Oxidation-Reduction

氧化还原
  • 文章类型: Journal Article
    重金属在自然界中遇到,并用于多种人类活动,包括牙齿填充物。众所周知,金属的安全性取决于它们的化学形态,以及生物系统暴露于它们的剂量和途径。这里,我们使用Nauphoetacinerea模型来检查牙科填充物中使用的重金属盐-银和汞-发挥其神经毒性的机制。若虫暴露在重金属中,由于花费更多时间不动,因此运动和探索能力降低,尤其是在一个新物体的外围,与对照若虫相比,覆盖的距离更短。暴露于AgNO3和HgCl2也加剧了氧化应激标志物(MDA和ROS)和神经递质调节因子-AChE和MAO的水平,同时减少抗氧化活性标志物,在生物化学(硫醇和GST)和RT-qPCR(TRX,GST,SOD,过氧化氢酶)检查,蟑螂的神经组织。观察到的神经运动控制中断,突触传递和氧化还原平衡解释了重金属盐如何使生物体易患神经系统疾病。
    Heavy metals are encountered in nature, and are used in several human endeavors, including in dental fillings. It is well known that the safety of metals depends on their chemical form, as well as the dose and route through which biological systems are exposed to them. Here, we used the Nauphoeta cinerea model to examine the mechanism by which salts of the heavy metals used in dental fillings - silver and mercury - exert their neurotoxicity. Nymphs exposed to heavy metals presented with reduced motor and exploratory abilities as they spent more time immobile, especially in the periphery of a novel object, and covered less distance compared with control nymphs. Exposure to AgNO3 and HgCl2 also exacerbated levels of oxidative stress markers (MDA & ROS) and the neurotransmitter regulators - AChE and MAO, while reducing antioxidant activity markers, both in biochemical (thiol & GST) and RT-qPCR (TRX, GST, SOD, Catalase) examinations, in neural tissues of the cockroach. The observed disruptions in neurolocomotor control, synaptic transmission and redox balance explain how heavy metal salts may predispose organisms to neurological disorders.
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  • 文章类型: Journal Article
    大多数生物拥有三种生物振荡器,生物钟,细胞周期,和氧化还原节律,它们是自主的,但相互作用。然而,它们的相互作用和自主性是否对生物体有益尚不清楚。这里,我们建模了一个耦合振荡器系统,其中每个振荡器影响其他振荡器的相位。我们发现,多种类型的偶联可以防止M期细胞中的高H2O2水平。因此,我们假设在M期H2O2敏感性较高,并发现适度的耦合通过在三个节律之间产生适当的相位关系来减少由于氧化应激引起的细胞损伤。而强耦合通过增加平均H2O2水平并破坏细胞周期而导致细胞损伤升高。此外,多细胞模型表明,细胞之间的相位变化赋予与环境同步的灵活性,以牺牲对最佳环境的适应性为代价。因此,振荡器之间的自主性和同步性对于协调它们的相位关系以最小化氧化应激是重要的,和联轴器根据环境来平衡它们。
    Most organisms possess three biological oscillators, circadian clock, cell cycle, and redox rhythm, which are autonomous but interact each other. However, whether their interactions and autonomy are beneficial for organisms remains unclear. Here, we modeled a coupled oscillator system where each oscillator affected the phase of the other oscillators. We found that multiple types of coupling prevent a high H2O2 level in cells at M phase. Consequently, we hypothesized a high H2O2 sensitivity at the M phase and found that moderate coupling reduced cell damage due to oxidative stress by generating appropriate phase relationships between three rhythms, whereas strong coupling resulted in an elevated cell damage by increasing the average H2O2 level and disrupted the cell cycle. Furthermore, the multicellularity model revealed that phase variations among cells confer flexibility in synchronization with environments at the expense of adaptability to the optimal environment. Thus, both autonomy and synchrony among the oscillators are important for coordinating their phase relationships to minimize oxidative stress, and couplings balance them depending on environments.
