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Gadolinium-Based NMR Spin Relaxation Measurements of Near-Surface Electrostatic Potentials of Biomolecules. 基于钆的核磁共振自旋弛豫测量生物大分子的近表面静电势
IF 14.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-19 DOI: 10.1021/jacs.4c04433
Binhan Yu, Nicolas Bolik-Coulon, Atul K Rangadurai, Lewis E Kay, Junji Iwahara

NMR spectroscopy is an important tool for the measurement of the electrostatic properties of biomolecules. To this point, paramagnetic relaxation enhancements (PREs) of 1H nuclei arising from nitroxide cosolutes in biomolecular solutions have been used to measure effective near-surface electrostatic potentials (ϕENS) of proteins and nucleic acids. Here, we present a gadolinium (Gd)-based NMR method, exploiting Gd chelates with different net charges, for measuring ϕENS values and demonstrate its utility through applications to a number of biomolecular systems. The use of Gd-based cosolutes offers several advantages over nitroxides for ϕENS measurements. First, unlike nitroxide compounds, Gd chelates enable electrostatic potential measurements on oxidation-sensitive proteins that require reducing agents. Second, the large electron spin quantum number of Gd (7/2) results in notably larger PREs for Gd chelates when used at the same concentrations as nitroxide radicals. Thus, it is possible to measure ϕENS values exclusively from + and - charged compounds even for highly charged biomolecules, avoiding the use of neutral cosolutes that, as we further establish here, limits the accuracy of the measured electrostatic potentials. In addition, the smaller concentrations of cosolutes required minimize potential binding to sites on macromolecules. Fourth, the closer proximity of the paramagnetic center and charged groups within Gd chelates, in comparison to the corresponding nitroxide compounds, enables more accurate predictions of ϕENS potentials for cross-validation of the experimental results. The Gd-based method described here, thus, broadens the applicability of studies of biomolecular electrostatics using solution NMR spectroscopy.

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引用次数: 0
Cryogenic and Dissolution DNP NMR on γ-Irradiated Organic Molecules.
IF 14.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-19 DOI: 10.1021/jacs.4c04041
Angeliki Giannoulis, Korin Butbul, Raanan Carmieli, Jihyun Kim, Elton Tadeu Montrazi, Kawarpal Singh, Lucio Frydman

Nuclear magnetic resonance (NMR) plays a central role in the elucidation of chemical structures but is often limited by low sensitivity. Dissolution dynamic nuclear polarization (dDNP) emerges as a transformative methodology for both solution-state NMR and metabolic NMR imaging, which could overcome this limitation. Typically, dDNP relies on combining a stable radical with the analyte within a uniform glass under cryogenic conditions. The electron polarization is then transferred through microwave irradiation to the nuclei. The present study explores the use of radicals introduced via γ-irradiation, as bearers of the electron spins that will enhance 1H or 13C nuclides. 1H solid-state NMR spectra of γ-irradiated powders at 1-5 K revealed, upon microwave irradiation, signal enhancements that, in general, were higher than those achieved through conventional glass-based DNP. Transfer of these samples to a solution-state NMR spectrometer via a rapid dissolution driven by a superheated water provided significant enhancements of solution-state 1H NMR signals. Enhancements of 13C signals in the γ-irradiated solids were more modest, as a combined consequence of a low radical concentration and of the dilute concentration of 13C in the natural abundant samples examined. Nevertheless, ca. 700-800-fold enhancements in 13C solution NMR spectra of certain sites recorded at 11.7 T could still be achieved. A total disappearance of the radicals upon performing a dDNP-like aqueous dissolution and a high stability of the samples were found. Overall, the study showcases the advantages and limitations of γ-irradiated radicals as candidates for advancing spectroscopic dDNP-enhanced NMR.

