Cations, Monovalent

Cations,单价
  • 文章类型: Journal Article
    在本文中,我们研究了不同阳离子价和浓度对纠缠的λDNA溶液流变学的影响。我们表明,单价阳离子主要通过稳定λDNA“单体”的线性串联通过其粘性末端的杂交来适度增加溶液的粘弹性。相反,二价阳离子对溶液的流变学具有更为复杂和显着的影响,我们观察到Mg2分子间DNA-DNA桥接的证据。我们认为,这些结果在单链和双链DNA的密集溶液的背景下可能是有趣的,例如,在体内或生物技术应用如DNA折纸和DNA水凝胶中。
    In this paper we investigate the effects of varying cation valency and concentration on the rheology of entangled λDNA solutions. We show that monovalent cations moderately increase the viscoelasticty of the solutions mainly by stabilising linear concatenation of λDNA \"monomers\" via hybridisation of their sticky ends. On the contrary, divalent cations have a far more complex and dramatic effect on the rheology of the solution and we observe evidence of inter-molecular DNA-DNA bridging by Mg2+. We argue that these results may be interesting in the context of dense solutions of single and double stranded DNA, e.g. in vivo or in biotechnology applications such as DNA origami and DNA hydrogels.
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  • 文章类型: Journal Article
    关于G-四链体结构的数据,非规范核酸形式,评论中考虑了它们可能参与基因表达调节以响应细胞内Nai/Ki比率变化的想法。G-四链体的结构多样性,一价阳离子在这种结构形成中的作用,描述了G-四链体的热力学稳定性。提供了有关它们在细胞中的鉴定方法和这些结构的生物学功能的数据。分析了有关G-四链体与某些蛋白质的特异性相互作用的信息,以及它们可能参与某些病理状况的发展,特别是,癌症和神经退行性疾病,被考虑。特别注意G-四体复合物作为细胞内Nai/Ki比率传感器的合理作用,因为这个参数的改变会影响G-四链体的折叠,改变它们的稳定性,因此,核酸调控元件的组织。结论部分中提供的数据表明,在细胞和组织的某些生理条件下,一些早期反应基因的表达发生了显着变化,具体取决于细胞内Nai/Ki比率。
    Data on the structure of G-quadruplexes, noncanonical nucleic acid forms, supporting an idea of their potential participation in regulation of gene expression in response to the change in intracellular Na+i/K+i ratio are considered in the review. Structural variety of G-quadruplexes, role of monovalent cations in formation of this structure, and thermodynamic stability of G-quadruplexes are described. Data on the methods of their identification in the cells and biological functions of these structures are presented. Analysis of information about specific interactions of G-quadruplexes with some proteins was conducted, and their potential participation in the development of some pathological conditions, in particular, cancer and neurodegenerative diseases, is considered. Special attention is given to the plausible role of G-quadruplexes as sensors of intracellular Na+i/K+i ratio, because alteration of this parameter affects folding of G-quadruplexes changing their stability and, thereby, organization of the regulatory elements of nucleic acids. The data presented in the conclusion section demonstrate significant change in the expression of some early response genes under certain physiological conditions of cells and tissues depending on the intracellular Na+i/K+i ratio.
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  • 文章类型: Journal Article
    通过使用最合适的盐诱导AgNPs聚集,提高了基于银纳米粒子(AgNPs)的比色生物传感器的传感灵敏度。至于由低亲和力阴离子和一价阳离子组成的盐,阳离子依赖性电荷筛选效应是AgNPs聚集的驱动力。除了电荷屏蔽效应,多价阳离子与AgNP表面配体的桥接以及阴离子与Ag之间的相互作用都有助于诱导AgNP的聚集。考虑到AgNP的较高聚集效率导致较窄的感测范围,由低亲和力阴离子和一价阳离子组成的盐被推荐用于基于AgNPs的比色分析,这通过使用NaF比NaCl检测DNA-21的灵敏度高四倍来证实。这项工作启发了从胶体表面科学的角度进一步思考提高基于金属纳米材料的传感器的传感性能。
    The sensing sensitivity was improved for silver nanoparticles (AgNPs)-based colorimetric biosensors by using the most suitable salt to induce AgNPs aggregation. As for the salt composed of low-affinity anion and monovalent cation, the cation-dependent charge screening effect was the driving force for AgNPs aggregation. Apart from the charge screening effect, both the bridging of multivalent cation to the surface ligand of AgNP and the interaction between anion and Ag contributed to inducing AgNPs aggregation. Considering the higher aggregation efficiency of AgNPs resulted in a narrower sensing range, salt composed of low-affinity anion and monovalent cation was recommended for AgNPs-based colorimetric analysis, which was confirmed by fourfold higher sensitivity of DNA-21 detection using NaF than NaCl. This work inspires further thinking on improving the sensing performance of metal nanomaterials-based sensors from the point of colloidal surface science.