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  • 文章类型: Journal Article
    从沉香人工湿地沉积物中分离出的BacillusvelezensisM3-1菌株可有效地将NO3--N转化为NO2--N,对碳源添加的要求不是很严格。这项工作表明,第一次,研究了利用厌氧氨氧化和贝氏芽孢杆菌M3-1微生物协同脱氮的可行性。在这项研究中,在厌氧反应器中验证了M3-1将厌氧氨氧化产生的NO3--N转化为NO2--N的可能性。研究了M3-1和反硝化细菌在不同C/N条件下偶联体系中NO3--N的还原能力,发现M3-1优先使用碳源,而不是反硝化细菌。通过调整NH4+-N与NO2--N的比例,发现M3-1从NO3--N转化而来的NO2--N参与了原始的厌氧氨氧化。耦合系统的脱氮效率(NRE)提高了12.1%,与对照组的厌氧氨氧化系统相比,C/N=2:1。功能基因表明它可能是硝酸盐还原细菌。这项研究表明,由BacillusvelezensisM3-1实现的硝酸盐还原率可以足够高,以去除由anammox工艺产生的硝酸盐,这将能够改善废水中的氮去除。
    Bacillus velezensis M3-1 strain isolated from the sediment of Myriophyllum aquatium constructed wetlands was found to efficiently convert NO3--N to NO2--N, and the requirements for carbon source addition were not very rigorous. This work demonstrates, for the first time, the feasibility of using the synergy of anammox and Bacillus velezensis M3-1 microorganisms for nitrogen removal. In this study, the possibility of M3-1 that converted NO3--N produced by anammox to NO2--N was verified in an anaerobic reactor. The NO3--N reduction ability of M3-1 and denitrifying bacteria in coupling system was investigated under different C/N conditions, and it was found that M3-1 used carbon sources preferentially over denitrifying bacteria. By adjusting the ratio of NH4+-N to NO2--N, it was found that the NO2--N converted from NO3--N by M3-1 participated in the original anammox.The nitrogen removal efficacy (NRE) of the coupled system was increased by 12.1%, compared to the control group anammox system at C/N = 2:1. Functional gene indicated that it might be a nitrate reducing bacterium.This study shows that the nitrate reduction rate achieved by the Bacillus velezensis M3-1 can be high enough for removing nitrate produced by anammox process, which would enable improve nitrogen removal from wastewater.
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  • 文章类型: Journal Article
    非均相铁基催化剂由于其丰富的性质,在过硫酸盐的高级氧化中引起了越来越多的关注,对环境没有二次污染,以及过去几年的低成本。在本文中,从两个方面综述了非均相铁基催化剂活化过硫酸盐研究的最新进展,就合成催化剂(Fe0,Fe2O3,Fe3O4,FeOOH)和天然铁矿石催化剂(黄铁矿,磁铁矿,赤铁矿,菱铁矿,针铁矿,水铁矿,钛铁矿和锂辉石)专注于改善催化剂性能的努力。总结了合成催化剂和天然铁矿石的优缺点。催化剂/PS/污染物系统中用于去除有机污染物的活化机理受到了特别的关注。还讨论了在现场应用背景下的未来研究挑战。
    Heterogeneous iron-based catalysts have drawn increasing attention in the advanced oxidation of persulfates due to their abundance in nature, the lack of secondary pollution to the environment, and their low cost over the last a few years. In this paper, the latest progress in the research on the activation of persulfate by heterogeneous iron-based catalysts is reviewed from two aspects, in terms of synthesized catalysts (Fe0, Fe2O3, Fe3O4, FeOOH) and natural iron ore catalysts (pyrite, magnetite, hematite, siderite, goethite, ferrohydrite, ilmenite and lepidocrocite) focusing on efforts made to improve the performance of catalysts. The advantages and disadvantages of the synthesized catalysts and natural iron ore were summarized. Particular interests were paid to the activation mechanisms in the catalyst/PS/pollutant system for removal of organic pollutants. Future research challenges in the context of field application were also discussed.
