covalent bonding

共价键合
  • 文章类型: Journal Article
    铌酸锂(LiNbO3)正在成为具有更高复杂性的集成光学应用的有吸引力的候选者,由于其固有的丰富的光电特性。为了弥补LiNbO3无法产生难以区分的单光子,在III-V化合物半导体之间构建的渐逝耦合异质界面(例如,InP)和LiNbO3通过等离子体活化为平衡集成效率和界面稳定性提供了可行的解决方案,同时实现了器件之间的亚50nm对准精度,从而为经典光电子学和量子光学提供超紧密片上光源。然而,由于热膨胀系数的巨大不匹配,在InP/LiNbO3平台的形成中仍然存在挑战。这里,我们使用不对称等离子体激活策略演示了InP/LiNbO3共价异质界面。不同的等离子体分别用于InP和LiNbO3的活化,有效地平衡表面官能团密度的增强和避免缺陷的产生。更重要的是,结合表面综合特性和界面性能,我们确定,氨溶液的引入使表面羟基“有效”,因为LiNbO3表面弛豫增加了-OH基团接触的机会。因此,在80°C下,在InP/LiNbO3界面上建立了强大的共价键网络,增强了9.7MPa的键合强度。此外,设计了一种基于InP/LiNbO3平台的混合量子光子芯片,用于计算耦合效率和失调对其的影响,展示了将平台扩展到混合集成量子系统的潜力。
    Lithium niobate (LiNbO3) is emerging as an appealing candidate for integrated optical applications with enhanced complexity, owing to its inherent abundant optoelectronic properties. To compensate for the inability of LiNbO3 to generate indistinguishable single photons, the evanescent coupling heterointerface constructed between III-V compound semiconductors (e.g., InP) and LiNbO3 through plasma activation provides a feasible solution for balancing the integration efficiency and interfacial stability while achieving sub-50 nm alignment accuracy between devices, thus offering ultracompact on-chip light sources for classical optoelectronics and quantum optics. However, a challenge remains in the formation of the InP/LiNbO3 platform due to the huge mismatch in the coefficient of thermal expansion. Here, we demonstrate the InP/LiNbO3 covalent heterointerface using an asymmetric plasma activation strategy. Different plasmas are used for the activation of InP and LiNbO3 specifically, balancing the enhancement of surface functional group density with the avoidance of defect generation effectively. More importantly, combined with surface comprehensive characterizations and interface performance, we determine that the introduction of ammonia solution enables the surface hydroxyl groups to be \"effective\" as LiNbO3 surface relaxation increases the chance of -OH groups\' contact. Therefore, a robust covalent bond network is established across the InP/LiNbO3 interface at 80 °C with an enhanced bonding strength of 9.7 MPa. Moreover, a hybrid quantum photonic chip based on the InP/LiNbO3 platform is designed to compute the coupling efficiency and the impact of misalignment on it, demonstrating the potential of extending the platform to hybrid integrated quantum systems.
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  • 文章类型: Journal Article
    酶固定化的使用在饮料加工中变得越来越流行,由于这种方法具有显著的优势,如增强酶性能和扩大应用,同时允许通过简单的过滤过程容易终止。这篇文献综述分析了大约120篇文章,2000年至2023年在WebofScience上发表,重点研究了用于饮料加工应用的酶固定系统。固定化对酶活性的影响,包括对化学和动力学性质的影响,可回收性,在连续过程中的可行性,进行了评估。这些系统在饮料生产中的应用,比如葡萄酒,啤酒,果汁,牛奶,和植物性饮料,进行了检查。固定化过程有效地提高了pH值和热稳定性,但通过降低最大速度和米氏-门顿常数对动力学特性产生了负面影响。然而,它允许多次重复使用,并促进连续流动过程。封装还允许通过简单过滤简化从饮料中去除酶的过程控制。不需要昂贵的热处理,这可能会导致产品质量损失。
    The use of enzyme immobilisation is becoming increasingly popular in beverage processing, as this method offers significant advantages, such as enhanced enzyme performance and expanded applications, while allowing for easy process termination via simple filtration. This literature review analysed approximately 120 articles, published on the Web of Science between 2000 and 2023, focused on enzyme immobilisation systems for beverage processing applications. The impact of immobilisation on enzymatic activity, including the effects on the chemical and kinetic properties, recyclability, and feasibility in continuous processes, was evaluated. Applications of these systems to beverage production, such as wine, beer, fruit juices, milk, and plant-based beverages, were examined. The immobilisation process effectively enhanced the pH and thermal stability but caused negative impacts on the kinetic properties by reducing the maximum velocity and Michaelis-Menten constant. However, it allowed for multiple reuses and facilitated continuous flow processes. The encapsulation also allowed for easy process control by simplifying the removal of the enzymes from the beverages via simple filtration, negating the need for expensive heat treatments, which could result in product quality losses.
