Borohydrides

硼氢化物
  • 文章类型: Journal Article
    近几十年来,利用硼氢化物(B-NZVI)合成的纳米零价铁被广泛应用于环境修复。然而,硼在增强B-NZVI的固有反应性方面的贡献及其在去除六价铬[Cr(VI)]方面的有效性尚未得到很好的认识和量化。据我们所知,在这里,首次证明了B-NZVI的核-壳结构,其特征是氧化铁壳下方的Fe-B合金壳。合金硼可以降低H+,在B-NZVIs的酸消化过程中产生超过35.6%的H2。此外,合金B在Cr(VI)去除过程中为Fe3还原提供电子,防止反应性颗粒表面的原位钝化。同时,B-NZVI的无定形氧化物壳表现出增加的缺陷密度,促进壳外Fe2+的释放以减少Cr(VI),形成层状结构的沉淀物和强烈的Fe-O键。因此,B-NZVI的表面积归一化容量和表面反应速率比NZVI晶体高6.5和6.9倍,分别。这项研究揭示了合金B在使用B-NZVI去除Cr(VI)中的重要性,并提出了一种全面的方法来研究B-NZVI去除污染物所涉及的电子途径和机制。
    Nanoscale zerovalent iron synthesized using borohydride (B-NZVI) has been widely applied in environmental remediation in recent decades. However, the contribution of boron in enhancing the inherent reactivity of B-NZVI and its effectiveness in removing hexavalent chromium [Cr(VI)] have not been well recognized and quantified. To the best of our knowledge, herein, a core-shell structure of B-NZVI featuring an Fe-B alloy shell beneath the iron oxide shell is demonstrated for the first time. Alloyed boron can reduce H+, contributing to more than 35.6% of H2 generation during acid digestion of B-NZVIs. In addition, alloyed B provides electrons for Fe3+ reduction during Cr(VI) removal, preventing in situ passivation of the reactive particle surface. Meanwhile, the amorphous oxide shell of B-NZVI exhibits an increased defect density, promoting the release of Fe2+ outside the shell to reduce Cr(VI), forming layer-structured precipitates and intense Fe-O bonds. Consequently, the surface-area-normalized capacity and surface reaction rate of B-NZVI are 6.5 and 6.9 times higher than those of crystalline NZVI, respectively. This study reveals the importance of alloyed B in Cr(VI) removal using B-NZVI and presents a comprehensive approach for investigating electron pathways and mechanisms involved in B-NZVIs for contaminant removal.
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  • 文章类型: Journal Article
    RNA中表位基因组修饰的功能分析受到缺乏准确捕获其位置和水平的方法的限制。我们先前证明,RNA修饰N4-乙酰胞苷(ac4C)可以通过硼氢化钠还原为四氢乙酰胞苷(四氢-ac4C)以碱基分辨率定位,随后进行cDNA合成,使腺苷错误掺入相对于减少的ac4C位点,在乙酰化的胞苷(RedaC:T)处达到C:T错配。然而,这个过程相对低效,在18SrRNA中的完全修饰的ac4C位点处导致小于20%的C:T错配。考虑到包括mRNA在内的其他底物中的ac4C位置不太可能达到完全外显率,这种方法对于全面映射并不理想。这里,我们引入了“RetraC:T”(还原为四氢ac4C并用氨基dATP进行逆转录以诱导C:T错配)作为一种增强检测细胞RNA中ac4C的能力的方法。简而言之,RNA通过NaBH4或密切相关的试剂氰基硼氢化钠(NaCNBH3)还原,然后在修饰的DNA核苷酸存在下进行cDNA合成,2-氨基-dATP,优先结合四氢-ac4C。引入改良的dNTP大大提高了C:T失配率,在18SrRNA中达到ac4C的化学计量检测。重要的是,2-氨基-dATP不会导致截短的cDNA产物,也不会增加其他位置的错配。因此,修改后的dNTP作为新添加到工具箱中,用于以基本分辨率检测ac4C。
    The functional analysis of epitranscriptomic modifications in RNA is constrained by a lack of methods that accurately capture their locations and levels. We previously demonstrated that the RNA modification N4-acetylcytidine (ac4C) can be mapped at base resolution through sodium borohydride reduction to tetrahydroacetylcytidine (tetrahydro-ac4C), followed by cDNA synthesis to misincorporate adenosine opposite reduced ac4C sites, culminating in C:T mismatches at acetylated cytidines (RedaC:T). However, this process is relatively inefficient, resulting in <20% C:T mismatches at a fully modified ac4C site in 18S rRNA. Considering that ac4C locations in other substrates including mRNA are unlikely to reach full penetrance, this method is not ideal for comprehensive mapping. Here, we introduce \"RetraC:T\" (reduction to tetrahydro-ac4C and reverse transcription with amino-dATP to induce C:T mismatches) as a method with enhanced ability to detect ac4C in cellular RNA. In brief, RNA is reduced through NaBH4 or the closely related reagent sodium cyanoborohydride (NaCNBH3) followed by cDNA synthesis in the presence of a modified DNA nucleotide, 2-amino-dATP, that preferentially binds to tetrahydro-ac4C. Incorporation of the modified dNTP substantially improved C:T mismatch rates, reaching stoichiometric detection of ac4C in 18S rRNA. Importantly, 2-amino-dATP did not result in truncated cDNA products nor increase mismatches at other locations. Thus, modified dNTPs are introduced as a new addition to the toolbox for detecting ac4C at base resolution.