核磁共振(NMR)在阐明化学结构方面发挥着核心作用,但往往因灵敏度低而受到限制。溶解动态核极化(dDNP)是溶液态核磁共振和代谢核磁共振成像的一种变革性方法,可以克服这一局限。通常,dDNP 依赖于在低温条件下将稳定基与均匀玻璃中的分析物结合在一起。然后通过微波照射将电子极化转移到原子核上。本研究探讨了如何利用通过γ-辐照引入的自由基作为电子自旋的携带者,从而增强 1H 或 13C 核素。在 1-5 K 的温度下,γ-辐照粉末的 1H 固态核磁共振光谱显示,在微波辐照下,信号增强的程度总体上高于传统的玻璃基 DNP。通过过热水的快速溶解,将这些样品转移到溶液态 NMR 光谱仪中,可显著增强溶液态 1H NMR 信号。γ-辐照固体中 13C 信号的增强幅度较小,这是由于自由基浓度较低以及所研究的天然富集样品中 13C 浓度较低的综合结果。不过,在 11.7 T 下记录的某些位点的 13C 溶液 NMR 光谱仍然可以达到约 700-800 倍的增强。在进行类似 dDNP 的水溶液溶解时,发现自由基完全消失,而且样品具有很高的稳定性。总之,这项研究展示了 γ 辐照自由基作为推进 dDNP 增强 NMR 光谱的候选材料的优势和局限性。
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引用次数: 0
Origins of High Air Sensitivity and Treatment Strategies in O3-Type NaMn1/3 Fe1/3Ni1/3O2. O3 型 NaMn1/3 Fe1/3Ni1/3O2 的高空气灵敏度起源和处理策略。
IF 14.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-19 DOI: 10.1021/jacs.4c05255
Xian-Qi Xu, Jun-Yan Chen, Yao Jiang, Bo Xu, Xin-Lu Li, Chu-Ying Ouyang, Jia-Xin Zheng

Sodium-ion layered oxides are one of the most highly regarded sodium-ion cathode materials and are expected to be used in electric vehicles and large-scale grid-level energy storage systems. However, highly air-sensitive issues limit sodium-ion layered oxide cathode materials to maximize cost advantages. Industrial and scientific researchers have been developing cost-effective air sensitivity treatment strategies with little success because the impurity formation mechanism is still unclear. Using density functional theory calculations and ab initio molecular dynamics simulations, this work shows that the poor air stability of O3-type NaMn1/3Fe1/3Ni1/3O2 (NMFNO) may be as follows: (1) low percentage of nonreactive (003) surface; (2) strong surface adsorption capacity and high surface reactivity; and (3) instability of the surface sodium ions. Our physical images point out that the high reactivity of the NMFNO surface originates from the increase in electron loss and unpaired electrons (magnetic moments) of the surface oxygen active site as well as the enhanced metal coactivation effect due to the large radius of the sodium ion. We also found that the hydrolysis reaction requires a higher reactivity of the surface oxygen active site, while the carbon hybridization mode transformation in carbonate formation depends mainly on metal activation and does not even require the involvement of surface oxygen active sites. Based on the calculation results and our proposed physical images, we discuss the feasibility of these treatment strategies (including surface morphology modulation, cation/anion substitution, and surface configuration design) for air-sensitive issues.

钠离子层状氧化物是最受推崇的钠离子阴极材料之一,有望用于电动汽车和大规模电网级储能系统。然而,对空气高度敏感的问题限制了钠离子层状氧化物阴极材料最大限度地发挥成本优势。工业和科学研究人员一直在开发具有成本效益的空气敏感性处理策略,但收效甚微,因为杂质的形成机制尚不清楚。这项工作利用密度泛函理论计算和 ab initio 分子动力学模拟,表明 O3 型 NaMn1/3Fe1/3Ni1/3O2 (NMFNO) 空气稳定性差的原因可能如下:(1) 非反应性(003)表面比例低;(2) 表面吸附能力强,表面反应性高;(3) 表面钠离子不稳定。我们的物理图像表明,NMFNO 表面的高反应活性源于表面氧活性位点的电子损耗和未配对电子(磁矩)的增加,以及钠离子半径大导致的金属共激活效应的增强。我们还发现,水解反应需要表面氧活性位点具有更高的反应活性,而碳酸盐形成过程中的碳杂化模式转化主要取决于金属活化,甚至不需要表面氧活性位点的参与。基于计算结果和我们提出的物理图像,我们讨论了这些处理策略(包括表面形态调节、阳离子/阴离子置换和表面构型设计)在空气敏感问题上的可行性。
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引用次数: 0
M/P Helicity Switching and Chiral Amplification in Double-Helical Monometallofoldamers. 双螺旋单甲酰折叠酰胺中的 M/P 螺旋性转换和手性放大。
IF 14.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-19 DOI: 10.1021/jacs.4c06560
Kotaro Matsumura, Keigo Kinjo, Kotaro Tateno, Kosuke Ono, Yoshitaka Tsuchido, Hidetoshi Kawai