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  • 文章类型: Journal Article
    作为一种实用的化学能转换技术,电催化可用于能源转化和环境保护等领域。近年来,大量的研究工作已经致力于高性能电催化剂的设计和开发,因为催化剂的合理设计对于提高电催化性能至关重要。通过在界面处形成不同组分之间的相互作用来产生电催化剂是控制和提高性能的重要手段。因此,本文首次系统地总结了合成电催化剂的几种常见界面结合力。讨论围绕这些结合力在各种电催化反应过程中发挥的关键作用。该综述还涉及能够证明这些界面结合力存在的各种表征技术。最后,提出了利用界面结合力设计和研究材料的一些前景和挑战。
    As a practical chemical energy conversion technology, electrocatalysis could be used in fields of energy conversion and environmental protection. In recent years, significant research efforts have been devoted to the design and development of high-performance electrocatalysts because the rational design of catalysts is crucial for enhancing electrocatalytic performance. Creating electrocatalysts by forming interactions between different components at the interface is an important means of controlling and improving performance. Therefore, several common interfacial binding forces used for synthesizing electrocatalysts was systematically summarized in this review for the first time. The discussion revolves around the crucial roles these binding forces play in various electrocatalytic reaction processes. Various characterization techniques capable of proving the existence of these interfacial binding forces was also involved in the review. Finally, some prospects and challenges for designing and researching materials through the utilization of interfacial binding forces were presented.
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  • 文章类型: Journal Article
    在全球抗击由高度传染性SARS-CoV-2病毒引起的COVID-19大流行的斗争中,寻找有效的药物至关重要。通过对SARS-CoV-2木瓜蛋白酶(PLpro)作为一个有前途的治疗靶标的重点研究,由于其在病毒复制和免疫调节中的关键作用,包含Cys111,His272和Asp286的PLpro的催化三联体强调Cys111是与配体潜在共价键的有趣的亲核中心。结合位点的详细分析揭示了与疏水和极性残基的关键相互作用,展示腔的结构见解,加深我们对其分子景观的理解。关注变体中PLpro的序列(Alpha,Beta,Gamma,Delta和Omicron)和最近感兴趣的变体,JN.1保持保守,在活性位点没有突变。此外,对apo的彻底探索,非共价结合,共价结合的PLpro构象暴露了环区的显著构象变化,为配体-蛋白质复合物形成的复杂动力学提供了宝贵的见解。采用战略性的电子药物再利用,这项研究迅速确定了潜在的目标抑制分子。在共价对接研究和分子动力学领域,使用报道的抑制剂和临床测试的分子阐明了与半胱氨酸残基形成稳定的共价键,为潜在的治疗应用奠定了坚实的基础。这些细节不仅加深了我们对PLpro抑制的理解,而且在塑造COVID-19治疗策略的动态格局中起着关键作用。
    In the global fight against the COVID-19 pandemic caused by the highly transmissible SARS-CoV-2 virus, the search for potent medications is paramount. With a focused investigation on the SARS-CoV-2 papain-like protease (PLpro) as a promising therapeutic target due to its pivotal role in viral replication and immune modulation, the catalytic triad of PLpro comprising Cys111, His272, and Asp286, highlights Cys111 as an intriguing nucleophilic center for potential covalent bonds with ligands. The detailed analysis of the binding site unveils crucial interactions with both hydrophobic and polar residues, demonstrating the structural insights of the cavity and deepening our understanding of its molecular landscape. The sequence of PLpro among variants of concern (Alpha, Beta, Gamma, Delta and Omicron) and the recent variant of interest, JN.1, remains conserved with no mutations at the active site. Moreover, a thorough exploration of apo, non-covalently bound, and covalently bound PLpro conformations exposes significant conformational changes in loop regions, offering invaluable insights into the intricate dynamics of ligand-protein complex formation. Employing strategic in silico medication repurposing, this study swiftly identifies potential molecules for target inhibition. Within the domain of covalent docking studies and molecular dynamics, using reported inhibitors and clinically tested molecules elucidate the formation of stable covalent bonds with the cysteine residue, laying a robust foundation for potential therapeutic applications. These details not only deepen our comprehension of PLpro inhibition but also play a pivotal role in shaping the dynamic landscape of COVID-19 treatment strategies.
