chirality

手性
  • 文章类型: Journal Article
    提出了由一种手性形式(S)的分子组成的同斜(铁电SmC*)和反斜(反铁电SmCA*)近晶液晶的介电性能,并与外消旋混合物的性能进行了比较(R,S),显示SmC和SmCA相。外消旋混合物完全失去其铁电和反铁电特性。令人惊讶的是,在反铁电SmCA*相中观察到的仅一种介电模式在外消旋SmCA相的介电响应中消失。此外,我们观察到在SmC阶段,在外消旋混合物中看到,检测到弱介电模式(称为X模式),这似乎是外消旋SmCA中存在的PL模式的延续。此外,外消旋SmC中的这种模式与Goldstone模式无关,典型的SmC*相。本文详细描述了在有和没有DC场的情况下,对映体和外消旋体在近晶相中介电常数的实部和虚部,比较X和PL模式的属性,并讨论了对映体和外消旋体的介电模式的完整方案。
    The dielectric properties of synclinic (ferroelectric SmC*) and anticlinic (antiferroelectric SmCA*) smectic liquid crystals composed of molecules of one chiral version (S) are presented and compared with properties of racemic mixture (R, S), showing SmC and SmCA phases. The racemic mixture completely loses its ferroelectric and antiferroelectric properties. Surprisingly, only one dielectric mode observed in the antiferroelectric SmCA* phase disappeared in the dielectric response of the racemic SmCA phase. Additionally, we observed that in the SmC phase, seen in the racemic mixture, the weak dielectric mode (named the X mode) is detected, which seems to be the continuation of the PL mode existing in the racemic SmCA. Moreover, this mode in the racemic SmC has nothing to do with the Goldstone mode, typical for the SmC* phase. This paper describes in detail the real and imaginary parts of dielectric permittivity in smectic phases for the enantiomer and racemate with and without a DC field, compares the properties of the X and PL modes, and discusses the full scheme of dielectric modes in enantiomer and racemate.
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  • 文章类型: Journal Article
    强烈的圆二色性(CD)响应的动态控制在工程应用中至关重要,例如偏振操纵,传感,和成像。这里,我们提出并通过实验证明了在二维拓扑保护的超表面中通过连续介质(BIC)中的束束态实现宽带可调谐双CD响应,该超表面由全电介质Si手性光栅结构组成,该结构产生一对混合和退化的BIC模式和圆形二向色模式(CDM)作为CD操纵中的附加自由度。发现当BIC在垂直入射下隐藏时,通过CDM可以在1.6μm处实现近100%的奇异CD峰,而CD峰可以分为两个,其中当BIC模式在倾斜入射下激发时,峰值波长可以通过入射角在180nm的带宽上精确线性调谐。此外,由于BIC将Γ点处的各种偏振状态解耦到K空间中的不同位置,因此在引入手性光栅上的不对称扰动时,可以通过控制入射角来在CD峰值处任意实现从线性到圆形的输出偏振状态的动态调制。所提出的手性光栅超表面表现出独特的角度敏感可调谐CD光谱特性,使其成为高光谱和自旋选择性波前整形的理想选择,并在各种应用中拥有重要的前景,如光学安全,角度传感器,手性激光器,非线性滤波器,和其他有源手性光学器件。
    Dynamic control for a strong circular dichroism (CD) response is essential in engineering applications such as polarization manipulation, sensing, and imaging. Here, we propose and experimentally demonstrate a broadband tunable dual CD response via bound states in the continuum (BICs) in two-dimensional topologically protected metasurfaces composed of all-dielectric Si chiral grating structures that generate a pair of mixed and degenerated BIC mode and circular dichroic mode (CDM) as an additional degree of freedom in CD manipulation. It is found that a singular CD peak of nearly 100% at 1.6 μm can be achieved by CDM when BIC is hidden under normal incidence, while the CD peak can be split into two in which peak wavelengths can be precisely and linearly tuned over a bandwidth of 180 nm by the incident angle when the BIC mode is excited under oblique incidence. Additionally, dynamic modulation of output polarization states from linear to circular can be arbitrarily achieved at the split CD peaks by controlling the incident angle when asymmetry perturbations on chiral gratings are introduced due to the decoupling of various polarization states at Γ point by BIC to different positions in K space. The proposed chiral grating metasurface exhibits unique angle-sensitive tunable CD spectral characteristics, making it ideal for hyperspectral and spin-selective wavefront shaping, and holds significant promise in various applications such as optical security, angle sensors, chiral lasers, nonlinear filters, and other active chiral optical devices.
