Understanding the Chloride Affinity of Barbiturates for Anion Receptor Design

Due to their potential binding sites, barbituric acid (BA) and its derivatives have been used in metal coordination chemistry. Yet their abilities to recognize anions remain unexplored. In this work, we were able to identify four structural features of barbiturates that are responsible for a certain anion affinity. The set of coordination interactions can be finely tuned with covalent decorations at the methylene group. DFT-D computations at the BLYP-D3(BJ)/aug-cc-pVDZ level of theory show that the C−H bond is as effective as the N−H bond to coordinate chloride. An analysis of the electron charge density at the C−H⋅⋅⋅Cl⁻ and N−H⋅⋅⋅Cl⁻ bond critical points elucidates their similarities in covalent character. Our results reveal that the special acidity of the C−H bond shows up when the methylene group moves out of the ring plane and it is mainly governed by the orbital interaction energy. The amide and carboxyl groups are the best choices to coordinate the ion when they act together with the C−H bond. We finally show how can we use this information to rationally improve the recognition capability of a small cage-like complex that is able to coordinate NaCl.     

Focal Point Evaluation of Energies for Tautomers and Isomers for 3-hydroxy-2-butenamide: Evaluation of Competing Internal Hydrogen Bonds of Types -OH…O=, -OH…N, -NH…O=, and CH…X (X=O and N)

The title compound is a small molecule with many structural variations; it can illustrate a variety of internal hydrogen bonds, among other noncovalent interactions. Here we examine structures displaying hydrogen bonding between carbonyl oxygen and hydroxyl H; between carbonyl oxygen and amino H; hydroxyl H and amino N; hydroxyl O and amino H. We also consider H-bonding in its tautomer 2-oxopropanamide. By extrapolation algorithms applied to Hartree-Fock and correlation energies as estimated in HF, MP2, and CCSD calculations using the cc-pVNZ correlation-consistent basis sets (N = 2, 3, and 4) we obtain reliable relative energies of the isomeric forms. Assuming that such energy differences may be attributed to the presence of the various types of hydrogen bonding, we attempt to infer relative strengths of types of H-bonding. The Atoms in Molecules theory of Bader and the Local Vibrational Modes analysis of Cremer and Kraka are applied to this task. Hydrogen bonds are ranked by relative strength as measured by local stretching force constants, with the stronger =O…HO- > NH…O= > -OH…N well separated from a cluster > NH…O= ≈ >NH…OH ≈ CH…O= of comparable and intermediate strength. Weaker but still significant interactions are of type CH…N which is stronger than CH…OH.     

稀有气体卤化物准分子激光器工作气体实时补给技术

为延长稀有气体卤化物准分子激光器工作气体使用寿命,在原有供气设备基础上增加了工作气体实时补给技术.该技术采用FPGA控制系统将逐步提高放电电压、补充卤素气体和更换部分混合气体等操作有效组合起来.随着激光脉冲能量的下降,逐步提高放电电压;当放电电压达到最大值时,开始补充卤素气体,并恢复放电电压;当补充卤素气体效果不明显时,更换部分混合工作气体.将该技术应用于医用型ArF准分子激光器中进行实验研究,结果表明:在没有使用工作气体实时补给技术的情况下,激光器累计工作14.38 h后,输出单脉冲激光能量下降了17.2％;采用工作气体实时补给技术后,激光器输出能量下降速率明显降低,累计工作14.38 h,其单脉冲能量下降率能控制在3％范围内.因此,采用该技术可延长激光器工作气体的使用寿命、提高输出激光能量稳定性、减少停机次数并降低运行成本.     

Continuum model for low-frequency phonons of boron nitride nanotubes

A continuum model is employed to calculate the low-frequency phonons of boron nitride nanotubes. We find an excellent agreement of the optically active modes calculated within this approach and those from more elaborate calculations within an energy and wavelength window that can be established beforehand, from the choice of the bulk input parameters. We verify that this model describes correctly the dependence of radial breathing mode with the radius, the existence of parabolic modes at small wavevectors, and other general characteristics of the dispersion relations of these systems.     

Facile Synthesis of Dibenzopentalene Dianions and Their Application as New π‐Extended Ligands

Reduction of phenyl(silyl)ethynes with potassium followed by quenching with iodine gave dibenzopentalenes in moderate yields. The intermediates of the reactions, dipotassium dibenzopentalenides, were isolated. The first dibenzopentalene–transition‐metal complex was successfully synthesized. The ruthenium atoms are located above the six‐membered rings. However, X‐ray diffraction analysis and theoretical calculations revealed that the aromatic nature of the five‐membered rings was retained. The cyclic voltammetry of the Ru complex revealed two oxidation waves with relatively large separation.     