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  • 文章类型: Journal Article
    伤口渗出物中生物标志物的监测对伤口护理和治疗具有重要意义。和高灵敏度的电化学生物传感器可能用于此目的。然而,传统的电化学生物传感器在复杂的伤口渗出物中进行时总是遭受严重的生物污染。在这里,基于伤口敷料开发了一种用于检测伤口渗出物中总蛋白的防污电化学生物传感器,氧化细菌纤维素(OxBC)和季铵化壳聚糖(QCS)复合水凝胶。采用原位化学氧化和物理共混法制备OxBC/QCS水凝胶,并优化了OxBC和QCS的比例,以实现电中性和增强的亲水性,因此,水凝胶具有特殊的防污和抗菌性能。将包合蛋白SY5抗体共价结合到OxBC/QCS水凝胶上构建生物传感器,它的检测下限低至0.45pgmL-1,线性检测范围为1.0pgmL-1至1.0μgmL-1,并且能够检测伤口渗出物中的靶标。至关重要的是,OxBC/QCS水凝胶独特的防污和抗菌能力不仅延长了其有效寿命,而且保证了生物传感器的传感性能。这种伤口敷料的成功应用,OxBC/QCS水凝胶用于伤口渗出物中的总蛋白检测显示出其在伤口愈合监测中的有希望的潜力。
    The monitoring of biomarkers in wound exudate is of great importance for wound care and treatment, and electrochemical biosensors with high sensitivity are potentially useful for this purpose. However, conventional electrochemical biosensors always suffer from severe biofouling when performed in the complex wound exudate. Herein, an antifouling electrochemical biosensor for the detection of involucrin in wound exudate was developed based on a wound dressing, oxidized bacterial cellulose (OxBC) and quaternized chitosan (QCS) composite hydrogel. The OxBC/QCS hydrogel was prepared using an in-situ chemical oxidation and physical blending method, and the proportion of OxBC and QCS was optimized to achieve electrical neutrality and enhanced hydrophilicity, therefore endowing the hydrogel with exceptional antifouling and antimicrobial properties. The involucrin antibody SY5 was covalently bound to the OxBC/QCS hydrogel to construct the biosensor, and it demonstrated a low limit of detection down to 0.45 pg mL-1 and a linear detection range from 1.0 pg mL-1 to 1.0 μg mL-1, and it was capable of detecting targets in wound exudate. Crucially, the unique antifouling and antimicrobial capability of the OxBC/QCS hydrogel not only extends its effective lifespan but also guarantees the sensing performance of the biosensor. The successful application of this wound dressing, OxBC/QCS hydrogel for involucrin detection in wound exudate demonstrates its promising potential in wound healing monitoring.
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  • 文章类型: Journal Article
    叉指电极(IDE)通过分析物分子的重复还原和氧化实现电化学信号增强。这些电极上的孔隙率通常用于降低阻抗背景。然而,其高电容电流和信号干扰具有氧还原极限电化学检测能力。我们提出了在纳米多孔金(NPG)电极上利用链烷硫醇修饰来降低其背景电容并化学钝化它们免受氧还原引起的干扰,同时保持其快速的电子转移速率,与平面金电极相比,阳极和阴极峰之间的间隔较低(ΔE)和较低的电荷转移电阻(Rct)值得到了验证。基于这种修饰的氧化还原扩增能够灵敏地检测各种小分子,包括绿脓苷,对氨基苯酚,以及在抗坏血酸存在下选择性检测多巴胺。将烷基硫醇NPG阵列用作孔板内的多重传感器测试床,以通过使用夹心测定法将PAPP(4-氨基苯基磷酸酯)转化为PAP(对-氨基苯酚)来筛选各种肽受体与SARSCOV2S蛋白的结合,通过AP(碱性磷酸酶)的作用,这针对肽的光学ELISA筛选进行了验证。这种阵列在具有复杂样品的小体积分析设置中尤其令人感兴趣。其中光学方法是不合适的。
    Interdigitated electrodes (IDEs) enable electrochemical signal enhancement through repeated reduction and oxidation of the analyte molecule. Porosity on these electrodes is often used to lower the impedance background. However, their high capacitive current and signal interferences with oxygen reduction limit electrochemical detection ability. We present utilization of alkanethiol modification on nanoporous gold (NPG) electrodes to lower their background capacitance and chemically passivate them from interferences due to oxygen reduction, while maintaining their fast electron transfer rates, as validated by lower separation between anodic and cathodic peaks (ΔE) and lower charge transfer resistance (Rct) values in comparison to planar gold electrodes. Redox amplification based on this modification enables sensitive detection of various small molecules, including pyocyanin, p-aminophenol, and selective detection of dopamine in the presence of ascorbic acid. Alkanethiol NPG arrays are applied as a multiplexed sensor testbed within a well plate to screen binding of various peptide receptors to the SARS COV2 S-protein by using a sandwich assay for conversion of PAPP (4-aminophenyl phosphate) to PAP (p-aminophenol), by the action of AP (alkaline phosphatase), which is validated against optical ELISA screens of the peptides. Such arrays are especially of interest in small volume analytical settings with complex samples, wherein optical methods are unsuitable.