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  • 文章类型: Journal Article
    在这项研究中,通过共价键合方法在先前合成并表征的聚(N-乙烯基吡咯烷酮-co-丙烯酸丁酯-co-N羟甲基丙烯酰胺)三元共聚物膜上进行转化酶的固定。使用戊二醛(GA)作为交联剂,使用牛血清白蛋白(BSA)作为结合剂。最佳pH值,温度,聚合物的量,底物浓度,测定游离酶和固定化酶的BSA量和GA值的量。最佳pH值和温度值为pH=5.0,T=55°C,游离和固定化酶的pH=7.0和T=80°C,分别。特别是,固定化酶的最佳温度为80°C提供了其商业使用的潜力。使用众所周知的Lineweaver-Burk方法确定游离酶和固定化酶的动力学参数。发现游离酶(13.4μM/min)和固定化酶(12.2μM/min)的Vmax值彼此接近,而固定化酶的Km值(8.33mM)远低于游离酶的Km值(29.41mM)。在用桃汁和橙汁进行的重复使用研究中,经测定,即使在1个月内重复使用30次后,固定化酶仍保留约90%的活性。
    In this study, immobilization of invertase enzyme was performed on a previously synthesized and characterized poly(N-vinylpyrrolidone-co-butylacrylate-co-N hydroxymethylacrylamide) terpolymer membranes by covalent bonding method. Glutaraldehyde(GA) was used as the crosslinker and Bovine Serum Albumin(BSA) was used as the binding agent. Optimum pH, temperature, amount of polymer, substrate concentration, amount of BSA and amount of GA values were determined for both free and immobilized enzyme. Optimum pH and temperature values were found as pH = 5.0, T = 55 °C, pH = 7.0 and T = 80 °C for free and immobilized enzyme, respectively. In particular, the optimum temperature of 80 °C for the immobilized enzyme provides its potential to be used commercially. The kinetic parameters of the free enzyme and the immobilized enzyme were determined using the well known Lineweaver-Burk method. The Vmax values for free (13.4 μM/min) and immobilized enzyme (12.2 μM/min) were found as close to each other, while the Km value of the immobilized enzyme (8.33 mM) was much lower than that of the free enzyme (29.41 mM). In reuse studies conducted with peach and orange juices, it was determined that the immobilized enzyme retained approximately 90% of its activity even after 30 reuses within 1 month.
