之前我们报道了乙烯基修饰的BINAP配体,; (S)-5,5-divinyl-BINAP,将其与不同单体共聚后得到了一系列具有不同孔结构的有机聚合物.其负载的Rh基催化剂在苯乙烯不对称氢甲酰; 化反应中,表现出比均相更高的产物对映体选择性.本文采用不同的溴代步骤,合成了(S)-4,4-divinyl-BINAP配体.将这两种具有乙烯基官; 能团的手性配体按相同的摩尔比与二乙烯基苯(DVB)共聚,得到两种不同的有机聚合物.负载[RuCl_2(benzene)]_2后,分别得到Ru/4; -BINAP@POPs和Ru/5-BINAP@POPs-l.采用一锅法合成了催化剂Ru/5-BINAP@POPs-2;以[RuCl_2(p-cy; me)]_2和RuCl_3分别合成了Ru/5-BINAP@POPs-3和Ru/5-BINAP@POPs-4催化剂.; N_2物理吸附结果显示,Ru/4-BINAP@POPs和Ru/5-BINAP@POPs-l催化剂具有相似的孔道结构;而采用一锅法合成的Ru/5-; BINAP@POPs-2催化剂的介孔孔径较大.4-BINAP@POPs和5-BINAP@POPs聚合物的~(13)C核磁显示,其均在145,13; 7和128 ppm处有明显的吸收峰,可归结为萘环和苯环上的碳振动峰;在44.0; ppm处的峰归属为亚甲基上的碳振动峰;~(31)P核磁显示,在聚合物中P基本没有被氧化.将所得到的Ru/POPs催化剂应用于乙酰乙酸甲酯的多相不; 对称加氢反应中,Ru/5-BINAP@POPs-1催化剂具有与Ru/4-BINAP@POPs更快的反应速率.在相同反应条件下,催化剂活性大小为R; u/5-BINAP@POPs-l > Ru/5-BINAP@POPs-3 > Ru/5-BINAP@POPs-4 >; Ru/5-BINAP@POPs-2.另外Ru/5-BINAP@POPs-1催化剂对beta-酮酸酯有着较好的底物适应性,且在釜式反应中可循环使用; 6次而活性基本不变.分析发现,使用前后的催化剂均没有明显的Ru-Ru键的存在.表明Ru金属高度分散于催化剂上,且具有较高的稳定性,金属不易聚集,; 这也是其具有高活性和稳定性的原因.Two vinyl-functionalized chiral 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP) ligands, (S)-4,4'-divinyl-BINAP and (S)-5,5'-divinyl-BINAP, were successfully synthesized. Chiral BINAP-based porous organic polymers (POPs), denoted as 4-BINAP@POPs and 5-BINAP@POPs, were efficiently prepared via the copolymerization of vinyl-functionalized BINAP with divinyl benzene under solvothermal conditions. Thorough characterization using nuclear magnetic resonance spectroscopy, thermogravimetric analysis, extended X-ray absorption fine structure analysis, and high-angle annular dark-field scanning transmission electron microscopy, we confirmed that chiral BINAP groups were successfully incorporated into the structure of the materials considered to contain hierarchical pores. Ru was introduced as a catalytic species into the POPs using different synthetic routes. Systematic investigation of the resultant chiral Ru/POP catalysts for heterogeneous-asymmetric hydrogenation of beta-keto esters revealed their excellent chiral inducibility as well as high activity and stability. Our work thereby paves a path towards the use of advanced hierarchical porous polymers as solid chiral platforms for heterogeneous asymmetric catalysis. (c) 2017, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.Chinese Academy of Sciences [XDB17020400

Feed types driven differentiation of microbial community and functionality in marine integrated multitrophic aquaculture system