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  • 文章类型: Journal Article
    Nanostructured metal hydrides with unique morphology and improved hydrogen storage properties have attracted intense interests. However, the study of the growth process of highly active borohydrides remains challenging. Herein, for the first time the synthesis of LiBH4 nanorods through a hydrogen-assisted one-pot solvothermal reaction is reported. Reaction of n-butyl lithium with triethylamine borane in n-hexane under 50 bar of H2 at 40-100 °C gives rise to the formation of the [100]-oriented LiBH4 nanorods with 500-800 nm in diameter, whose growth is driven by orientated attachment and ligand adsorption. The unique morphology enables the LiBH4 nanorods to release hydrogen from ≈184 °C, 94 °C lower than the commercial sample (≈278 °C). Hydrogen release amounts to 13 wt% within 40 min at 450 °C with a stable cyclability, remarkably superior to the commercial LiBH4 (≈9.1 wt%). More importantly, up to 180 °C reduction in the onset temperature of hydrogenation is successfully attained by the nanorod sample with respect to the commercial counterpart. The LiBH4 nanorods show no foaming during dehydrogenation, which improves the hydrogen cycling performance. The new approach will shed light on the preparation of nanostructured metal borohydrides as advanced functional materials.
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  • 文章类型: Journal Article
    在当代语境中,在液相过程中执行光氧化剂和还原剂驱动的反应仍然具有挑战性,主要是由于缺乏了解纳米功能催化剂反应潜力的通用工具。在这项研究中,双活性纳米金属(Au和掺杂Au的Cu)覆盖在大豆卵磷脂(SL)中,被开发和表征,结合灵活性和液相催化剂的催化优势和稳定性。合成的SL-Au(LG)和SL-Au-Cu(LGC)催化剂有效降解了罗丹明B(RB,100%)在4.5h内宽pH范围(3-7)和对硝基苯酚(p-NP,>90%的降解在pH7)在NaBH4的存在下,在缓慢的动力学搅拌(〜72小时)。RB降解遵循具有较高r2的伪二级动力学模型,p-NP降解遵循一级动力学。嵌入SL排列的结构顺序中的活性位点显示出提高的催化活性,通过悬浮在磷脂中的金属(LG和LGC)内的中间/激发态和带电元素的运动进一步增强。这些催化剂的物理化学特性的自我调节可调性为现代双活性(氧化还原)催化剂转化为动态均相当量提供了方便且可推广的平台。
    In the contemporary context, executing light-oxidant- and reductant-driven reactions in solution-phase processes remains challenging mainly due to the lack of general tools for understanding the reactive potential of nano-functional catalysts. In this study, dual-active nanometals (Au and Cu doped with Au) capped within soy lecithin (SL), were developed and characterized, combining flexibility with the catalytic advantages and stability of liquid-phase catalysts. The as-synthesized SL-Au (LG) and SL-Au-Cu (LGC) catalysts were efficiently degraded rhodamine B (RB, 100%) in the presence of H2O2 under light irradiation (350 W lamp) at wide pH range (3-7) within 4.5 h and p-nitrophenol (p-NP, >90% degradation at pH 7) in the presence of NaBH4 under normal stirring with slower kinetics (∼72 h). RB degradation followed a pseudo-second-order kinetic model with a higher r2, and p-NP degradation followed first-order kinetics. The active sites embedded within the structural order of SL arrangement displayed elevated catalytic activity, which was further enhanced by the movement of intermediate/excited states and charged elements within the metal suspended in the phospholipid (LG and LGC). The self-regulating tunability of the physicochemical characteristics of these catalysts provides a convenient and generalizable platform for the transformation of modern dual-active (redox) catalysts into dynamic homogeneous equivalents.
