transition metals

过渡金属
  • 文章类型: Journal Article
    基本过渡金属在氧传输中具有关键作用,神经递质合成,核酸修复,细胞结构的维持和稳定性,氧化磷酸化,和新陈代谢。金属缺乏和过量之间的平衡通常由几种参与摄取的细胞外和细胞内机制来确保。分布,和排泄。然而,无论是内在因素还是外在因素,过量的铁,锌,铜,或锰在慢性或急性暴露时会导致细胞损伤,经常归因于氧化应激。细胞内,线粒体是需要最严格控制活性氧产生的细胞器,这不可避免地让它们成为金属毒性最脆弱的目标之一。目前对抗金属过载的疗法主要集中在螯合剂上,这往往会导致降低患者生活质量的副作用。基于合成或天然抗氧化剂的新治疗选择已被证明对金属中毒具有积极作用。在这次审查中,我们简要介绍了过渡金属的细胞代谢,它们过载的后果,和目前的治疗方法,其次是它们在诱导氧化应激中的潜在作用及其补救措施。
    Essential transition metals have key roles in oxygen transport, neurotransmitter synthesis, nucleic acid repair, cellular structure maintenance and stability, oxidative phosphorylation, and metabolism. The balance between metal deficiency and excess is typically ensured by several extracellular and intracellular mechanisms involved in uptake, distribution, and excretion. However, provoked by either intrinsic or extrinsic factors, excess iron, zinc, copper, or manganese can lead to cellular damage upon chronic or acute exposure, frequently attributed to oxidative stress. Intracellularly, mitochondria are the organelles that require the tightest control concerning reactive oxygen species production, which inevitably leaves them to be one of the most vulnerable targets of metal toxicity. Current therapies to counteract metal overload are focused on chelators, which often cause secondary effects decreasing patients\' quality of life. New therapeutic options based on synthetic or natural antioxidants have proven positive effects against metal intoxication. In this review, we briefly address the cellular metabolism of transition metals, consequences of their overload, and current therapies, followed by their potential role in inducing oxidative stress and remedies thereof.
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  • 文章类型: Journal Article
    过渡金属催化有助于新方法的发现和天然产物的制备,以及增加药物发现计划中化学空间的新机会。在海洋药物的情况下,这一策略被用来实现选择性,可持续和有效的转型,否则无法获得。从这个角度来看,我们的目标是展示在过去几年中,各种过渡金属如何在各种类似海洋药物的支架中提供了富有成效的连接,通过加速这些有价值的分子的生产。
    Transition metal catalysis has contributed to the discovery of novel methodologies and the preparation of natural products, as well as new chances to increase the chemical space in drug discovery programs. In the case of marine drugs, this strategy has been used to achieve selective, sustainable and efficient transformations, which cannot be obtained otherwise. In this perspective, we aim to showcase how a variety of transition metals have provided fruitful couplings in a wide variety of marine drug-like scaffolds over the past few years, by accelerating the production of these valuable molecules.
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  • 文章类型: Journal Article
    多年来,作为药物发现计划的一部分,金属-类黄酮复合物已被广泛研究,但是在过去的十年中,它们在材料科学中的重要性显着增加。对金属离子和类黄酮在构建简单复合物和更先进的混合网络中的作用的更深入理解将促进具有定制结构和功能的材料的组装。在这篇评论中,我们强调了金属-类黄酮系统的最基本数据,在混合无机-有机材料的设计中提出了有希望的替代方案。我们主要关注含有CuII/I和FeIII/II离子的系统,这在天然和工业催化中是必需的。我们讨论了两种通常确保金属-类黄酮系统形成的相互作用,即配位和氧化还原反应。我们的目的是涵盖金属类黄酮系统的基本原理,以展示这些知识如何从小分子转移到复杂的材料。
    For many years, metal-flavonoid complexes have been widely studied as a part of drug discovery programs, but in the last decade their importance in materials science has increased significantly. A deeper understanding of the role of metal ions and flavonoids in constructing simple complexes and more advanced hybrid networks will facilitate the assembly of materials with tailored architecture and functionality. In this Review, we highlight the most essential data on metal-flavonoid systems, presenting a promising alternative in the design of hybrid inorganic-organic materials. We focus mainly on systems containing CuII/I and FeIII/II ions, which are necessary in natural and industrial catalysis. We discuss two kinds of interactions that typically ensure the formation of metal-flavonoid systems, namely coordination and redox reactions. Our intention is to cover the fundamentals of metal-flavonoid systems to show how this knowledge has been already transferred from small molecules to complex materials.