Integrated multi trophic aquaculture (IMTA) improves the production of aquatic animals by promoting nutrient utilization through different tropical levels. Microorganisms play an important role in elements cycling, energy flow and farmed-species health. The aim of this study was to evaluate how feed types, fresh frozen fish diet (FFD) or formulated diet (FD), influence the microbial community diversity and functionality in both water and sediment in a marine IMTA system. Preferable water quality, higher animal yields and higher cost efficiency were achieved in the FD pond. Feed types changed the pond bacterial community distribution, especially in the rearing water. The FFD pond was dominated with Cyanobacteria in the water, which played an important role in nitrogen fixation through photosynthesis due to the high nitrogen input of the frozen fish diet. The high carbohydrate composition in the formulated diet triggered higher metabolic pathways related to carbon and lipid metabolism in the water of the FD pond. Sediment had significantly higher microbial diversity than the rearing water. In sediment, the dominating genus, Sulfurovum and Desulfobulbus, were found to be positively correlated by network analysis, which had similar functionality in sulfur transformation. The relatively higher rates of antibiotic biosynthesis in the FFD sediment might be related to the pathogenic bacteria introduced by the trash fish diet. The difference in microbial community composition and metabolic pathways may be associated with the different pathways for nutrient cycling and animal growth performance. The formulated diet was determined to be more ecologically and economically sustainable than the frozen fish diet for marine IMTA pond systems.</p

Porous Rh/BINAP polymers as efficient heterogeneous catalysts for asymmetric hydroformylation of styrene: Enhanced enantioselectivity realized by flexible chiral nanopockets

不对称氢甲酰化是合成具有单一光学活性物质(如光学活性的醛、alpha-氨基酸和醇等)最为重要的反应之一.尽管不对称氢甲酰化反应的研究超过40年,; 但仍然是催化体系中具有挑战性的课题.该反应涉及到产物的化学选择性、立体选择性和对映体选择性的优化.目前,在Rh催化体系中,使用磷-亚磷酸酯手性配; 体或双亚磷酸酯配体可以在不对称氢甲酰化反应中取得优异的催化性能.然而在Rh/手性双膦配体催化体系中,不对称氢甲酰化反应性能通常很低.以BINAP; 配体为例,负载Rh金属后,在催化苯乙烯不对称氢甲酰化反应中,产物的ee值只有25%.同时,由于均相催化体系存在催化剂回收和产物提纯等问题,因此有; 必要研究多相不对称氢甲酰化反应催化剂.本文使用乙烯基修饰的BINAP配体5,5'-divinyl-BINAP与具有不同结构的共聚单体二乙烯基苯或; 1,3,5-三乙烯基苯基苯共聚,得到具有不同孔结构的聚合物Poly-1和Poly-2.为了比较,利用线性共聚单体乙二醇二甲基丙烯酸甲酯与乙烯基; BINAP共聚得到聚合物Poly-3.上述三种聚合物材料负载金属Rh后,用作苯乙烯不对称氢甲酰化反应的催化剂.固体13C核磁分析表明,三种聚合物; 材料负载金属后仍然保持较为稳定的C骨架结构.通过31P核磁可以看到,嵌入在材料骨架中的BIANP仍然保持未被氧化的状态.N2物理吸附结果发现Po; ly-1和Poly-2具有较大的比表面积和孔体积,而; Poly-3的比表面积最小.热重分析显示,这些材料具有较高的热稳定性.在不同反应溶剂中催化剂活性差异较大.通过优化反应温度和合成气压力后,催化剂; Rh/Poly-1在80 °C和0.2; MPa下产物的对映体选择性可高达58.9%,支链醛与直链醛的比值为8.5;而在相同反应条件下,均相催化剂Rh-BINAP的ee值仅为35.3%,; 但高于Rh/Poly-3.这是由于三个多相催化剂骨架中BINAP周围环境不同所致.前两个催化剂中,BINAP与空间位阻较大的单体相连接,使得反应; 底物按照特定方向与催化活性位点接触,形成了类似于手性口袋的结构.而Rh/Poly-3中,BIANP周围是线性的共聚单体,不能形成有效的手性口袋结; 构.Rh/Poly-1重复使用7次后,催化活性没有显著下降.拓展X射线吸收精细结构表征结果表明,Rh/Poly-1催化剂使用前没有Rh-Rh键存; 在,但经重复使用后,Rh金属部分聚集,生成了Rh-Rh键.球差电镜照片也证实了这一点.A new chiral monomer, (S)-5,5'-divinyl-BINAP, was successfully synthesized and embedded into two different porous organic polymers (Poly-1 and Poly-2). After loading a Rh species, the catalysts were applied for the heterogeneous asymmetric hydroformylation of styrene. Compared with the homogeneous BINAP analogue, the enantioselectivity of Rh/Poly-1 catalyst was drastically increased by approximately 70%. The improved enantioselectivity of the porous Rh/BINAP polymers was attributed to the presence of flexible chiral nanopockets resulting from the increased bulk of the R groups near the catalytic center. (C) 2017, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.Strategic priority Research Program of the Chinese Academy of Sciences; [XDB17020400