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  • 文章类型: Journal Article
    使用两种还原剂的组合:硼氢化钠(SBH)和柠檬酸三钠(TSC),以受控方式合成了直径为几nm至100nm的纳米球形式的银纳米颗粒(AgNP)。用不同浓度的AgNPs对铜绿假单胞菌(PA)和金黄色葡萄球菌(SA)两种细菌的抗菌活性进行了研究,阳性对照为氨苄西林(Amp)50µg/mL,阴性对照为水。AgNPs进行了形态学研究,使用透射电子显微镜(TEM)和动态光散射(DLS)测量的尺寸和尺寸分布。通过记录它们的UV-Vis吸收光谱来研究AgNPs的光学性质。使用圆盘扩散法测定AgNP的抗微生物活性。结果表明,AgNPs的抗菌能力取决于浓度和粒径。颗粒浓度为50微克/毫升,抗菌能力最好。颗粒尺寸越小,抗菌能力越高。同时使用两种还原剂TSC和SBH是合成AgNP颗粒的新颖之处,所述颗粒在控制颗粒尺寸的同时具有均匀的形状和尺寸。在这个基础上,它们的抗菌性能增加。
    Silver nanoparticles (AgNPs) in the form of nanospheres from a few nm to 100 nm in diameter were synthesized in a controlled manner using a combination of two reducing agents: sodium borohydride (SBH) and trisodium citrate (TSC). The influence of the size of AgNPs on antibacterial activity was investigated with different concentrations of AgNPs on two types of bacteria:Pseudomonas aeruginosa(PA) andStaphylococcus aureusresistant (SA) while the positive control wasAmpicillin (Amp)50μg/ml and the negative control was water. AgNPs were investigated for morphology, size and size distribution using transmission electron microscopy (TEM) and dynamic light scattering (DLS) measurements. The optical properties of the AgNPs were investigated by recording their UV-vis absorption spectra. The antimicrobial activity of AgNPs was determined using the disc diffusion method. The results showed that the antibacterial ability of AgNPs depends on both concentration and particle size. With a particle concentration of 50μg ml-1, the antibacterial ability is the best. The smaller the particle size, the higher the antibacterial ability. The simultaneous use of two reducing agents TSC and SBH is the novelty of the article to synthesize AgNPs particles that are uniform in shape and size while controlling the particle size. On that basis, their antibacterial performance is increased.