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  • 文章类型: Journal Article
    污染物对水质的定性影响主要与其性质及其浓度有关,但无论如何,它们决定了对相关生态系统的强烈影响。特别是,难熔有机化合物代表了一个关键的挑战,并且已经研究和开发了几种降解过程来去除它们。其中,非均相Fenton处理是一种有前途的废水和液体废物修复技术。这里,我们开发了基于Co的单金属和双金属配方,Cu,Fe,Mn,对三种模型有机染料(亚甲基蓝,罗丹明B,和孔雀石绿)。然后通过UV-vis分光光度法技术分析处理的样品。双金属铁基材料在非常短的时间内实现了所有三种模型分子的几乎完全降解。Mn-Fe催化剂产生了最佳配方,在pH5下5分钟内几乎完全降解了亚甲基蓝和孔雀石绿,在pH3下30分钟内几乎完全降解了罗丹明B。结果表明,这些制剂可用于处理包含复杂和可变有机污染物的大范围液体废物。与文献中报道的其它体系相比,所研究的催化剂是非常有前途的。
    The qualitative impact of pollutants on water quality is mainly related to their nature and their concentration, but in any case, they determine a strong impact on the involved ecosystems. In particular, refractory organic compounds represent a critical challenge, and several degradation processes have been studied and developed for their removal. Among them, heterogeneous Fenton treatment is a promising technology for wastewater and liquid waste remediation. Here, we have developed mono- and bimetallic formulations based on Co, Cu, Fe, and Mn, which were investigated for the degradation of three model organic dyes (methylene blue, rhodamine B, and malachite green). The treated samples were then analyzed by means of UV-vis spectrophotometry techniques. Bimetallic iron-based materials achieved almost complete degradation of all three model molecules in very short time. The Mn-Fe catalyst resulted in the best formulation with an almost complete degradation of methylene blue and malachite green at pH 5 in 5 min and of rhodamine B at pH 3 in 30 min. The results suggest that these formulations can be applied for the treatment of a broad range of liquid wastes comprising complex and variable organic pollutants. The investigated catalysts are extremely promising when compared to other systems reported in the literature.
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  • 文章类型: Journal Article
    近年来,新的技术和技术今天允许生产受控的建筑材料。虽然自体骨移植替代品仍然是黄金标准,巨大的缺陷需要补充的同种异体替代品来重建。最近已经出于同样的目的探索了聚合物,并且自过去十年以来,它们的生物学性能一直在研究中。这篇综述的目的是分析三维树脂骨替代物的颌面部重建。进行了问题干预比较结果(PICO)分析,并在Cochrane数据库中进行了搜索,PubMed,GoogleScholar等数据库并进行了手工搜索以收集相关文献。仔细检查了所有使用三维树脂骨替代物进行颌面重建的文章。从1990年到2021年5月出版的手稿都包含在这篇评论中。从基于PICO的关键字搜索中总共获得了106篇文章,排除副本后,共检索到91份手稿。在这57份手稿中,根据标题和摘要被排除在外。从剩下的34项研究中,17人在阅读全文后根据纳入和排除标准被排除。在数据提取过程中,四项研究被删除,最后,这项研究包括13项研究。从这次范围审查来看,我们可以得出结论,聚甲基丙烯酸甲酯和聚乳酸配方是非常有前途的树脂骨替代物,用于颌面部缺损的3维重建。然而,需要严格的长期临床试验来验证这一结论.