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  • 文章类型: Journal Article
    铁是生命的基本要素,因为它能够参与各种氧化还原反应。然而,铁依赖性氧化还原循环的失调也会产生氧化应激,有助于细胞生长,扩散,和衰老背后的死亡途径,癌症,神经变性,和代谢性疾病。选择性监测松散结合的Fe(II)离子的荧光探针,被称为不稳定的铁池,是研究这种金属营养素的潜在强大工具;然而,这些生物可利用的金属库的动态时空性质和有效的荧光猝灭能力对其检测提出了挑战。这里,我们报告了一种串联的基于活动的传感和标记策略,该策略通过增强细胞滞留,能够对活细胞中不稳定的铁池进行成像.铁绿-1氟甲基(IG1-FM)使用内过氧化物触发剂与Fe(II)选择性反应,释放醌甲基化染料,随后附着于近端生物亲核试剂,在升高的不稳定铁的部位提供永久性荧光染色。IG1-FM成像显示,主要的铁储存蛋白铁蛋白通过铁吞噬的降解扩大了不稳定的铁库,而核因子-红系2相关因子2(NRF2)抗氧化反应元件(AREs)的激活会耗尽它。我们进一步表明,肺癌细胞具有增强的NRF2激活,从而降低了基础不稳定铁,当用铁螯合剂处理时具有降低的活力。通过将不稳定的铁池和NRF2-ARE活动与癌症中依赖金属的药物脆弱性联系起来,这项工作为更广泛地研究过渡金属和抗氧化剂信号通路在健康和疾病中的作用提供了起点.
    Iron is an essential element for life owing to its ability to participate in a diverse array of oxidation-reduction reactions. However, misregulation of iron-dependent redox cycling can also produce oxidative stress, contributing to cell growth, proliferation, and death pathways underlying aging, cancer, neurodegeneration, and metabolic diseases. Fluorescent probes that selectively monitor loosely bound Fe(II) ions, termed the labile iron pool, are potentially powerful tools for studies of this metal nutrient; however, the dynamic spatiotemporal nature and potent fluorescence quenching capacity of these bioavailable metal stores pose challenges for their detection. Here, we report a tandem activity-based sensing and labeling strategy that enables imaging of labile iron pools in live cells through enhancement in cellular retention. Iron green-1 fluoromethyl (IG1-FM) reacts selectively with Fe(II) using an endoperoxide trigger to release a quinone methide dye for subsequent attachment to proximal biological nucleophiles, providing a permanent fluorescent stain at sites of elevated labile iron. IG1-FM imaging reveals that degradation of the major iron storage protein ferritin through ferritinophagy expands the labile iron pool, while activation of nuclear factor-erythroid 2-related factor 2 (NRF2) antioxidant response elements (AREs) depletes it. We further show that lung cancer cells with heightened NRF2 activation, and thus lower basal labile iron, have reduced viability when treated with an iron chelator. By connecting labile iron pools and NRF2-ARE activity to a druggable metal-dependent vulnerability in cancer, this work provides a starting point for broader investigations into the roles of transition metal and antioxidant signaling pathways in health and disease.
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  • 文章类型: Journal Article
    表面功能化策略正成为从磁性纳米粒子(MNPs)到其广泛生物应用的关键桥梁。为了实现MNPs的多种功能,如磁操纵,目标捕获,和信号放大在他们使用电化学生物传感,本文提出了通过结合超敏感氧化还原部分和特异性生物探针来构建双官能化MNPs的共交联策略。在这项工作中,通过用于胺化和PEG化的共沉淀来合成TEM尺寸为10nm的MNPs,以在分散于高离子强度缓冲液(例如磷酸盐缓冲盐水)中时保持胶体稳定性。然后,通过双(磺基琥珀酰亚胺基)辛二酸盐(BS3)交联剂将这些IgG缀合到MNP表面上制备MNPs@IgG。结合效率为73%。要构建双官能化MNPs,这些二茂铁-NHS(Fc)的氧化还原探针共交联到MNP表面,与IgG一起,使用BS3。通过SDS-PAGE对开发的MNPs@Redox@IgG进行表征,以鉴定IgG结合,并通过方波伏安法(SWV)验证氧化还原信号。此外,选择抗CD63抗体用于开发MNPs@抗CD63,用于外泌体样品捕获的生物测试。因此,共交联策略为开发双官能化的MNPs铺平了道路,这可以帮助它们在诊断测定或电化学方法中的潜在利用。
    Surface functionalization strategy is becoming a crucial bridge from magnetic nanoparticles (MNPs) to their broad bio-application. To realize the multiple functions of MNPs such as magnetic manipulation, target capture, and signal amplification in their use of electrochemical biosensing, co-crosslinking strategy was proposed here to construct dual-functionalized MNPs by combining ultra-sensitive redox moieties and specific biological probes. In this work, MNPs with a TEM size of 10 nm were synthesized by co-precipitation for amination and PEGylation to maintain colloid stability once dispersed in high-ionic-strength buffer (such as phosphate-buffered saline). Then, MNPs@IgG were prepared via the bis(sulfosuccinimidyl) suberate (BS3) cross-linker to conjugate these IgG onto the MNP surface, with a binding efficiency of 73%. To construct dual-functionalized MNPs, these redox probes of ferrocene-NHS (Fc) were co-crosslinked onto the MNP surface, together with IgG, by using BS3. The developed MNPs@Redox@IgG were characterized by SDS‒PAGE to identify IgG binding and by square wave voltammetry (SWV) to validate the redox signal. Additionally, the anti-CD63 antibodies were selected for the development of MNPs@anti-CD63 for use in the bio-testing of exosome sample capture. Therefore, co-crosslinking strategy paved a way to develop dual-functionalized MNPs that can be an aid of their potential utilization in diagnostic assay or electrochemical methods.