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  • 文章类型: Journal Article
    我们研究了Cs吸附后粘土矿物的结构变化,并使用离子交换剂了解了它们的低解吸效率。我们专注于中间层在2:1粘土矿物中Cs吸附和解吸中的作用,即伊利石,水黑云母,和蒙脱石,使用批量实验以及XRD和EXAFS分析。利用阳离子交换容量(CEC)分析了粘土矿物的吸附特性,最大吸附等温线(Qmax),和放射性铯截获潜力(RIP)实验。虽然伊利石表现出较低的CEC值,它对具有相对高的RIP/CEC比率的Cs表现出高选择性。用NaCl离子交换剂处理后,伊利石的Cs解吸效率最高(74.3%),其次是水黑云母(45.5%)和蒙脱石(30.3%);因此,Cs吸附在平面位点上,而不是在夹层或磨损的边缘位点(FES)上,很容易解吸。NaCl处理后,XRD分析表明,解吸效率低的原因是层间固定的Cs塌陷,由于二价阳离子(Mg2或Ca2)与一价阳离子(Na)的离子交换,使夹层\'水黑云母变窄。此外,EXAFS分析表明,水黑云母在NaCl解吸后形成内球结构,表明由于水黑云母和蒙脱石夹层的塌陷以及伊利石在FES中的牢固结合,很难从NaCl解吸中去除Cs。相比之下,使用草酸的螯合解吸有效地溶解了水黑云母(98%)和蒙脱石(85.26%)的狭窄夹层,提高解吸效率。因此,由于一价阳离子和二价阳离子之间的交换,夹层塌陷导致使用离子交换剂的Cs粘土的解吸效率低。
    We investigated the structural changes in clay minerals after Cs adsorption and understood their low desorption efficiency using an ion-exchanger. We focused on the role of interlayers in Cs adsorption and desorption in 2:1 clay minerals, namely illite, hydrobiotite, and montmorillonite, using batch experiments and XRD and EXAFS analyses. The adsorption characteristics of the clay minerals were analyzed using cation exchange capacity (CEC), maximum adsorption isotherms (Qmax), and radiocesium interception potential (RIP) experiments. Although illite showed a low CEC value, it exhibited high selectivity for Cs with a relatively high RIP/CEC ratio. The Cs desorption efficiency after treatment with a NaCl ion exchanger was the highest for illite (74.3%), followed by hydrobiotite (45.5%) and montmorillonite (30.3%); thus, Cs adsorbed onto planar sites, rather than on interlayers or frayed edge sites (FESs), is easily desorbed. After NaCl treatment, XRD analysis showed that the low desorption efficiency was due to the collapse of the interlayer-fixed Cs, which tightly narrowed the interlayers\' hydrobiotite due to the ion exchange of divalent cations (Mg2+ or Ca2+) into the monovalent cation (Na+). Moreover, EXAFS analysis showed that hydrobiotite formed inner-sphere structures after NaCl desorption, indicating that it was difficult to remove Cs from NaCl desorption due to the collapsed hydrobiotite and montmorillonite interlayers as well as the strong bonding in FESs of illite. In contrast, chelation desorption using oxalic acid effectively dissolved the narrowed interlayers of hydrobiotite (98%) and montmorillonite (85.26%), enhancing the desorption efficiency. Therefore, low desorption efficiency for Cs clays using an ion exchanger was caused by the collapsed interlayer due to the exchange between monovalent cation and divalent cation.