    In recent years, novel technologies and techniques have allowed today the production of controlled architecture materials. Although autogenous bone graft substitutes remain the gold standard, enormous defects require supplementary alloplastic substitutes for reconstruction. Polymers have lately been explored for the same purpose and their biological performance has been under research since the last decade. The aim of this review is to analyse maxillofacial reconstruction with three-dimensional resin bone substitutes. A Problem Intervention Comparison Outcomes (PICO) analysis was done and a search was carried out in the Cochrane Database, PubMed, Google Scholar etc databases and a hand search was done to collect the related literature. All articles for maxillofacial reconstruction with three-dimensional resin bone substitutes were scrutinised. The manuscripts published from 1990 till May 2021, were included in this review. A total of 106 articles were obtained from a PICO-based keyword search, and 91 manuscripts were retrieved after excluding the duplicates. Out of these 57 manuscripts were excluded on the basis of title and abstract. From the remaining 34 studies, 17 were excluded after reading the full text based on the inclusion and exclusion criteria. During data extraction, four studies were removed and finally, 13 studies were included in this research. From this scoping review, we could conclude that polymethylmethacrylate and polylactic acid formulations are very promising resin bone substitutes for 3-dimensional reconstruction of maxillofacial defects. However, rigorous long-term clinical trials are needed to validate this conclusion.
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  • 文章类型: Journal Article
    金属蛋白普遍存在于所有生物体中,并参与非常广泛的生物过程。出于这个原因,它们的实验表征对于获得有关其结构和生物学功能的更多知识至关重要。三维结构表示高度相关的信息,因为它提供了对金属离子和蛋白质折叠之间的相互作用的洞察。这种相互作用决定了结合金属的化学反应性。可用的PDB结构可能包含由于实验因素(例如差的分辨率和辐射损伤)而导致的误差。在细化和验证过程中缺乏使用距离限制也会影响结构质量。这里,目的是通过对基于蛋白质中超过115,000个金属结合位点的数据集进行统计分析,全面了解金属离子与其供体原子之间的距离分布。这种分析不仅产生了可以被实验主义者用来支持结构确定过程的参考数据,例如,作为细化约束,但也提高了对不同金属的蛋白质配位是如何发生的以及它们的结合相互作用的性质的认识。特别是,考察了羧酸盐配位的特征,这是几乎所有金属普遍存在的唯一类型的相互作用。
    Metalloproteins are ubiquitous in all living organisms and take part in a very wide range of biological processes. For this reason, their experimental characterization is crucial to obtain improved knowledge of their structure and biological functions. The three-dimensional structure represents highly relevant information since it provides insight into the interaction between the metal ion(s) and the protein fold. Such interactions determine the chemical reactivity of the bound metal. The available PDB structures can contain errors due to experimental factors such as poor resolution and radiation damage. A lack of use of distance restraints during the refinement and validation process also impacts the structure quality. Here, the aim was to obtain a thorough overview of the distribution of the distances between metal ions and their donor atoms through the statistical analysis of a data set based on more than 115 000 metal-binding sites in proteins. This analysis not only produced reference data that can be used by experimentalists to support the structure-determination process, for example as refinement restraints, but also resulted in an improved insight into how protein coordination occurs for different metals and the nature of their binding interactions. In particular, the features of carboxylate coordination were inspected, which is the only type of interaction that is commonly present for nearly all metals.
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  • 文章类型: Journal Article
    在钠冷快堆中,钠与材料的润湿性与钠相关操作和仪器和仪表的检测精度密切相关,因此如何实现不同润湿性要求的材料选择是工程设计中的一个关键问题。为了满足这些要求,利用扫描电子显微镜(SEM)研究了9种过渡金属对液态钠的润湿行为,X射线衍射(XRD)和分子动力学(MD)模拟。结果表明,金属如锌和金,与钠反应在界面处形成金属间化合物,表现出优异的润湿性。其次是具有强烈原子间相互作用的金属,即使它们不与钠反应或彼此溶解,比如钴,镍和铜,而这些体系的润湿性在低温下往往较差。彼此不反应或具有强原子间亲和力的系统被证明是最难润湿的。值得注意的是,具有fcc和hcp最紧密堆积晶体结构的金属通常比具有bcc结构的金属具有更好的润湿性。它们可以为实验研究和技术控制提供有价值的指导。
    In sodium-cooled fast reactors, the wettability of sodium with materials is closely related to sodium-related operations and the detection accuracy of instruments and meters, so how to achieve the selection of materials with different wettability requirements is a key problem in engineering design. To meet these requirements, the wetting behaviors of liquid sodium with nine transition metals were investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), and molecular dynamics (MD) simulations. The results show that metals such as zinc and gold, which react with sodium to form intermetallic compounds at the interface, exhibit superior wettability. Followed by the metals that have strong interatomic interactions even though they do not react with sodium or dissolve each other, such as cobalt, nickel and copper, while the wettability of these systems tends to be poor at low temperatures. Systems that do not react with each other or have strong interatomic affinities proved to be the most difficult to wet. Notably, metals with the closest-packed crystal structures of fcc and hcp generally have better wettability than those with a bcc structure. They can be a valuable guide for experimental research and technical control.