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  • 文章类型: Journal Article
    背景:本文考虑了几种氨基酸及其二肽的结构和偶极矩的特征,这些氨基酸及其二肽在基于它们的肽纳米管的形成中起着重要作用。考虑了它们的手性特征(左L和右D)和氨基酸的α-螺旋构象的影响。特别是,带有芳香环的氨基酸,如苯丙氨酸(Phe/F),和支链氨基酸(BCAAs)-亮氨酸(Leu/L)和异亮氨酸(Ile/I)-以及相应的二肽(二苯丙氨酸(FF),二亮氨酸(LL),和二异亮氨酸(II))。这些二肽结构和肽纳米管(PNTs)的主要特征和性质,基于它们,使用计算分子建模和量子化学半经验计算进行了研究。他们的极地,压电,并对光电特性和特征进行了详细的研究。偶极矩和极化的计算结果,以及压电系数和带隙宽度,对于不同类型的螺旋肽纳米管。给出了各种纳米管的手性指数的计算值,取决于初始二肽的手性-随着分子结构的层次变得更加复杂,获得的结果与手性类型的变化规律一致。估计了纳米管内腔中水分子对其物理性质的影响。提出并讨论了通过各种计算方法将这些计算结果与可用的实验数据进行比较。
    方法:这项工作中对所有研究的纳米结构进行分子建模的主要工具是HyperChem8.01软件包。这里使用的主要方法是Hartree-Fock(HF)自洽场(SCF),在受限的Hartree-Fock(RHF)和非受限的Hartree-Fock(UHF)近似中具有各种量子化学半经验方法(AM1,PM3,RM1)。在这项工作中,使用Polak-Ribeire算法(共轭梯度法)进行了分子系统的优化及其最佳几何结构的搜索,它在最小总能量点确定优化的几何形状。对于这种优化的结构,偶极矩D和电子能级(如EHOMO和ELUMO),以及带隙Eg=ELUMO-EHOMO,然后计算。对于每个优化的分子结构,使用也在HyperChem软件包中实施的QSAR程序计算体积.
    BACKGROUND: The paper considers the features of the structure and dipole moments of several amino acids and their dipeptides which play an important role in the formation of the peptide nanotubes based on them. The influence of the features of their chirality (left L and right D) and the alpha-helix conformations of amino acids are taken into account. In particular, amino acids with aromatic rings, such as phenylalanine (Phe/F), and branched-chain amino acids (BCAAs)-leucine (Leu/L) and isoleucine (Ile/I)-as well as corresponding dipeptides (diphenylalanine (FF), dileucine (LL), and diisoleucine (II)) are considered. The main features and properties of these dipeptide structures and peptide nanotubes (PNTs), based on them, are investigated using computational molecular modeling and quantum-chemical semi-empirical calculations. Their polar, piezoelectric, and photoelectronic properties and features are studied in detail. The results of calculations of dipole moments and polarization, as well as piezoelectric coefficients and band gap width, for different types of helical peptide nanotubes are presented. The calculated values of the chirality indices of various nanotubes are given, depending on the chirality of the initial dipeptides-the results obtained are consistent with the law of changes in the type of chirality as the hierarchy of molecular structures becomes more complex. The influence of water molecules in the internal cavity of nanotubes on their physical properties is estimated. A comparison of the results of these calculations by various computational methods with the available experimental data is presented and discussed.
    METHODS: The main tool for molecular modeling of all studied nanostructures in this work was the HyperChem 8.01 software package. The main approach used here is the Hartree-Fock (HF) self-consistent field (SCF) with various quantum-chemical semi-empirical methods (AM1, PM3, RM1) in the restricted Hartree-Fock (RHF) and in the unrestricted Hartree-Fock (UHF) approximations. Optimization of molecular systems and the search for their optimal geometry is carried out in this work using the Polak-Ribeire algorithm (conjugate gradient method), which determines the optimized geometry at the point of their minimum total energy. For such optimized structures, dipole moments D and electronic energy levels (such as EHOMO and ELUMO), as well as the band gap Eg = ELUMO - EHOMO, were then calculated. For each optimized molecular structure, the volume was calculated using the QSAR program implemented also in the HyperChem software package.