Comprehensive evaluation of the effectiveness of endemic disease prevention and control in Jiangsu Province, China, 2013–2022

As a strong economic and populous province in China, Jiangsu is home to four endemic diseases. Despite efforts in the past decade, the prevention and control of these four endemic diseases are not uniform because of the different etiological chains and influencing factors of these diseases. Among the evaluation methodologies for endemic disease control, only one method is currently available for each disease. In this study, we selected 14 indicators to comprehensively evaluate the effectiveness of endemic disease control in Jiangsu between 2013 and 2022. We improved the method for calculating the weights of the indicators and established a fuzzy comprehensive evaluation model based on the weighted Technique for Order Preference by Similarity to an Ideal Solution model and a weighted grey relational analysis model. The results of the comprehensive evaluation showed that the progress of endemic disease control in Jiangsu was not always in line with our expectations of improvement, with the top five years of better control occurring in 2015, 2013, 2021, 2022, and 2014. The results of the sensitivity analysis confirm the reliability and accuracy of these findings. We discovered that measures such as the reform of the salt industry, use of thyroid ultrasound, and new water supply projects for residents in Jiangsu affected the progress of endemic disease prevention and control. The tracking of endemic disease status should consider the potential effects of changes in policies implemented in other industries on endemic disease prevention and control. Additionally, the results of this study provide a theoretical basis for enhancing prevention and control practices in other regions of China

Resident Immune Cells of the Liver in the Tumor Microenvironment

The liver is a central immunomodulator that ensures a homeostatic balance between protection and immunotolerance. A hallmark of hepatocellular carcinoma (HCC) is the deregulation of this tightly controlled immunological network. Immune response in the liver involves a complex interplay between resident innate, innate, and adaptive immune cells. The immune response in the liver is modulated by its continuous exposure to toxic molecules and microorganisms that requires a degree of immune tolerance to protect normal tissue from damage. In HCC pathogenesis, immune cells must balance a dual role that includes the elimination of malignant cells, as well as the repair of damaged liver tissue to maintain homeostasis. Immune response in the innate and adaptive immune systems extends to the cross-talk and interaction involving immune-regulating non-hematopoietic cells, myeloid immune cells, and lymphoid immune cells. In this review, we discuss the different immune responses of resident immune cells in the tumor microenvironment. Current FDA-approved targeted therapies, including immunotherapy options, have produced modest results to date for the treatment of advanced HCC. Although immunotherapy therapy to date has demonstrated its potential efficacy, immune cell pathways need to be better understood. In this review article, we summarize the roles of specific resident immune cell subsets and their cross-talk subversion in HCC pathogenesis, with a view to identifying potential new biomarkers and therapy options