Short-stranded double-helical monometallofoldamers capable of M/P-switching were constructed by the complexation of two strands, each with two L-shaped units linked by a 2,2'-bipyridine, with a Zn(II) cation. The helix terminals of the "double-helical form" folded by π-π interactions can unfold in solution to equilibrate with the "open forms" that are favored at higher temperatures. Interestingly, the helical chirality of the monometallofoldamers with chiral side chains induced a single-handed helix sense and controlled M/P-switching depending on achiral solvent stimuli. For instance, the (M)-helicity was favored in nonpolarized solvents (toluene, hexane, Et2O), whereas the (P)-helicity was favored in Lewis basic solvents (acetone, DMSO). Circular dichroism (CD) and rotating-frame overhauser enhancement spectroscopy (ROESY) measurements revealed that the conformational change of the chiral side chains due to interaction of Lewis basic solvents with the double helices induced helicity bias. These novel double-helical monometallofoldamers possessed a stable helical structure and exhibited switchable chiroptical properties (gabs ∼ 10-3-10-2). In addition, the chiral strand exhibited chiral transfer and amplification abilities through the formation of chiral heteroleptic double-helical monometallofoldamers when mixed with an achiral strand.

通过将两条链(每条链都有两个由 2,2'-联吡啶连接的 L 形单元)与 Zn(II)阳离子复配,构建了能够进行 M/P 切换的短链双螺旋单金属叠层物。通过 π-π 相互作用折叠的 "双螺旋形式 "的螺旋末端可以在溶液中展开,与在较高温度下更受欢迎的 "开放形式 "达到平衡。有趣的是,带有手性侧链的单甲氧基折叠酰胺的螺旋手性会诱导单手螺旋感,并根据非手性溶剂的刺激控制 M/P 切换。例如,在非极性溶剂(甲苯、己烷、Et2O)中,(M)-手性更受青睐,而在路易斯碱性溶剂(丙酮、DMSO)中,(P)-手性更受青睐。圆二色性(CD)和旋转框架超豪斯增强光谱(ROESY)测量结果表明,由于路易斯碱性溶剂与双螺旋相互作用,手性侧链的构象发生了变化,从而诱发了螺旋偏向。这些新型双螺旋单金属叠层物具有稳定的螺旋结构,并表现出可切换的手性特性(gabs ∼ 10-3-10-2)。此外,当手性链与非手性链混合时,通过形成手性异谱双螺旋单甲基叠层聚合物,手性链还表现出手性转移和放大能力。
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引用次数: 0
Fluorogenic Peptide Sensor Array Derived from Angiotensin-Converting Enzyme 2 Classifies Severe Acute Respiratory Syndrome Coronavirus 2 Variants of Concern.
IF 14.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-19 DOI: 10.1021/jacs.4c06172
Wei-Tao Dou, Pei-Hong Tong, Man Xing, Jiao-Jiao Liu, Xi-Le Hu, Tony D James, Dong-Ming Zhou, Xiao-Peng He