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  • 文章类型: Journal Article
    在150K下测量4-苄基-1H-吡唑(C10H10N2,1)和3,5-二氨基-4-苄基-1H-吡唑(C10H12N4,2)的晶体结构。尽管其不同的构象异构体和atropenanti-异构体很容易在溶液中通过环形互变异构和/或围绕C(吡唑)-C(CH2)NMR1H单键的取代基旋转而相互转化1在非中心对称空间群P21中结晶。在它的晶体结构中,吡唑和苯基芳族部分被组织成交替的双层。吡唑和苯基层都由沿两个正交方向堆叠成柱的芳环组成。在吡唑层中,吡唑环通过N-H-N氢键形成平行的基团。化合物2采用类似的双层结构,尽管在中心对称空间群P21/c中,以吡唑N-H质子为供体,与相邻的吡唑环形成N-H-π氢键,和NH2质子作为N-H-N氢键与相邻的吡唑和其他NH2部分的供体。1和2的晶体结构和超分子特征与它们的类似物的两个已知结构形成对比。3,5-二甲基-4-苄基-1H-吡唑和3,5-二苯基-4-苄基-1H-吡唑。
    The crystal structures of 4-benzyl-1H-pyrazole (C10H10N2, 1) and 3,5-di-amino-4-benzyl-1H-pyrazole (C10H12N4, 2) were measured at 150 K. Although its different conformers and atropenanti-omers easily inter-convert in solution by annular tautomerism and/or rotation of the benzyl substituent around the C(pyrazole)-C(CH2) single bond (as revealed by 1H NMR spectroscopy), 1 crystallizes in the non-centrosymmetric space group P21. Within its crystal structure, the pyrazole and phenyl aromatic moieties are organized into alternating bilayers. Both pyrazole and phenyl layers consist of aromatic rings stacked into columns in two orthogonal directions. Within the pyrazole layer, the pyrazole rings form parallel catemers by N-H⋯N hydrogen bonding. Compound 2 adopts a similar bilayer structure, albeit in the centrosymmetric space group P21/c, with pyrazole N-H protons as donors in N-H⋯π hydrogen bonds with neighboring pyrazole rings, and NH2 protons as donors in N-H⋯N hydrogen bonds with adjacent pyrazoles and other NH2 moieties. The crystal structures and supra-molecular features of 1 and 2 are contrasted with the two known structures of their analogs, 3,5-dimethyl-4-benzyl-1H-pyrazole and 3,5-diphenyl-4-benzyl-1H-pyrazole.
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  • 文章类型: Journal Article
    具有可控几何形状的DNA纳米管具有广泛的跨学科应用。当制备不同宽度或不同手性的DNA纳米管时,现有的方法需要反复设计和合成特定的DNA序列,这可能是昂贵和费力的。这里,我们提出了一种嵌入剂辅助的DNA瓦片组装方法,该方法可以使用相同的DNA链生产不同宽度和手性的DNA纳米管。通过在组装过程中调节嵌入剂的浓度,可以调节DNA瓦片的扭曲方向和程度,导致形成具有可控宽度和手性的DNA纳米管。此外,通过引入额外的嵌入剂和二次退火,右旋纳米管可以重新配置成不同的左旋纳米管。我们期望这种方法可以普遍应用于调节各种DNA瓦片和其他手性材料的自组装途径,推进DNA瓷砖组装的景观。
    DNA nanotubes with controllable geometries hold a wide range of interdisciplinary applications. When preparing DNA nanotubes of varying widths or distinct chirality, existing methods require repeatedly designing and synthesizing specific DNA sequences, which can be costly and laborious. Here, we proposed an intercalator-assisted DNA tile assembly method which enables the production of DNA nanotubes of diverse widths and chirality using identical DNA strands. Through adjusting the concentration of intercalators during assembly, the twisting direction and extent of DNA tiles could be modulated, leading to the formation of DNA nanotubes featuring controllable widths and chirality. Moreover, through introducing additional intercalators and secondary annealing, right-handed nanotubes could be reconfigured into distinct left-handed nanotubes. We expect that this method could be universally applied to modulating the self-assembly pathways of various DNA tiles and other chiral materials, advancing the landscape of DNA tile assembly.