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  • 文章类型: Journal Article
    巯基聚酰亚胺是通过硫内酯单体的亲核开环反应合成的(BPDA-T,ODPA-T,BTDA-T)与聚乙烯亚胺(PEI),它们被涂覆在碳纳米管上作为基质材料(BPTP@CNT,ODTP@CNT,和BTTP@CNT)的硫阴极。BPTP@CNT/S,ODTP@CNT/S,和BTTP@CNT/S作为阴极材料,不仅促进了硫和多硫化物与巯基聚酰亚胺的共价键合,而且降低了可溶性多硫化物在氧化还原过程中的穿梭效应。此外,基于巯基的聚酰亚胺可以帮助改善硫和导电碳之间的相容性和界面接触,同时减轻阴极的体积膨胀。此外,碳纳米管的导电网络提高了阴极材料的电子导电性。BTTP@CNT/S阴极显示出优越的稳定性(1C时初始容量为902mAhg-1,500次循环后的容量保持率为88.58%),当硫载量为4.8mgcm-2(电解质/硫比:10μLmg-1)时,初始容量可以达到718mAhg-1,这充分证明了巯基基聚酰亚胺材料大规模应用的可行性。
    Sulfhydryl-based polyimides were synthesized by the nucleophilic ring-opening reaction of thiolactone monomers (BPDA-T, ODPA-T, BTDA-T) with polyethylenimine (PEI), and they were coated on carbon nanotubes as host materials (BPTP@CNT, ODTP@CNT, and BTTP@CNT) of the sulfur cathode. BPTP@CNT/S, ODTP@CNT/S, and BTTP@CNT/S as cathode materials not only promote the covalent bonding of sulfur and polysulfide with sulfhydryl-based polyimides but also reduce the shuttle effect of soluble polysulfide in the redox process. Moreover, sulfhydryl-based polyimides can help improve the compatibility and interfacial contact between sulfur and conductive carbon while alleviating the volume expansion of the cathode. In addition, the conductive network of carbon nanotubes improves the electronic conductivity of the cathode materials. The BTTP@CNT/S cathode showed superior stability (the initial capacity was 902 mAh g-1 at 1C, and the capacity retention rate was 88.58% after 500 cycles) and the initial capacity could reach 718 mAh g-1 when the sulfur loading was 4.8 mg cm-2 (electrolyte/sulfur ratio: 10 μL mg-1), which fully proves the feasibility of the large-scale application of sulfhydryl-based polyimide materials.
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  • 文章类型: Journal Article
    价电子是固体催化剂和催化反应中的主要参与者之一,因为它们涉及几个相关的现象,如化学键合,磁性,化学吸附,和债券激活。在含有d-过渡金属的固体催化剂的情况下尤其如此,表现出广泛的磁现象,从顺磁性到集体行为。的确,外部d壳的电子是,一方面,参与在催化剂结构内和其表面上形成键,and,另一方面,它们对材料的磁性负责。出于这个原因,自20世纪中叶以来,磁性与多相催化之间的关系一直引起人们的极大兴趣。在过去的十年里,这个话题获得了很多关注,由于量子自旋交换相互作用的轨道工程以及外部磁场在几种催化反应中作为增强工具的广泛应用。通过实验示例和固体结构中磁性与共价键之间相互作用的证据以及化学吸附过程中的相互作用来讨论该主题。讨论了共价键合,因为它代表了对材料中遇到的键的最强贡献之一。
    Valence electrons are one of the main players in solid catalysts and in catalytic reactions, since they are involved in several correlated phenomena like chemical bonding, magnetism, chemisorption, and bond activation. This is particularly true in the case of solid catalysts containing d-transition metals, which exhibit a wide range of magnetic phenomena, from paramagnetism to collective behaviour. Indeed, the electrons of the outer d-shells are, on one hand, involved in the formation of bonds within the structure of a catalyst and on its surface, and, on the other, they are accountable for the magnetic properties of the material. For this reason, the relationship between magnetism and heterogeneous catalysis has been a source of great interest since the mid-20th century. The subject has gained a lot of attention in the last decade, thanks to the orbital engineering of quantum spin-exchange interactions and to the widespread application of external magnetic fields as boosting tools in several catalytic reactions. The topic is discussed here through experimental examples and evidences of the interplay between magnetism and covalent bonding in the structure of solids and during the chemisorption process. Covalent bonding is discussed since it represents one of the strongest contributions to bonds encountered in materials.