The devastating COVID-19 pandemic caused by severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) has made society acutely aware of the urgency in developing effective techniques to timely monitor the outbreak of previously unknown viral species as well as their mutants, which could be even more lethal and/or contagious. Here, we report a fluorogenic sensor array consisting of peptides truncated from the binding domain of human angiotensin-converting enzyme 2 (hACE2) for SARS-CoV-2. A set of five fluorescently tagged peptides were used to construct the senor array in the presence of different low-dimensional quenching materials. When orthogonally incubated with the wild-type SARS-CoV-2 and its variants of concern (VOCs), the fluorescence of each peptide probe was specifically recovered, and the different recovery rates provide a "fingerprint" characteristic of each viral strain. This, in turn, allows them to be differentiated from each other using principal component analysis. Interestingly, the classification result from our sensor array agrees well with the evolutionary relationship similarity of the VOCs. This study offers insight into the development of effective sensing tools for highly contagious viruses and their mutants based on rationally truncating peptide ligands from human receptors.

由严重急性呼吸系统综合征冠状病毒 2(SARS-CoV-2)引起的 COVID-19 大流行的破坏性使社会深刻认识到开发有效技术的紧迫性,以便及时监测以前未知的病毒种类及其突变体的爆发,因为它们可能更具致命性和/或传染性。在这里,我们报告了一种荧光传感器阵列,该阵列由从人血管紧张素转换酶 2(hACE2)结合域截短的肽组成,用于监测 SARS-CoV-2 。在不同的低维淬火材料存在下,一组五种荧光标记肽被用于构建传感器阵列。当与野生型 SARS-CoV-2 及其相关变种(VOCs)正交孵育时,每种肽探针的荧光都能被特异性地回收,不同的回收率提供了每种病毒株的 "指纹 "特征。这反过来又允许使用主成分分析法将它们相互区分开来。有趣的是,我们的传感器阵列的分类结果与挥发性有机化合物的进化关系相似性非常吻合。这项研究为基于合理截短的人类受体肽配体开发针对高传染性病毒及其突变体的有效传感工具提供了启示。
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引用次数: 0
Solid Solutions of Plastic/Ferroelectric Crystals: Toward Tailor-Made Functional Materials. 塑料/热电晶体的固溶体:实现定制功能材料。
IF 14.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-18 DOI: 10.1021/jacs.4c07676
Jun Harada, Mika Takehisa, Yuto Kawamura, Hiroyuki Hasegawa, Tomoyasu Usui

Plastic crystals that show ferroelectricity are highly promising materials for a wide range of applications. Their inherent remarkable malleability and highly symmetric cubic structures in the plastic crystal phase ensure that their ferroelectricity and related properties are retained in their bulk polycrystals. To develop functional materials based on such plastic/ferroelectric crystals, methods to tune their properties for specific applications are required. Here, we report the preparation of solid solutions of plastic/ferroelectric ionic crystals by mixing crystals with a common anion but different cations, or crystals with a common cation but different anions, which allows a continuous modification of the Curie temperature of the ferroelectric system over a range of 100 K. This adjustment of the Curie temperature allows the flexible tuning of the pyroelectric properties of the solid solutions, including a significant enhancement of room-temperature performance. The solid solutions also exhibit morphotropic phase boundaries in the composition-temperature phase diagrams, which shows an abrupt change in crystal structures with a variation of composition. This study showcases a simple and versatile property-tuning method that can be expected to pave the way for major progress in the development of materials based on plastic/ferroelectric crystals, which will eventually advance to the stage of pursuing tailor-made functional materials with desired properties.

具有铁电性的塑料晶体是极具应用前景的材料。塑性晶体固有的出色延展性和塑性晶体相中的高度对称立方结构确保了它们的铁电性和相关特性在块状多晶体中得以保留。要开发基于此类塑性/铁电晶体的功能材料,就需要有针对特定应用调整其特性的方法。在此,我们报告了通过混合具有相同阴离子但不同阳离子的晶体,或具有相同阳离子但不同阴离子的晶体,制备塑性/铁电离子晶体固溶体的方法,从而可以在 100 K 的范围内持续调节铁电系统的居里温度。固溶体在成分-温度相图中还表现出各向异性相界,这表明晶体结构会随着成分的变化而发生突变。这项研究展示了一种简单而多用途的性能调谐方法,有望为基于塑性/铁电晶体的材料开发取得重大进展铺平道路,最终迈向追求具有所需性能的定制功能材料的阶段。
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引用次数: 0
Mixed Valence {Ni2+Ni1+} Clusters as Models of Acetyl Coenzyme A Synthase Intermediates. 作为乙酰辅酶 A 合成酶中间体模型的混合价{Ni2+Ni1+}簇。
IF 14.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-18 DOI: 10.1021/jacs.4c06241
Daniel W N Wilson, Benedict C Thompson, Alberto Collauto, Reagan X Hooper, Caroline E Knapp, Maxie M Roessler, Rebecca A Musgrave