co2cnanoprismsforsyngasconversiontolowerolefinswithhighselectivity

低碳烯烃(乙烯、丙烯、丁烯)是十分重要的有机化工原料,在传统工业中,主要通过石脑油,石油气和凝析油裂解得到.由于石油资源的日益减少和C1化学的迅速发展,为缓解对石油资源的依赖,急需寻找一种烯烃制备的工艺过程替代石油路线.主流的非石油路线主要是指利用煤炭、天然气、生物质等含碳资源通过合成气直接或间接制备烯烃.间接过程是由合成气转化制得甲醇,然后通过甲醇转化路线(包括甲醇制烯烃的MTO工艺和甲醇制丙烯的MTP工艺)生产烯烃产品.无疑,如能减少反应步骤,将合成气直接高选择性合成低碳烯烃,将体现出流程更短能耗更低的优势,有较强的竞争力.国内外的研究学者一直致力于制备含两种组元的双功能催化剂,试图将甲醇合成及脱水制备烯烃两步耦合在一起,合并为一步法,从而简化工业过程.由于低温下MTO反应几乎无活性,目前该类双功能复合催化剂多采用较高的反应温度.鉴于传统的Cu-Zn-Al催化剂在高温下极低的甲醇选择性,而Zn与其它过渡金属复合氧化物(如ZnZr及ZnCr)可在高温下高选择性合成甲醇,故经常被考虑作为耦合催化剂进行研究.基于上述理念,大化所包信和等提出了全新的OX-ZEO过程,OX(复合氧化物)用来活化CO分子并形成相应中间体,这些中间体可以在ZEO(分子筛)的酸性位上形成相应的烯烃.他们报道的ZnCrOx/MSAPO催化剂,在较高的CO转化率(17%)下,低碳烯烃选择性高达80%.与此同时,厦门大学王野等采用ZnZr二元氧化物与SAPO-34分子筛物理混合的双功能催化剂,也可实现很高的低碳烯烃选择性(74%).合成气经费托路线直接制烯烃(FTO)反应与费托(FT)反应类似,传统FT催化剂均可用于FTO的改性研究.由于Fe基催化剂的加氢能力相对较弱,产物中烯/烷比较高,所以被广泛用于FTO反应的研究中.deJong研究小组采用惰性载体负载的Fe基催化剂,并浸渍Na,S元素作为助剂进行FTO反应的研究,实现了61%的低碳烯烃的选择性,但由于反应温度较高(300–350°C),催化剂容易失活,稳定性不佳.此外,由于产物受到ASF分布的限制,甲烷选择性很高.目前FTO研究的挑战在于开发全新的催化活性位结构新方法,摆脱ASF分布的限制,在较温和的反应条件下同时呈现低甲烷选择性及高烯烃选择性.一般认为,金属Co纳米颗粒是Co基费托催化剂的活性相,主要产物为C5+长链饱和烷烃,而Co2C则被视为Co基FT催化剂失活的主要原因之一,即在合成气转化过程中Co2C活性很低且CH4选择性很高.但是,最近中国科学院上海高等研究院低碳转化科学与工程重点实验室的钟良枢及孙予罕领导的研究小组发现,暴露(020)及(101)晶面的Co2C纳米棱柱结构对合成气转化具有异乎寻常的催化性能.该催化剂在温和的反应条件(250°C和0.1–0.5MPa)下可实现合成气高选择性直接制备烯烃,甲烷选择性可低至5%,低碳烯烃选择性能够达到60%,而总烯烃选择性高达80%以上(以上所谈到的选择性都是去除了CO2产物),同时烯/烷比大于30,产物分布完全不服从经典的ASF规律,并且该催化剂具有良好的稳定性,反应600h仍未出现明显失活.他们通过深入的构效关系研究并结合DFT理论计算,揭示了Co2C存在显著的晶面效应,相比于其它暴露面,(101)晶面非常有利于烯烃的生成,同时(101)和(020)晶面可有效抑制甲烷的形成