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  • 文章类型: Journal Article
    放置在90°C热水(HW)中的铝(Al)由于与水的反应而变得粗糙,形成氢氧化铝和氧化铝,以及释放氢气。因此,粗糙的表面是亲水的,并且具有大大增加的表面积,可用于需要亲水性和增加表面积的应用,如大气水分收集。另一方面,当使用HW粗糙化Al基板的指定区域时,保护其他地区免受HW攻击的方法是必要的。我们证明了氟化膦酸(FPA,在Al膜的天然氧化物上衍生的CF3(CF2)13(CH2)2P(=O)(OH)2)保护了下面的金属衬底免受HW攻击。使用接触角测量检查了经过HW处理的FPA衍生化Al的完整润湿性和表面形态,扫描电子显微镜和原子力显微镜,分别。此外,通过飞行时间二次离子质谱(ToF-SIMS)研究了HW处理前后FPA衍生化Al的表面和界面化学,验证FPASAMs在HW治疗后是否完好无损。因此,ToF-SIMS结果进行了解释,在分子水平上,为什么HW治疗根本不影响下面的Al。因此,当与HW处理组合时,预期FPA衍生化被开发为用于在Al上形成亲水和疏水区域的图案化方法。
    Aluminum (Al) placed in hot water (HW) at 90 °C is roughened due to its reaction with water, forming Al hydroxide and Al oxide, as well as releasing hydrogen gas. The roughened surface is thus hydrophilic and possesses a hugely increased surface area, which can be useful in applications requiring hydrophilicity and increased surface area, such as atmospheric moisture harvesting. On the other hand, when using HW to roughen specified areas of an Al substrate, ways to protect the other areas from HW attacks are necessary. We demonstrated that self-assembled monolayers (SAMs) of a fluorinated phosphonic acid (FPA, CF3(CF2)13(CH2)2P(=O)(OH)2) derivatized on the native oxide of an Al film protected the underneath metal substrate from HW attack. The intact wettability and surface morphology of FPA-derivatized Al subjected to HW treatment were examined using contact angle measurement, and scanning electron microscopy and atomic force microscopy, respectively. Moreover, the surface and interface chemistry of FPA-derivatized Al before and after HW treatment were investigated by time-of-flight secondary ion mass spectrometry (ToF-SIMS), verifying that the FPA SAMs were intact upon HW treatment. The ToF-SIMS results therefore explained, on the molecular level, why HW treatment did not affect the underneath Al at all. FPA derivatization is thus expected to be developed as a patterning method for the formation of hydrophilic and hydrophobic areas on Al when combined with HW treatment.
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  • 文章类型: Journal Article
    背景:酶交联是一种可用于使用多酚修饰印加花生白蛋白(IPA)的方法,并提供理想的功能;然而,多酚结构对共轭性质的影响尚不清楚。在这项研究中,我们选择了四种具有不同数量酚羟基的多酚[对羟基苯甲酸(HBA),原儿茶酸(PCA),没食子酸(GA),和表没食子儿茶素没食子酸酯(EGCG)]通过酶交联共价修饰IPA,并探讨了IPA-多酚共轭物的结构-功能变化。
    结果:十二烷基硫酸钠-聚丙烯酰胺凝胶电泳(SDS-PAGE)和基质辅助激光解吸/电离飞行时间质谱(MALDI-TOF-MS)分析表明,漆酶成功地促进了IPA与多酚的共价交联,共轭程度的顺序为EGCG>GA>PCA>HBA,IPA-EGCG缀合物显示出最高的多酚结合当量(98.35gkg-1蛋白),以及游离氨基含量的显著降低,巯基,和酪氨酸组。漆酶对多酚的氧化形成与IPA的反应性基团共价交联的醌或半醌自由基,导致IPA的二级和三级结构发生重大变化,球形结构转变为致密的层状结构。IPA-EGCG偶联物的2,2-二苯基-1-吡啶酰肼(DPPH)自由基清除能力和乳化稳定性提高了近6倍和2.7倍,分别,与未修饰的IPA相比。
    结论:这些数据表明,多酚羟基的数量越高,IPA-多酚共轭程度越高;此外,酶交联可以显著提高IPA的功能性能。©2024化学工业学会。
    BACKGROUND: Enzymatic crosslinking is a method that can be used to modify Inca peanut albumin (IPA) using polyphenols, and provides desirable functionalities; however, the effect of polyphenol structures on conjugate properties is unclear. In this study, we selected four polyphenols with different numbers of phenolic hydroxyl groups [para-hydroxybenzoic acid (HBA), protocatechuic acid (PCA), gallic acid (GA), and epigallocatechin gallate (EGCG)] for covalent modification of IPA by enzymatic crosslinking, and explored the structure-function changes of the IPA-polyphenol conjugates.