Acetyl coenzyme A synthase (ACS) catalyzes the formation and deconstruction of the key biological metabolite, acetyl coenzyme A (acetyl-CoA). The active site of ACS features a {NiNi} cluster bridged to a [Fe4S4]n+ cubane known as the A-cluster. The mechanism by which the A-cluster functions is debated, with few model complexes able to replicate the oxidation states, coordination features, or reactivity proposed in the catalytic cycle. In this work, we isolate the first bimetallic models of two hypothesized intermediates on the paramagnetic pathway of the ACS function. The heteroligated {Ni2+Ni1+} cluster, [K(12-crown-4)2][1], effectively replicates the coordination number and oxidation state of the proposed "Ared" state of the A-cluster. Addition of carbon monoxide to [1]- allows for isolation of a dinuclear {Ni2+Ni1+(CO)} complex, [K(12-crown-2)n][2] (n = 1-2), which bears similarity to the "ANiFeC" enzyme intermediate. Structural and electronic properties of each cluster are elucidated by X-ray diffraction, nuclear magnetic resonance, cyclic voltammetry, and UV/vis and electron paramagnetic resonance spectroscopies, which are supplemented by density functional theory (DFT) calculations. Calculations indicate that the pseudo-T-shaped geometry of the three-coordinate nickel in [1]- is more stable than the Y-conformation by 22 kcal mol-1, and that binding of CO to Ni1+ is barrierless and exergonic by 6 kcal mol-1. UV/vis absorption spectroscopy on [2]- in conjunction with time-dependent DFT calculations indicates that the square-planar nickel site is involved in electron transfer to the CO π*-orbital. Further, we demonstrate that [2]- promotes thioester synthesis in a reaction analogous to the production of acetyl coenzyme A by ACS.

乙酰辅酶 A 合成酶(ACS)催化关键生物代谢物乙酰辅酶 A(乙酰-CoA)的形成和解构。ACS 的活性位点是一个与 [Fe4S4]n+ 立方体桥接的{NiNi}簇,称为 A 簇。关于 A 簇的作用机制还存在争议,很少有模型复合物能够复制催化循环中的氧化态、配位特征或反应性。在这项工作中,我们首次分离出了 ACS 功能顺磁途径上两个假设中间体的双金属模型。异质化的{Ni2+Ni1+}簇[K(12-crown-4)2][1]有效地复制了所提出的 A 簇 "Ared "态的配位数和氧化态。在[1]-中加入一氧化碳可以分离出双核{Ni2+Ni1+(CO)}复合物[K(12-crown-2)n][2](n = 1-2),它与 "ANiFeC "酶中间体相似。通过 X 射线衍射、核磁共振、循环伏安法、紫外/可见光谱和电子顺磁共振光谱,并辅以密度泛函理论(DFT)计算,阐明了每个簇合物的结构和电子特性。计算结果表明,[1]- 中三配位镍的假 T 形几何形状比 Y 形稳定 22 kcal mol-1,CO 与 Ni1+ 的结合是无障碍的,且放热 6 kcal mol-1。[2]-的紫外/可见吸收光谱以及随时间变化的 DFT 计算表明,方形平面镍位点参与了向 CO π* 轨道的电子转移。此外,我们还证明了 [2]- 在类似于 ACS 生成乙酰辅酶 A 的反应中促进硫酯的合成。
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引用次数: 0
Ultrafine Asymmetric Soft/Stiff Nanohybrids with Tunable Patchiness via a Dynamic Surface-Mediated Assembly. 通过表面动态组装实现具有可调斑块度的超细非对称软/硬纳米杂交。
IF 14.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-18 DOI: 10.1021/jacs.4c05072
Zaiwang Zhao, Mengli Liu, Linlin Duan, Runfeng Lin, Lipeng Wang, Pengfei Zhang, Jun Li, Bing Ma, Yang Yang, Fanxing Bu, Ruicong Wang, Wanhai Zhou, Dongliang Chao, Yujuan Zhao, Sixing Yin, Lei Tang, Weian Zhang, Xiaomin Li, Dongyuan Zhao