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  • 文章类型: Journal Article
    促进分子间电子转移的氧化还原酶在代谢途径中是关键的。基于黄素的电子分叉(FBEB),最近发现的氧化还原酶的能量耦合机制,能够将电子对可逆地分成两个受体,桥接exergonic和其他不可行的endergonic反应。本章探讨了四个不同的FBEB复杂家族,并强调了对FBEB复杂的十年结构见解。在这一章中,我们讨论建筑,电子转移路线,以及所有FBEB家族的构象变化,揭示了促进这些显著功能的结构基础。
    Oxidoreductases facilitating electron transfer between molecules are pivotal in metabolic pathways. Flavin-based electron bifurcation (FBEB), a recently discovered energy coupling mechanism in oxidoreductases, enables the reversible division of electron pairs into two acceptors, bridging exergonic and otherwise unfeasible endergonic reactions. This chapter explores the four distinct FBEB complex families and highlights a decade of structural insights into FBEB complexes. In this chapter, we discuss the architecture, electron transfer routes, and conformational changes across all FBEB families, revealing the structural foundation that facilitate these remarkable functions.
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    文章类型: Journal Article
    抗氧化剂由于其结合自由基的能力而广泛用于医学-活性生物分子破坏细胞的遗传装置及其膜结构,这使得可以降低体内氧化过程的强度。在活的有机体中,自由基参与各种过程,但是它们的活性是由抗氧化剂控制的。这项工作的目的是进行一系列研究,以确定一系列草酸二酰胺的新合成化合物在体内和体外实验白鼠脑和肝组织中的抗氧化活性,以及确定其潜在的药理特性。这些研究是在远交的白色雄性大鼠上进行的,重180-200克,保持正常饮食。尸检后,大脑和肝脏被分离,用盐水冲洗,清除血管,并在Tris-HCl缓冲液(pH-7.4)中匀浆(体外)。研究结果表明,所有化合物的抗氧化活性(AOA)均具有不同的功效。化合物SV-425在脑和肝组织中证明了最显著的活性。化合物SV-427显示出最小的活性,脑组织和肝组织中的水平。此外,所研究化合物的所有物理化学描述符均符合Lipinski的5条规则,以确定用于治疗氧化应激的新分子。从获得的数据来看,可以得出结论,所研究的化合物具有抗氧化性能,帮助保护细胞免受氧化应激。这对于预防和治疗与自由基水平升高相关的疾病是重要的。
    Antioxidants are widely used in medicine due to their ability to bind free radicals - active biomolecules that destroy the genetic apparatus of cells and the structure of their membranes, which makes it possible to reduce the intensity of oxidative processes in the body. In a living organism, free radicals are involved in various processes, but their activity is controlled by antioxidants. The purpose of this work was to conduct a series of studies to identify the antioxidant activity of new synthesized compounds of a series of oxalic acid diamides in the brain and liver tissue of white rats in vivo and in vitro experiments, as well as to determine their potential pharmacological properties. The studies were conducted on outbred white male rats, weighing 180-200 g, kept on a normal diet. After autopsy, the brain and liver were isolated, washed with saline, cleared of blood vessels, and homogenized in Tris-HCl buffer (pH-7.4) (in vitro). The research results showed significant antioxidant activity (AOA) of all compounds with varying effectiveness. The most pronounced activity was demonstrated by compound SV-425 in both brain and liver tissues. Compound SV-427 demonstrated the least activity, with levels in brain tissue and liver tissue. In addition, all physicochemical descriptors of the studied compounds comply with Lipinski\'s rule of five to identify new molecules for the treatment of oxidative stress. From the data obtained, it can be concluded that the studied compounds have antioxidant properties, helping to protect cells from oxidative stress. This is important for the prevention and treatment of diseases associated with increased levels of free radicals.
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