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  • 文章类型: Journal Article
    农作物农药残留的环境监测对于食品安全和环境保护都至关重要。传统的方法面临的挑战,由于在果皮和牙髓组织内源性化合物的干扰,通常是侵入性的,劳动密集型,不足以实时观察有害物质的分布。在这项研究中,动态硼氢化物还原的纳米粒子被用作增强的底物。第一次,利用表面增强拉曼光谱(SERS)成像来实现农药残留的全过程视觉检测。所开发的方法既稳定又灵敏,检测下限低于1pg/mL,再加上强大的定量分析能力。该技术已成功用于检测各种作物和果汁中的残留信号。此外,SERS成像用于绘制从水果和蔬菜外部到内部的农药残留分布图。顶点成分分析通过减轻植物自发荧光的干扰进一步完善了该过程。总的来说,这一创新战略促进了全面的农药残留监测,为控制农作物中的有害物质提供了有力的工具。它的潜在应用范围超出了食品安全,对可持续农业生产和加强环境保护抱有重大希望。
    Environmental monitoring of pesticide residues in crops is essential for both food safety and environmental protection. Traditional methodologies face challenges due to the interference of endogenous compounds in peel and pulp tissues, often being invasive, labor-intensive, and inadequate for real-time observation of hazardous substance distribution. In this study, dynamic borohydride-reduced nanoparticles were employed as enhanced substrates. For the first time, surface-enhanced Raman spectroscopy (SERS) imaging was harnessed to enable whole-process visual detection of pesticide residues. The developed method is both stable and sensitive, boasting a detection lower limit below 1 pg/mL, coupled with robust quantitative analytical capabilities. This technique was successfully employed to detect residue signals across various crops and fruit juices. Furthermore, SERS imaging was utilized to map the distribution of pesticide residues from the exterior to the interior of fruits and vegetables. Vertex component analysis further refined the process by mitigating interference from plant autofluorescence. Collectively, this innovative strategy facilitates comprehensive pesticide residue monitoring, offering a potent tool for controlling hazardous substances in crops. Its potential applications extend beyond food safety, holding significant promise for sustainable agricultural production and enhanced environmental safeguarding.
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  • 文章类型: Journal Article
    提出了一种创造性地设计的新型两步增强技术,其中B族维生素分子被硼氢化钠动态吸附到银纳米颗粒的表面上,随后在阳离子(钙离子)存在下进行局部等离子体共振,最终在同一分子上实现化学和物理协同增强,并构建维生素检测的“表面热点”两步增强平台。促进的维生素分子的拉曼信号增强了9个数量级。在随后的研究中,观察到维生素B2分子在银纳米颗粒的表面上处于接近垂直的图像中,这也可能有助于拉曼信号增强。结合深度学习技术,该方法已成功应用于体液中B族维生素的检测。作为一个准确的,快速,可重复,非侵入性,和多功能测定平台,它为智能识别食品中的痕量B分子带来了巨大的希望,制药,和人体。
    A creatively designed novel two-step enhancement technique is presented in which B vitamin molecules are dynamically adsorbed onto the surface of silver nanoparticles by sodium borohydride, followed by local plasmon resonance in the presence of cations (calcium ions), ultimately achieving synergistic chemical and physical enhancement on the same molecule and constructing a \"surface hot spots\" two-step enhancement platform for vitamin detection. The Raman signal of the promoted vitamin molecule is enhanced by nine orders of magnitude. In a subsequent study it was observed that the vitamin B2 molecules were in a near-vertical image on the surface of the silver nanoparticles, which may also contribute to the Raman signal enhancement. Combined with deep learning techniques, the method has been successfully applied to the detection of B vitamins in body fluids. As an accurate, rapid, reproducible, non-invasive, and versatile assay platform, it holds great promise for the intelligent identification of trace B molecules in food, pharmaceuticals, and the human body.
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  • 文章类型: Journal Article
    在弱配位非质子环境中通过离子复分解反应合成了四甲基硼氢化物。[(CH3)4P]BH4,与倾向于在四方晶系中结晶的相关[(CH3)4N]化合物相反,采用扭曲的纤锌矿结构(P63mc),类似于一些含有类似As和Sb离子的盐。[(CH3)4P]BH4在上述几个吸热和放热步骤中热分解。240°C。这使得它比[(CH3)4N]BH4更稳定,分解起始温度降低了约1。20°C和单独观察到的放热过程。在0-10GPa范围内测得的拉曼光谱表明,在0.53-1.86GPa内发生了多态转变,这由周期性DFT计算进一步证实。后者表明约0.8GPa的相变为[(CH3)4N]BH4的高压相。P63mc相似乎在高压下由于相对更紧密的二氢相互作用而不稳定,包括C-H...H-C触点.