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  • 文章类型: Journal Article
    材料的固有特性在光物质相互作用中起着重要作用,影响散装金属和纳米结构。虽然等离子体纳米结构通过等离子体共振表现出与光子的强相互作用,在其他过渡金属中实现有效的光吸收/散射仍然是一个挑战,阻碍与光电子相关的各种应用,化学,和能量收集。这里,我们提出了一个普遍的策略来增强光-物质的相互作用,通过在金属纳米颗粒的表面上引入空隙。该策略涵盖九种金属,包括传统上被认为是光学惰性的金属。空隙填充的纳米颗粒的吸收截面超过等离子体(Ag/Au)对应物的值,其在宽的光谱范围内具有可调谐的共振峰。值得注意的是,这种增强是在任意极化和变化的颗粒大小以及存在几何无序的情况下实现的,突出了普遍的适应性。我们的战略有望激发光催化领域的新兴设备,生物成像,光学传感,超越,特别是当优选金或银以外的金属时。
    The intrinsic properties of materials play a substantial role in light-matter interactions, impacting both bulk metals and nanostructures. While plasmonic nanostructures exhibit strong interactions with photons via plasmon resonances, achieving efficient light absorption/scattering in other transition metals remains a challenge, impeding various applications related to optoelectronics, chemistry, and energy harvesting. Here, we propose a universal strategy to enhance light-matter interaction, through introducing voids onto the surface of metallic nanoparticles. This strategy spans nine metals including those traditionally considered optically inactive. The absorption cross section of void-filled nanoparticles surpasses the value of plasmonic (Ag/Au) counterparts with tunable resonance peaks across a broad spectral range. Notably, this enhancement is achieved under arbitrary polarizations and varied particle sizes and in the presence of geometric disorder, highlighting the universal adaptability. Our strategy holds promise for inspiring emerging devices in photocatalysis, bioimaging, optical sensing, and beyond, particularly when metals other than gold or silver are preferred.
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  • 文章类型: Journal Article
    代谢起源的自养理论认为,第一个细胞满足了二氧化碳对碳的需求,并且是从H2获得能量和电子的化学自养生物。由于其古老性,因此固定CO2的乙酰辅酶A途径是该观点的核心:在已知的CO2固定途径中,它是i)exergonic的唯一途径,ii)发生在细菌和古细菌中,和iii)可以在体外用单一过渡金属催化剂功能上完全取代。然而,为了在pH值接近7的细胞中操作,乙酰辅酶A途径需要复杂的多酶系统,该系统能够基于黄素的电子分叉,从而减少低电位铁氧还蛋白-乙酰辅酶A途径中电子的生理供体-来自H2的电子。如果需要基于黄素的电子分叉,乙酰辅酶A途径怎么可能是原始的?这里,我们表明,天然铁(Fe0),但不是Ni0,Co0,Mo0,NiFe,Ni2Fe,Ni3Fe,或Fe3O4,在40°C下的几小时内,在pH8.5或更高的条件下,促进水性巴氏梭菌铁氧还蛋白的H2依赖性还原,提供基于黄素的电子分叉的生理功能,但没有酶或有机氧化还原辅因子的帮助。铁还原H2依赖性铁氧还蛋白将原始铁氧还蛋白还原和早期代谢演化与固态铁促进的地壳化学过程联系起来,一种今天仍沉积在蛇形热液喷口中的金属。
    Autotrophic theories for the origin of metabolism posit that the first cells satisfied their carbon needs from CO2 and were chemolithoautotrophs that obtained their energy and electrons from H2. The acetyl-CoA pathway of CO2 fixation is central to that view because of its antiquity: Among known CO2 fixing pathways it is the only one that is i) exergonic, ii) occurs in both bacteria and archaea, and iii) can be functionally replaced in full by single transition metal catalysts in vitro. In order to operate in cells at a pH close to 7, however, the acetyl-CoA pathway requires complex multi-enzyme systems capable of flavin-based electron bifurcation that reduce low potential ferredoxin-the physiological donor of electrons in the acetyl-CoA pathway-with electrons from H2. How can the acetyl-CoA pathway be primordial if it requires flavin-based electron bifurcation? Here, we show that native iron (Fe0), but not Ni0, Co0, Mo0, NiFe, Ni2Fe, Ni3Fe, or Fe3O4, promotes the H2-dependent reduction of aqueous Clostridium pasteurianum ferredoxin at pH 8.5 or higher within a few hours at 40 °C, providing the physiological function of flavin-based electron bifurcation, but without the help of enzymes or organic redox cofactors. H2-dependent ferredoxin reduction by iron ties primordial ferredoxin reduction and early metabolic evolution to a chemical process in the Earth\'s crust promoted by solid-state iron, a metal that is still deposited in serpentinizing hydrothermal vents today.