Asymmetric soft-stiff patch nanohybrids with small size, spatially separated organics and inorganics, controllable configuration, and appealing functionality are important in applications, while the synthesis remains a great challenge. Herein, based on polymeric single micelles (the smallest assembly subunit of mesoporous materials), we report a dynamic surface-mediated anisotropic assembly approach to fabricate a new type of small asymmetric organic/inorganic patch nanohybrid for the first time. The size of this asymmetric organic/inorganic nanohybrid is ∼20 nm, which contains dual distinct subunits of a soft organic PS-PVP-PEO single micelle nanosphere (12 nm in size and 632 MPa in Young' modulus) and stiff inorganic SiO2 nanobulge (∼8 nm, 2275 MPa). Moreover, the number of SiO2 nanobulges anchored on each micelle can be quantitatively controlled (from 1 to 6) by dynamically tuning the density (fluffy or dense state) of the surface cap organic groups. This small asymmetric patch nanohybrid also exhibits a dramatically enhanced uptake level of which the total amount of intracellular endocytosis is about three times higher than that of the conventional nanohybrids.

具有小尺寸、有机物和无机物空间分离、可控构型和吸引人的功能性的不对称软硬贴片纳米混合物在应用中非常重要,但其合成仍然是一个巨大的挑战。在此,我们以聚合物单胶束(介孔材料的最小组装亚单元)为基础,首次报道了一种动态表面介导的各向异性组装方法,从而制备出一种新型的小型非对称有机/无机贴片纳米杂化物。这种非对称有机/无机纳米杂化物的尺寸为20纳米,包含柔软的有机PS-PVP-PEO单胶束纳米球(尺寸为12纳米,杨氏模量为632兆帕)和坚硬的无机SiO2纳米泡(尺寸为8纳米,杨氏模量为2275兆帕)两个不同的亚单位。此外,通过动态调节表面盖有机基团的密度(蓬松或致密状态),可以定量控制每个胶束上锚定的二氧化硅纳米泡的数量(1 至 6 个)。这种小型非对称贴片纳米杂交技术还能显著提高吸收水平,其细胞内吞总量约为传统纳米杂交技术的三倍。
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引用次数: 0
Contribution of Electrostatic CH3-π Interactions to Recognition of Histone Asymmetric Dimethylarginine by the SPIN1 Triple Tudor Domain. 静电 CH3-π 相互作用对 SPIN1 三重都铎结构域识别组蛋白不对称二甲基精氨酸的贡献。
IF 14.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-18 DOI: 10.1021/jacs.4c03463
Christopher R Travis, Ryan G Dumais, Joseph W Treacy, Kelsey M Kean, K N Houk, Marcey L Waters

Methylation of arginine (Arg) residues on histones creates a new binding epitope, enabling recognition by aromatic cage binding pockets in Tudor domains; these protein-protein interactions (PPIs) govern gene expression. Despite their biological importance, the molecular details of methylated Arg recognition are poorly understood. While the desolvation, hydrogen bonding, and guanidinium stacking of methylated Arg have been explored in model systems and proposed to contribute to binding, direct interactions between the methyl groups and the aromatic residues in the binding pocket have not previously been investigated. Herein, we mechanistically study the CH3-π interactions between the SPIN1 triple Tudor domain and histone asymmetric dimethylarginine. We find that these CH3-π interactions are electrostatically tunable, exhibiting cation-π character, albeit attenuated relative to cation-π interactions with quaternary ammonium ions, offering key insight into how methylation of Arg alters its binding epitope to enable new PPIs.