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  • 文章类型: Journal Article
    核酸中磷酸二酯键的切割和形成是通过由蛋白质和RNA组成的大型细胞机器完成的。长期以来一直认为依靠双金属离子机制进行催化,结构比较显示许多含有高度空间保守的第二壳一价阳离子,其精确功能仍然难以捉摸。最近的一个高分辨率的剪接体结构,对于真核生物中的前mRNA剪接至关重要,在活性部位发现了钾离子.这里,我们采用偏量子力学/分子力学分子动力学来阐明这种一价离子在剪接中的作用。我们发现K+离子通过硬化活性位点并通过形成关键氢键稳定催化前和催化后状态的底物来调节第一剪接步骤的动力学和热力学。我们的工作支持K离子在催化过程中的直接作用,并提供了可能由其他核酸加工酶共享的机理假设。
    Cleavage and formation of phosphodiester bonds in nucleic acids is accomplished by large cellular machineries composed of both protein and RNA. Long thought to rely on a two-metal-ion mechanism for catalysis, structure comparisons revealed many contain highly spatially conserved second-shell monovalent cations, whose precise function remains elusive. A recent high-resolution structure of the spliceosome, essential for pre-mRNA splicing in eukaryotes, revealed a potassium ion in the active site. Here, we employ biased quantum mechanics/ molecular mechanics molecular dynamics to elucidate the function of this monovalent ion in splicing. We discover that the K+ ion regulates the kinetics and thermodynamics of the first splicing step by rigidifying the active site and stabilizing the substrate in the pre- and post-catalytic state via formation of key hydrogen bonds. Our work supports a direct role for the K+ ion during catalysis and provides a mechanistic hypothesis likely shared by other nucleic acid processing enzymes.
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  • 文章类型: Journal Article
    毛细管电泳已用于测量一系列26个碱基对(bp)DNA寡聚物的游离溶液迁移率,这些寡聚物包含两个阶段的A4T1in-tracts,嵌入在包含0至11个额外ATbps的侧翼序列中。具有12个分离的ATbps的随机序列26bp寡聚物用作参考。在含有小单价阳离子和四丁基铵(TBA)或四丙基铵(TPA)离子的混合物的背景电解质(BGE)中测量迁移率比(A-tract/参考)。在0.3MTBA中观察到的迁移率>1.00,表明TBA离子与参考和A区侧翼序列中的ATbp形成了静电接触对,降低两种低聚物的迁移率。可以通过增加BGE中的小一价阳离子的浓度来消除TBA-AT配对相互作用。在0.3MTPA+中,在侧翼序列和A束中形成有ATbps的静电接触对。有趣的是,A4T1in-tract低聚物观察到的迁移率比曲线的形状取决于低聚物中AT残基的总数。
    Capillary electrophoresis has been used to measure the free solution mobilities of a series of 26-base pair (bp) DNA oligomers containing two phased A4T1in-tracts embedded in flanking sequences containing 0 to 11 additional AT bps. A random-sequence 26-bp oligomer with 12 isolated AT bps was used as the reference. Mobility ratios (A-tract/reference) were measured in background electrolytes (BGEs) containing mixtures of small monovalent cations and tetrabutylammonium (TBA+ ) or tetrapropylammonium (TPA+ ) ions. The mobility ratios observed in 0.3 M TBA+ were >1.00, suggesting that the TBA+ ions had formed electrostatic contact pairs with the AT bp in the reference and in the A-tract flanking sequences, decreasing the mobilities of both oligomers. The TBA-AT pairing interactions could be eliminated by increasing the concentration of small monovalent cations in the BGE. In 0.3 M TPA+ , electrostatic contact pairs were formed with the AT bps in the flanking sequences and in the A-tracts. Interestingly, the shapes of the mobility ratio profiles observed for the A4T1in-tract oligomers depended on the total number of A + T residues in the oligomer.
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  • 文章类型: Journal Article
    一价阳离子质子反转运蛋白(CPAs)在离子和pH稳态中起着至关重要的作用,这对植物发育和环境适应至关重要,包括耐盐性。这里,在大豆中鉴定出68个CPA基因,系统发育分为11个Na+/H+交换剂(NHX),12K+外排反载体(KEAs),和45个阳离子/H+交换剂(CHXs)。GmCPA基因在20条染色体上分布不均,并且可能很大程度上由于大豆中的分段复制而扩展。GmCPA家族进行了净化选择,而不是中性或阳性选择。顺式元素分析和公开可用的转录组数据表明,GmCPAs参与发育和各种环境适应,特别是耐盐性。基于RNA-seq数据,使用qRT-PCR确认了十二个选择的GmCPA基因在盐或渗透胁迫下的差异表达。其中,选择GmCHX20a是由于其在盐胁迫下的高度诱导,以探索其在拟南芥中通过异位表达对盐反应的生物学功能。结果表明,GmCHX20a的过表达通过改变氧化还原系统来增加对盐胁迫的敏感性。总的来说,这项研究提供了对大豆中CPA家族的全面见解,并有可能为开发耐盐大豆品种提供新的候选基因。
    Monovalent cation proton antiporters (CPAs) play crucial roles in ion and pH homeostasis, which is essential for plant development and environmental adaptation, including salt tolerance. Here, 68 CPA genes were identified in soybean, phylogenetically dividing into 11 Na+/H+ exchangers (NHXs), 12 K+ efflux antiporters (KEAs), and 45 cation/H+ exchangers (CHXs). The GmCPA genes are unevenly distributed across the 20 chromosomes and might expand largely due to segmental duplication in soybean. The GmCPA family underwent purifying selection rather than neutral or positive selections. The cis-element analysis and the publicly available transcriptome data indicated that GmCPAs are involved in development and various environmental adaptations, especially for salt tolerance. Based on the RNA-seq data, twelve of the chosen GmCPA genes were confirmed for their differentially expression under salt or osmotic stresses using qRT-PCR. Among them, GmCHX20a was selected due to its high induction under salt stress for the exploration of its biological function on salt responses by ectopic expressing in Arabidopsis. The results suggest that the overexpression of GmCHX20a increases the sensitivity to salt stress by altering the redox system. Overall, this study provides comprehensive insights into the CPA family in soybean and has the potential to supply new candidate genes to develop salt-tolerant soybean varieties.