co2cnanoprismsforsyngasconversiontolowerolefinswithhighselectivity

低碳烯烃(乙烯、丙烯、丁烯)是十分重要的有机化工原料,在传统工业中,主要通过石脑油,石油气和凝析油裂解得到.由于石油资源的日益减少和C1化学的迅速发展,为缓解对石油资源的依赖,急需寻找一种烯烃制备的工艺过程替代石油路线.主流的非石油路线主要是指利用煤炭、天然气、生物质等含碳资源通过合成气直接或间接制备烯烃.间接过程是由合成气转化制得甲醇,然后通过甲醇转化路线(包括甲醇制烯烃的MTO工艺和甲醇制丙烯的MTP工艺)生产烯烃产品.无疑,如能减少反应步骤,将合成气直接高选择性合成低碳烯烃,将体现出流程更短能耗更低的优势,有较强的竞争力.国内外的研究学者一直致力于制备含两种组元的双功能催化剂,试图将甲醇合成及脱水制备烯烃两步耦合在一起,合并为一步法,从而简化工业过程.由于低温下MTO反应几乎无活性,目前该类双功能复合催化剂多采用较高的反应温度.鉴于传统的Cu-Zn-Al催化剂在高温下极低的甲醇选择性,而Zn与其它过渡金属复合氧化物(如ZnZr及ZnCr)可在高温下高选择性合成甲醇,故经常被考虑作为耦合催化剂进行研究.基于上述理念,大化所包信和等提出了全新的OX-ZEO过程,OX(复合氧化物)用来活化CO分子并形成相应中间体,这些中间体可以在ZEO(分子筛)的酸性位上形成相应的烯烃.他们报道的ZnCrOx/MSAPO催化剂,在较高的CO转化率(17%)下,低碳烯烃选择性高达80%.与此同时,厦门大学王野等采用ZnZr二元氧化物与SAPO-34分子筛物理混合的双功能催化剂,也可实现很高的低碳烯烃选择性(74%).合成气经费托路线直接制烯烃(FTO)反应与费托(FT)反应类似,传统FT催化剂均可用于FTO的改性研究.由于Fe基催化剂的加氢能力相对较弱,产物中烯/烷比较高,所以被广泛用于FTO反应的研究中.deJong研究小组采用惰性载体负载的Fe基催化剂,并浸渍Na,S元素作为助剂进行FTO反应的研究,实现了61%的低碳烯烃的选择性,但由于反应温度较高(300–350°C),催化剂容易失活,稳定性不佳.此外,由于产物受到ASF分布的限制,甲烷选择性很高.目前FTO研究的挑战在于开发全新的催化活性位结构新方法,摆脱ASF分布的限制,在较温和的反应条件下同时呈现低甲烷选择性及高烯烃选择性.一般认为,金属Co纳米颗粒是Co基费托催化剂的活性相,主要产物为C5+长链饱和烷烃,而Co2C则被视为Co基FT催化剂失活的主要原因之一,即在合成气转化过程中Co2C活性很低且CH4选择性很高.但是,最近中国科学院上海高等研究院低碳转化科学与工程重点实验室的钟良枢及孙予罕领导的研究小组发现,暴露(020)及(101)晶面的Co2C纳米棱柱结构对合成气转化具有异乎寻常的催化性能.该催化剂在温和的反应条件(250°C和0.1–0.5MPa)下可实现合成气高选择性直接制备烯烃,甲烷选择性可低至5%,低碳烯烃选择性能够达到60%,而总烯烃选择性高达80%以上(以上所谈到的选择性都是去除了CO2产物),同时烯/烷比大于30,产物分布完全不服从经典的ASF规律,并且该催化剂具有良好的稳定性,反应600h仍未出现明显失活.他们通过深入的构效关系研究并结合DFT理论计算,揭示了Co2C存在显著的晶面效应,相比于其它暴露面,(101)晶面非常有利于烯烃的生成,同时(101)和(020)晶面可有效抑制甲烷的形成