组蛋白上精氨酸(Arg)残基的甲基化产生了一个新的结合表位,使其能够被 Tudor 结构域中的芳香笼结合口袋识别;这些蛋白质-蛋白质相互作用(PPI)控制着基因的表达。尽管甲基化 Arg 具有重要的生物学意义,但人们对其识别的分子细节却知之甚少。虽然甲基化 Arg 的脱溶、氢键和胍堆叠已在模型系统中进行了探索,并提出它们有助于结合,但甲基与结合口袋中的芳香残基之间的直接相互作用以前还没有研究过。在此,我们从机理上研究了 SPIN1 三重 Tudor 结构域与组蛋白不对称二甲基精氨酸之间的 CH3-π 相互作用。我们发现这些 CH3-π 相互作用具有静电可调性,表现出阳离子-π 特性,尽管相对于与季铵离子的阳离子-π 相互作用有所减弱,这为我们深入了解 Arg 甲基化如何改变其结合表位以实现新的 PPIs 提供了重要线索。
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引用次数: 0
Interfacial Charge-Transfer Excitonic Insulator in a Two-Dimensional Organic-Inorganic Superlattice. 二维有机无机超晶格中的界面电荷转移激子绝缘体。
IF 14.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-07-18 DOI: 10.1021/jacs.4c06216
Yang Liu, Haifeng Lv, Yuqiao Guo, Hongen Zhu, Zhengmin Shang, Yingcheng Zhao, Yue Lin, Xiaolin Tai, Ziyang Guo, Xuefeng Cui, Jiyin Zhao, Bingkai Yuan, Yi Liu, Guobin Zhang, Zhe Sun, Xiaojun Wu, Yi Xie, Changzheng Wu

Excitonic insulators are long-sought-after quantum materials predicted to spontaneously open a gap by the Bose condensation of bound electron-hole pairs, namely, excitons, in their ground state. Since the theoretical conjecture, extensive efforts have been devoted to pursuing excitonic insulator platforms for exploring macroscopic quantum phenomena in real materials. Reliable evidence of excitonic character has been obtained in layered chalcogenides as promising candidates. However, owing to the interference of intrinsic lattice instabilities, it is still debatable whether those features, such as the charge density wave and gap opening, are primarily driven by the excitonic effect or by the lattice transition. Herein, we develop an intercalation chemistry strategy for obtaining a novel charge-transfer excitonic insulator in organic-inorganic superlattice interfaces that serves as an ideal platform to decouple the excitonic effect from the lattice effect. In this system, we observe a narrow excitonic gap, formation of a charge density wave without periodic lattice distortion, and metal-insulator transition, providing visualized evidence of exciton condensation occurring in thermal equilibrium. Our findings identify self-assembly intercalation chemistry as a new strategy for developing novel excitonic insulators.

激子绝缘体是人们长期追求的量子材料,据预测,在其基态中,束缚的电子-空穴对(即激子)会通过玻色凝聚自发地打开一个空隙。自理论猜想提出以来,人们一直致力于寻求激子绝缘体平台,以探索真实材料中的宏观量子现象。层状钙钛矿作为有希望的候选材料,已经获得了激子特性的可靠证据。然而,由于内在晶格不稳定性的干扰,这些特征(如电荷密度波和间隙开口)主要是由激子效应还是由晶格转变驱动仍存在争议。在此,我们开发了一种插层化学策略,在有机-无机超晶格界面中获得了一种新型电荷转移激子绝缘体,它是将激子效应与晶格效应解耦的理想平台。在这一系统中,我们观察到了狭窄的激子间隙、无周期性晶格畸变的电荷密度波的形成以及金属-绝缘体转变,为激子凝聚在热平衡状态下发生提供了可视化证据。我们的研究结果表明,自组装插层化学是开发新型激子绝缘体的一种新策略。
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引用次数: 0
期刊
Journal of the American Chemical Society
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