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  • 文章类型: Journal Article
    硫酸盐试剂在BSP测定的硫化生物降解过程中作为电子受体起着至关重要的作用,以评估有机底物的厌氧生物降解性。然而,单价阳离子(钠或钾)在硫酸盐试剂中的具体作用和影响仍然未知。为了解决这个差距,进行了一系列分批测定以研究Na和K的机制作用。结果表明,当剂量超过8500mg/L时,钠对BSP测定具有抑制作用,而在钾试验中没有观察到不良反应(范围为1800至14400mg/L)。事实上,钾的存在甚至增强了有机底物的厌氧生物降解性,并探讨了潜在的机制。这些发现证实了BSP测定中阳离子对生物降解性评估的影响,并为BSP测定在厌氧生物技术中的应用提供了硫酸盐剂量策略的指导。
    The sulfate reagent plays a crucial role as an electron acceptor in the sulfidogenic biodegradation process of the BSP assay for assessing the anaerobic biodegradability of organic substrates. However, the specific role and influence of the monovalent cations (sodium or potassium) in the sulfate reagent remain unknown. To address this gap, a series of batch assays were conducted to investigate the mechanistic effects of Na+ and K+. The results demonstrated that sodium has inhibitory effects on BSP assay when the dosage exceeds 8500 mg/L, whereas no adverse effects were observed in the potassium tests (ranging from 1800 to 14400 mg/L). In fact, the presence of K+ even enhanced the anaerobic biodegradability of organic substrates, and the underlying mechanisms were explored. These findings confirm the influence of cations in the BSP assay for biodegradability assessment and also provide guidance on sulfate dosage strategies for BSP assay application in anaerobic biotechnologies.
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  • 文章类型: Journal Article
    双链DNA在所有生物聚合物中具有最高的线性负电荷密度(每个碱基对2e),导致与阳离子和偶极水的强烈相互作用,导致在DNA周围形成致密的“凝聚层”。涉及与DNA结合的蛋白质和配体的相互作用主要由强静电力控制。盐浓度的增加阻碍了这种静电相互作用-这种情况在海洋物种中普遍存在,因为它们的细胞质富含盐。然而,在拥挤的高盐环境中,这些相互作用的动力学如何受到影响仍未被探索。这里,我们采用DNA结合配体(DAPI)的稳态和时间分辨荧光斯托克斯位移(TRFSS)来研究DNA在两个二价阳离子存在下的静态和动态溶剂化特性,镁(Mg2+),和钙(Ca2+)在不同的高浓度到非常高的0.15M,1M和2M。我们将结果与在生理浓度(0.15M)的一价Na离子中获得的结果进行了比较。结合来自荧光飞秒光学门控(FOG)和时间相关单光子计数(TCSPC)技术的数据,在广泛的时间尺度上分析DNA中的动态荧光斯托克斯位移,从100fs到10ns。我们发现,虽然二价阳离子拥挤强烈影响DNA的稳定性和配体对DNA的结合亲和力,DNA溶剂化的动力学在五十年的大范围内保持着非常相似的,即使在高盐度的拥挤环境中,二价阳离子,与Na+离子的生理浓度相比。DNA凹槽结合配体的稳态和时间分辨数据似乎不受高盐溶液中离子拥挤的影响,可能是由于离子大部分被DNA结合的配体取代。此外,阳离子与附近水的动态耦合可能会对DNA中的整体集体溶剂化动力学产生净中性效应,由于它们的静电相互作用能量波动具有很强的反相关性。这样的动态情景可以持续在海洋生物的细胞环境和经历高盐条件的其他生物细胞内。
    Double-stranded DNA bears the highest linear negative charge density (2e- per base-pair) among all biopolymers, leading to strong interactions with cations and dipolar water, resulting in the formation of a dense \'condensation layer\' around DNA. Interactions involving proteins and ligands binding to DNA are primarily governed by strong electrostatic forces. Increased salt concentrations impede such electrostatic interactions - a situation that prevails in oceanic species due to their cytoplasm being enriched with salts. Nevertheless, how these interactions\' dynamics are affected in crowded hypersaline environments remains largely unexplored. Here, we employ steady-state and time-resolved fluorescence Stokes shifts (TRFSS) of a DNA-bound ligand (DAPI) to investigate the static and dynamic solvation properties of DNA in the presence of two divalent cations, magnesium (Mg2+), and calcium (Ca2+) at varying high to very-high concentrations of 