    Tetramethylphosphonium borohydride was synthesized via an ion metathesis reaction in a weakly-coordinating aprotic environment. [(CH3)4P]BH4, in contrast to related [(CH3)4N]+ compounds which tend to crystallize in a tetragonal system, adopts the distorted wurtzite structure (P63mc), resembling some salts containing analogous ions of As and Sb. [(CH3)4P]BH4 decomposes thermally in several endo- and exothermic steps above ca. 240 °C. This renders it more stable than [(CH3)4N]BH4, with a lowered temperature of decomposition onset by ca. 20 °C and solely exothermic processes observed. Raman spectra measured at the 0-10 GPa range indicate that a polymorphic transition occurs within 0.53-1.86 GPa, which is further confirmed by the periodic DFT calculations. The latter suggests a phase transition around 0.8 GPa to a high-pressure phase of [(CH3)4N]BH4. The P63mc phase seems to be destabilized under high pressure by relatively closer dihydrogen interactions, including the C-H…H-C contacts.
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  • 文章类型: Journal Article
    我们描述了一种独特的催化体系,该体系在反应网络中具有Ti和Cr催化剂的有效偶联,该反应网络允许使用[BH4]-作为催化自由基化学中的化学计量氢原子和电子供体。关键特征是在温和条件下从[BH4]-到Cr的中继氢原子转移产生活性催化剂。这使得环氧化物减少,区域相反的环氧化物开放和自由基环化,这与自由基的协同催化或通过Meinwald重排和随后的羰基还原的环氧化物还原是不可能的。没有观察到[BH4]-盐的典型SN2型反应性。
    We describe a unique catalytic system with an efficient coupling of Ti- and Cr-catalysis in a reaction network that allows the use of [BH4 ]- as stoichiometric hydrogen atom and electron donor in catalytic radical chemistry. The key feature is a relay hydrogen atom transfer from [BH4 ]- to Cr generating the active catalysts under mild conditions. This enables epoxide reductions, regiodivergent epoxide opening and radical cyclizations that are not possible with cooperative catalysis with radicals or by epoxide reductions via Meinwald rearrangement and ensuing carbonyl reduction. No typical SN 2-type reactivity of [BH4 ]- salts is observed.
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  • 文章类型: Journal Article
    石榴石型氧化物Li6.4La3Zr1.4Ta0.6O12(LLZTO)具有优异的离子导电性和对锂(Li)金属的良好稳定性,但是需要高温烧结(约1200°C),这会导致高制造成本,机械加工性差,和高界面电阻。这里,报道了一种包含LLZTO-4LiBH4/xLi3BN2H8的新型高性能三组分复合固体电解质(CSE),它是通过球磨LLZTO-4LiBH4混合物,然后用Li3BN2H8手工研磨制备的。通过在120°C下加热冷压CSE粉末制成的绿色颗粒可提供超快的室温离子电导率(在30°C下约为1.73×10-3Scm-1)和超高的锂离子迁移数(约0.9999),这使得Li|Li对称电池在30°C下以仅30mV的过电位循环超过1600h。此外,Li|CSE|TiS2全电池提供201mAhg-1的容量,具有长循环能力。这些出色的性能是由于电解质颗粒中的低开孔率以及Li3BN2H8的高固有离子电导率和易变形性。
    Garnet-type oxide Li6.4 La3 Zr1.4 Ta0.6 O12 (LLZTO) features superior ionic conductivity and good stability toward lithium (Li) metal, but requires high-temperature sintering (≈1200 °C) that induces high fabrication cost, poor mechanical processability, and high interface resistance. Here, a novel high-performance tricomponent composite solid electrolyte (CSE) comprising LLZTO-4LiBH4 /xLi3 BN2 H8 is reported, which is prepared by ball milling the LLZTO-4LiBH4  mixture followed by hand milling with Li3 BN2 H8 . Green pellets fabricated by heating the cold-pressed CSE powders at 120 °C offer ultrafast room-temperature ionic conductivity (≈1.73 × 10-3  S cm-1  at 30 °C) and ultrahigh Li-ion transference number (≈0.9999), which enable the Li|Li symmetrical cells to cycle over 1600 h at 30 °C with only 30 mV of overpotential. Moreover, the Li|CSE|TiS2  full cells deliver 201 mAh g-1  of capacity with long cyclability. These outstanding performances are due to the low open porosity in the electrolyte pellets as well as the high intrinsic ionic conductivity and easy deformability of Li3 BN2 H8 .
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