Regulating Charge Transfer of Lattice Oxygen in Single-Atom-Doped Titania for Hydrogen Evolution

Single-atom catalysts have attracted much attention. Reported herein is that regulating charge transfer of lattice oxygen atoms in serial single-atom-doped titania enables tunable hydrogen evolution reaction (HER) activity. First-principles calculations disclose that the activity of lattice oxygen for the HER can be regularly promoted by substituting its nearest metal atom, and doping-induced charge transfer plays an essential role. Besides, the realm of the charge transfer of the active site can be enlarged to the second nearest atom by creating oxygen vacancies, resulting in further optimization for the HER. Various single-atom-doped titania nanosheets were fabricated to validate the proposed model. Taking advantage of the localized charge transfer to the lattice atom is demonstrated to be feasible for realizing precise regulation of the electronic structures and thus catalytic activity of the nanosheets.     

Regulating Charge Transfer of Lattice Oxygen in Single‐Atom‐Doped Titania for Hydrogen Evolution

Single‐atom catalysts have attracted much attention. Reported herein is that regulating charge transfer of lattice oxygen atoms in serial single‐atom‐doped titania enables tunable hydrogen evolution reaction (HER) activity. First‐principles calculations disclose that the activity of lattice oxygen for the HER can be regularly promoted by substituting its nearest metal atom, and doping‐induced charge transfer plays an essential role. Besides, the realm of the charge transfer of the active site can be enlarged to the second nearest atom by creating oxygen vacancies, resulting in further optimization for the HER. Various single‐atom‐doped titania nanosheets were fabricated to validate the proposed model. Taking advantage of the localized charge transfer to the lattice atom is demonstrated to be feasible for realizing precise regulation of the electronic structures and thus catalytic activity of the nanosheets.     

Indole-Based Tubulin Inhibitors: Binding Modes and SARs Investigations

Tubulin inhibitors can interfere with normal cell mitosis and inhibit cell proliferation through interfering with the normal structure and function of microtubules, forming spindle filaments. Indole, as a privileged pharmacological skeleton, has been widely used in anti-cancer inhibitors. A variety of alkaloids containing an indole core obtained from natural sources have been proven to inhibit tubulin polymerization, and an ever-increasing number of synthetic indole-based tubulin inhibitors have been reported. Among these, several kinds of indole-based derivatives, such as TMP analogues, aroylindoles, arylthioindoles, fused indole, carbazoles, azacarbolines, alkaloid nortopsentin analogues and bis-indole derivatives, have shown good inhibition activities towards tubulin polymerization. The binding modes and SARs investigations of synthetic indole derivatives, along with a brief mechanism on their anti-tubulin activity, are presented in this review.     

The Phosphorus Bond,or the Phosphorus-Centered Pnictogen Bond: The Covalently Bound Phosphorus Atom in Molecular Entities and Crystals as a Pnictogen Bond Donor

The phosphorus bond in chemical systems, which is an inter- or intramolecular noncovalent interaction, occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a covalently or coordinately bonded phosphorus atom in a molecular entity and a nucleophile in another, or the same, molecular entity. It is the second member of the family of pnictogen bonds, formed by the second member of the pnictogen family of the periodic table. In this overview, we provide the reader with a snapshot of the nature, and possible occurrences, of phosphorus-centered pnictogen bonding in illustrative chemical crystal systems drawn from the ICSD (Inorganic Crystal Structure Database) and CSD (Cambridge Structural Database) databases, some of which date back to the latter part of the last century. The illustrative systems discussed are expected to assist as a guide to researchers in rationalizing phosphorus-centered pnictogen bonding in the rational design of molecular complexes, crystals, and materials and their subsequent characterization.     

Lossy mode resonance-based uniform core tapered fiber optic sensor for sensitivity enhancement

A lossy mode resonance (LMR)-supported fiber optic sensor in which a uniform fiber core is placed among two identical tapered regions, is investigated numerically. Indium tin oxide (ITO) and aluminum-doped zinc oxide (AZO) are considered as LMR active materials used to excite several lossy modes and gold and silver are used as surface plasmon resonance (SPR) active materials. In this probe design, a central uniform core coated with ITO/AZO is the active sensing region, whereas tapered regions are meant for bringing the incident angle close to the critical angle. The sensitivity of the present fiber optic bio-sensor is evaluated for first two LMRs utilizing both ITO and AZO separately, along with its variation with the taper ratio (TR). For ITO, the maximum sensitivity values are observed to be 18.425 μm RIU⁻¹ (refractive index unit) and 0.825 μm RIU⁻¹, corresponding to the first and second LMRs, respectively, at a TR of 1.6 and for AZO, equivalent values are 0.79 μm RIU⁻¹ and 0.35 μm RIU⁻¹, respectively, at a TR of 2.0. The results illustrate that the first LMR is more sensitive than the second LMR and the ITO-coated probe possesses greater sensitivity than the AZO-coated probe for both LMRs. Similarly, for the fiber optic SPR sensor, the maximum value of sensitivity is 5.6425 μm RIU⁻¹, in the case of gold and 5.0615 μm RIU⁻¹ in the case of silver, at a TR of 1.6. Hence, the result shows that the sensor with the present fiber optic probe design has around a 3-fold enhancement in sensitivity compared with conventional SPR sensors. This study will have applications in many sensing schemes where the requirement of large sensitivity is vital.