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  • 文章类型: Journal Article
    目前还没有很好地理解铪(Hf)在生物过程中的直接作用或其在生物中的关键功能。与氧气等关键元素不同,碳,氢气,和氮,这是生命所必需的,已知Hf不具有任何生物活性或功能。必须承认科学研究正在进行中,并且可能已经取得了新的发现。本系统综述旨在汇总和分析讨论Hf金属生物医学应用的研究。本系统审查是按照系统审查和荟萃分析(PRISMA)声明的首选报告项目指南进行的。使用了以下搜索策略:两名独立研究人员在包括PubMed在内的数据库中进行了电子搜索,Embase,Cochrane系统评价数据库,谷歌学者。搜索一直进行到2023年8月,使用医学主题词(MeSH)术语“过渡元素”,\"\"铪,“和”生物医学研究。\"布尔运算符\"AND\"和\"OR\"用于细化搜索。电子数据库,随着手搜索,共确定了38项研究。通过各种数据库搜索,共进行了38项研究,其中12个被排除为重复,和五个无法获得全文数据。然后根据纳入和排除标准对其余21篇全文进行资格评估,最后,本系统综述共纳入12项研究.在12项选定的研究中,6人接受癌症相关的靶向放疗或放化疗,五个是骨骼或磷灰石形成能力,其中之一是治疗炎症性肠病。常见的结果指标包括细胞增殖,成骨细胞形成,放疗强化,和免疫疗法。这篇综述概述了Hf金属的生物医学用途的全貌,一个过渡元素,作为一种有效的生物材料。总之,这个过渡元素,Hf,在生物医学领域有一定的前景,特别关注癌症放射治疗和成骨能力。
    The direct engagement of hafnium (Hf) in biological processes or its critical function in living things is not well understood as of now. Unlike key elements like oxygen, carbon, hydrogen, and nitrogen, which are necessary for life, Hf is not known to have any biological activities or functions. It is essential to acknowledge that scientific research is ongoing and that new findings may have been made. This systematic review aimed to aggregate and analyze the studies that discuss biomedical applications of Hf metal. This systematic review was conducted following the guidelines of the Preferred Reporting Items for Systematic Reviews and Meta-Analyses (PRISMA) Statement. The following search strategy was used: two independent researchers conducted electronic searches in databases including PubMed, Embase, Cochrane Database of Systematic Reviews, and Google Scholar. The search was conducted up to August 2023 using the Medical Subject Headings (MeSH) terms \"transition elements,\" \"hafnium,\" and \"biomedical research.\" Boolean operators \"AND\" and \"OR\" were used to refine the search. Electronic databases, along with hand searches, identified a total of 38 studies. The various database searches resulted in a total of 38 studies, of which 12 were excluded as duplicates, and five were unavailable for full-text data. The remaining 21 full-text articles were then assessed for their eligibility based on the inclusion and exclusion criteria, and finally, a total of 12 studies were included in the present systematic review. Among the 12 chosen studies, six were on cancer-related targeted radiotherapy or chemoradiotherapy, five were on bone or apatite-forming capabilities, and one was on the treatment of inflammatory bowel disease. The common outcome measures included cell proliferation, osteoblast formation, radiotherapy intensification, and immunotherapy. This review outlines an overall picture of the biomedical uses of Hf metal, a transition element, as a potent biomaterial. In conclusion, this transition element, Hf, has some promising scope in the fields of biomedicine, with a special focus in terms of cancer radiotherapy and osteogenic capabilities.
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