0.15 M, 1 M and 2 M. We compare the results to those obtained in physiological concentrations (0.15 M) of monovalent Na+ ions. Combining data from fluorescence femtosecond optical gating (FOG) and time-correlated single photon counting (TCSPC) techniques, dynamic fluorescence Stokes shifts in DNA are analysed over a broad range of time-scales, from 100 fs to 10 ns. We find that while divalent cation crowding strongly influences the DNA stability and ligand binding affinity to DNA, the dynamics of DNA solvation remain remarkably similar across a broad range of five decades in time, even in a high-salinity crowded environment with divalent cations, as compared to the physiological concentration of the Na+ ion. Steady-state and time-resolved data of the DNA-groove-bound ligand are seemingly unaffected by ion-crowding in hypersaline solution, possibly due to ions being mostly displaced by the DNA-bound ligand. Furthermore, the dynamic coupling of cations with nearby water may possibly contribute to a net-neutral effect on the overall collective solvation dynamics in DNA, owing to the strong anti-correlation of their electrostatic interaction energy fluctuations. Such dynamic scenarios may persist within the cellular environment of marine life and other biological cells that experience hypersaline conditions.
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  • 文章类型: Journal Article
    G-四体复合物(G4s)是普遍存在的核酸折叠基序,其表现出依赖于阳离子条件的结构多样性。在这项工作中,我们利用温度控制的单分子荧光共振能量转移(smFRET)来阐明一价阳离子(K+和Na+)影响具有三态折叠平衡的简单G-四链体序列(5'-GGG-(TAAGGG)3-3')折叠拓扑的动力学和热力学机制。动力学测量表明,Na和K以两种截然不同的方式影响G4的形成:Na的存在通过低亲和力(Kd=228±26mM)的诱导拟合(IF)机制适度增强了反平行G4拓扑结构,而K+通过构象选择(CS)机制以更高的亲和力(Kd=1.9±0.2mM)驱动G4进入并行/混合拓扑结构。此外,折叠速率常数和平衡比的温度依赖性研究表明,G4结合K+(ΔH°结合>0,ΔS°结合>0)与Na+(ΔH°结合<0,ΔS°结合<0)的热力学驱动力明显不同,这进一步阐明了单价促进G-四链体折叠的可能途径的多样性。
    G-Quadruplexes (G4s) are ubiquitous nucleic acid folding motifs that exhibit structural diversity that is dependent on cationic conditions. In this work, we exploit temperature-controlled single-molecule fluorescence resonance energy transfer (smFRET) to elucidate the kinetic and thermodynamic mechanisms by which monovalent cations (K+ and Na+) impact folding topologies for a simple G-quadruplex sequence (5\'-GGG-(TAAGGG)3-3\') with a three-state folding equilibrium. Kinetic measurements indicate that Na+ and K+ influence G4 formation in two distinctly different ways: the presence of Na+ modestly enhances an antiparallel G4 topology through an induced fit (IF) mechanism with a low affinity (Kd = 228 ± 26 mM), while K+ drives G4 into a parallel/hybrid topology via a conformational selection (CS) mechanism with much higher affinity (Kd = 1.9 ± 0.2 mM). Additionally, temperature-dependent studies of folding rate constants and equilibrium ratios reveal distinctly different thermodynamic driving forces behind G4 binding to K+ (ΔH°bind > 0, ΔS°bind > 0) versus Na+ (ΔH°bind < 0, ΔS°bind < 0), which further illuminates the diversity of the possible pathways for monovalent facilitation of G-quadruplex folding.
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