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  • 文章类型: Journal Article
    Chirality,具有镜像形式的分子的性质,在制药和生物医学研究中起着至关重要的作用。这篇评论强调了它日益增长的重要性,强调手性药物和纳米材料如何影响药物有效性,安全,和诊断。手性分子作为精确的诊断工具,通过独特的生物分子相互作用帮助准确的疾病检测。这篇文章广泛涵盖了手性药物在治疗心血管疾病中的应用,中枢神经系统疾病,局部麻醉,抗炎药,抗菌药物,和抗癌药物。此外,它探索了手性纳米材料的新兴领域,强调它们在诊断和治疗中的生物医学应用的适用性,加强医疗。
    Chirality, the property of molecules having mirror-image forms, plays a crucial role in pharmaceutical and biomedical research. This review highlights its growing importance, emphasizing how chiral drugs and nanomaterials impact drug effectiveness, safety, and diagnostics. Chiral molecules serve as precise diagnostic tools, aiding in accurate disease detection through unique biomolecule interactions. The article extensively covers chiral drug applications in treating cardiovascular diseases, CNS disorders, local anesthesia, anti-inflammatories, antimicrobials, and anticancer drugs. Additionally, it explores the emerging field of chiral nanomaterials, highlighting their suitability for biomedical applications in diagnostics and therapeutics, enhancing medical treatments.
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  • 文章类型: Journal Article
    蜂窝晶格是基本的二维(2D)网络,其产生令人惊讶的丰富电子特性。虽然它扩展到2D超分子组装在概念上很有吸引力,由于弱的分子间耦合和支撑衬底的强烈影响,其实现并不简单。这里,我们证明了具有吩嗪部分的三烯衍生物的应用,Trip-Phz,由于其强大的分子间π-π煎饼键合和非平面几何形状,解决了这个问题。我们的扫描隧道显微镜(STM)测量表明,Trip-Phz分子在Ag(111)表面上自组装,形成了手性和相称的蜂窝晶格。电子,该网络可以被视为蜂窝和kagome晶格的混合。通过总密度泛函理论(DFT)计算再现了由简单的紧密结合模型预测的狄拉克和平坦带,突出的保护分子带从Ag(111)衬底。目前的工作提供了一种合理的途径,用于创建可以同时容纳原始狄拉克和平坦带的手性2D超分子。
    The honeycomb lattice is a fundamental two-dimensional (2D) network that gives rise to surprisingly rich electronic properties. While its expansion to 2D supramolecular assembly is conceptually appealing, its realization is not straightforward because of weak intermolecular coupling and the strong influence of a supporting substrate. Here, we show that the application of a triptycene derivative with phenazine moieties, Trip-Phz, solves this problem due to its strong intermolecular π-π pancake bonding and nonplanar geometry. Our scanning tunneling microscopy (STM) measurements demonstrate that Trip-Phz molecules self-assemble on a Ag(111) surface to form chiral and commensurate honeycomb lattices. Electronically, the network can be viewed as a hybrid of honeycomb and kagome lattices. The Dirac and flat bands predicted by a simple tight-binding model are reproduced by total density functional theory (DFT) calculations, highlighting the protection of the molecular bands from the Ag(111) substrate. The present work offers a rational route for creating chiral 2D supramolecules that can simultaneously accommodate pristine Dirac and flat bands.
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  • 文章类型: Journal Article
    由不断远离热平衡的成分组成的活性流体可以支持自发流,并且可以被设计为具有非常规的传输特性。这里,我们报告了在对齐圆圈游泳者的计算机模拟中出现(元)稳定的游带。这些波段不同于极群,通过耦合阶段与质量传输,诱导具有垂直于传播方向的分量的块状颗粒电流,从而产生集体霍尔(或马格努斯)效应。行进带需要足够小的轨道,并且对于较大的轨道半径,会经历不连续过渡到具有瞬态极簇的同步状态。在最小流体动力学理论中,我们表明,这些带可以理解为非色散孤子解,充分说明了数值观察到的性质。
    Active fluids composed of constituents that are constantly driven away from thermal equilibrium can support spontaneous currents and can be engineered to have unconventional transport properties. Here, we report the emergence of (meta)stable traveling bands in computer simulations of aligning circle swimmers. These bands are different from polar flocks and, through coupling phase with mass transport, induce a bulk particle current with a component perpendicular to the propagation direction, thus giving rise to a collective Hall (or Magnus) effect. Traveling bands require sufficiently small orbits and undergo a discontinuous transition into a synchronized state with transient polar clusters for large orbital radii. Within a minimal hydrodynamic theory, we show that the bands can be understood as nondispersive soliton solutions fully accounting for the numerically observed properties.