    RESULTS: Sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) analysis showed that laccase successfully promoted covalent crosslinking of IPA with polyphenols, with the order of degree of conjugation as EGCG > GA > PCA > HBA, the IPA-EGCG conjugate showed the highest polyphenol binding equivalents (98.35 g kg-1 protein), and a significant reduction in the content of free amino, sulfhydryl, and tyrosine group. The oxidation of polyphenols by laccase forms quinone or semiquinone radicals that are covalently crosslinked to the reactive groups of IPA, leading to significant changes in the secondary and tertiary structures of IPA, with spherical structures transforming into dense lamellar structures. The 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging ability and emulsification stability of IPA-EGCG conjugates improved by almost 6-fold and 2.7-fold, respectively, compared with those of unmodified IPA.
    CONCLUSIONS: These data suggest that the higher the number of polyphenol hydroxyl groups, the higher the degree of IPA-polyphenol conjugation; additionally, enzymatic crosslinking can significantly improve the functional properties of IPA. © 2024 Society of Chemical Industry.
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  • 文章类型: Journal Article
    构建亲锂碳主体被认为是抑制Li枝晶形成和减轻Li金属阳极体积膨胀的有效策略。然而,传统的表面装饰方法在长期循环中限制了亲石碳主体的实际应用。在这项工作中,通过原位固态反应产生由共价键合到蜂窝状碳纳米纤维(MgF2/HCNFs)的超细MgF2纳米点组成的坚固主体。复合材料表现出超轻的重量,优异的亲岩性,和结构稳定性,有助于显着提高能源效率和电池的寿命。具体来说,强共价键不仅防止MgF2纳米点迁移和聚集,而且在熔融Li注入过程中增强Mg和Li之间的结合能。这允许有效且稳定地调节重复的Li电镀/剥离。因此,MgF2/HCNF-Li电极在200次循环后提供97%的高库仑效率,稳定循环超过2000小时。此外,具有LiFePO4阴极的全电池在0.5C下500次循环后实现85%的容量保持率。这项工作提供了一种策略,以指导无枝晶Li沉积模式朝着高性能Li金属电池的发展。
    Constructing lithiophilic carbon hosts has been regarded as an effective strategy for inhibiting Li dendrite formation and mitigating the volume expansion of Li metal anodes. However, the limitation of lithiophilic carbon hosts by conventional surface decoration methods over long-term cycling hinders their practical application. In this work, a robust host composed of ultrafine MgF2 nanodots covalently bonded to honeycomb carbon nanofibers (MgF2/HCNFs) is created through an in situ solid-state reaction. The composite exhibits ultralight weight, excellent lithiophilicity, and structural stability, contributing to a significantly enhanced energy efficiency and lifespan of the battery. Specifically, the strong covalent bond not only prevents MgF2 nanodots from migrating and aggregating but also enhances the binding energy between Mg and Li during the molten Li infusion process. This allows for the effective and stable regulation of repeated Li plating/stripping. As a result, the MgF2/HCNF-Li electrode delivers a high Coulombic efficiency of 97% after 200 cycles, cycling stably for more than 2000 h. Furthermore, the full cells with a LiFePO4 cathode achieve a capacity retention of 85% after 500 cycles at 0.5C. This work provides a strategy to guide dendrite-free Li deposition patterns toward the development of high-performance Li metal batteries.
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