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  • 文章类型: Journal Article
    手性在自然界中无处不在,与生物现象密切相关。源自自然的纳米材料,例如纤维素纳米晶体(CNCs)能够自组装成分层的手性向列型CNC膜,并赋予纳米和微米级的手性。然而,手性向列表面对细胞粘附的影响尚不清楚。在这里,我们提供的证据表明,与随机排列的各向同性CNC膜(I-CNC)相比,左手自组装的手性向列型CNC膜(L-CNC)显着改善了L929成纤维细胞的粘附。引入基于流体力显微镜(FluidFM)的单细胞力谱(SCFS)来评估L-CNC和I-CNC基底上的细胞粘附力,分别。使用这种方法,在L-CNC上培养24小时后,成熟L929成纤维细胞的最大粘附力为133.2nN,而L929成纤维细胞在相同条件下对I-CNC施加的最大粘附力为78.4nN。此外,瞬时单细胞力谱表明,细胞粘附力的这种差异在细胞粘附的早期阶段上升,L929成纤维细胞与L-CNC或I-CNC基底接触5s内。有趣的是,用RGD肽阻断跨膜整合素后,细胞粘附力的差异消失,表明整合素途径参与感测基底表面的手性。此外,免疫荧光染色和粘着斑蛋白的Westernblot分析表明,L-CNC底物上的talin表达和F-actin组装上调,而Y397-磷酸化粘着斑激酶(FAKY397)的表达无统计学差异,维古林,和α-肌动蛋白。我们的发现表明,talin的上调是促进细胞在L-CNC膜上粘附的关键因素。总的来说,这项工作提供了一个起点,通过自组装的纳米和微结构的手性向列型数控膜细胞粘附的调控,在组织工程和再生医学中具有潜在的实际应用。本文受版权保护。保留所有权利。
    Chirality is ubiquitous in nature, and closely related to biological phenomena. Nature-originated nanomaterials such as cellulose nanocrystals (CNCs) are able to self-assemble into hierarchical chiral nematic CNC films and impart handedness to nano and micro scale. However, the effects of the chiral nematic surfaces on cell adhesion are still unknown. Herein, this work presents evidence that the left-handed self-assembled chiral nematic CNC films (L-CNC) significantly improve the adhesion of L929 fibroblasts compared to randomly arranged isotropic CNC films (I-CNC). The fluidic force microscopy-based single-cell force spectroscopy is introduced to assess the cell adhesion forces on the substrates of L-CNC and I-CNC, respectively. With this method, a maximum adhesion force of 133.2 nN is quantified for mature L929 fibroblasts after culturing for 24 h on L-CNC, whereas the L929 fibroblasts exert a maximum adhesion force of 78.4 nN on I-CNC under the same condition. Moreover, the instant SCFS reveals that the integrin pathways are involved in sensing the chirality of substrate surfaces. Overall, this work offers a starting point for the regulation of cell adhesion via the self-assembled nano and micro architecture of chiral nematic CNC films, with potential practical applications in tissue engineering and regenerative medicine.
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  • 文章类型: Journal Article
    手性是各种系统固有的,包括固态和波物理。磁性材料中磁矩的进动(手性运动),形成自旋波,在磁学和自旋电子学中具有各种性质和许多应用。我们证明可以在等离子体纳米螺旋阵列中产生自旋波的光学模拟。这种光波是由携带自旋和轨道角动量的扭曲螺旋本征模式之间的相互作用引起的。我们证明了这些光学自旋波在对映体纳米螺旋的连续域之间的界面处反射,形成异手性晶格,而与晶格内的波传播方向无关。光学自旋波可以应用在涉及光子自旋的技术中,从数据处理和存储到量子光学。
    Chirality is inherent to a broad range of systems, including solid-state and wave physics. The precession (chiral motion) of the magnetic moments in magnetic materials, forming spin waves, has various properties and many applications in magnetism and spintronics. We show that an optical analogue of spin waves can be generated in arrays of plasmonic nanohelices. Such optical waves arise from the interaction between twisted helix eigenmodes carrying spin and orbital angular momenta. We demonstrate that these optical spin waves are reflected at the interface between successive domains of enantiomeric nanohelices, forming a heterochiral lattice regardless of the wave propagation direction within the lattice. Optical spin waves may be applied in techniques involving photon spin, ranging from data processing and storage to quantum optics.
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