Theoretical Insights into the Nature of Halogen Bonding in Prereactive Complexes

Benchmark quality geometries and interaction energies for the prereactive halogen‐bonded complexes of dihalogens and ammonia, including hypothetical astatine containing dihalogens, have been produced via explicitly correlated coupled cluster methods. The application of local electron correlation partitioning reveals dispersion, electrostatics and ionic substitutions all contribute significantly to the interaction energy, with a linear relationship between the ionic substitutions and the degree of charge transfer. Potential energy curves for H₃N???ClF show that as the relative orientations of the two subunits are manipulated appreciable interactions can be found at considerably angular displaced geometries, signifying lower directionality in halogen bonding than previously supposed.     

Experimental and Computational Probes of the Nature of Halogen Bonding: Complexes of Bromine‐Containing Molecules with Bromide Anions

The nature of halogen bonding is examined via experimental and computational characterizations of a series of associates between electrophilic bromocarbons R? Br (R? Br=CBr₃F, CBr₃NO₂, CBr₃COCBr₃, CBr₃CONH₂, CBr₃CN, etc.) and bromide anions. The [R? Br, Br^?] complexes show intense absorption bands in the 200–350 nm range which follow the same Mulliken correlation as those observed for the charge‐transfer associates of bromide anions with common organic π‐acceptors. For a wide range of the associates, intermolecular R? Br???Br^? separations decrease and intramolecular C? Br bond lengths increase proportionally to the Br^?→R? Br charge transfer; and the energies of R? Br???Br^? bonds are correlated with the linear combination of orbital (charge‐transfer) and electrostatic interactions. On the whole, spectral, structural and thermodynamic characteristics of the [R? Br, Br^?] complexes indicate that besides electrostatics, the orbital (charge‐transfer) interactions play a vital role in the R? Br???Br^? halogen bonding. This indicates that in addition to controlling the geometries of supramolecular assemblies, halogen bonding leads to electronic coupling between interacting species, and thus affects reactivity of halogenated molecules, as well as conducting and magnetic properties of their solid‐state materials.     

Double‐injection capillary electrophoresis for the identification of analytes

This paper presents a new approach for identifying analytes by CE. The compound to be identified is analyzed together with the corresponding reference standard during a double injection capillary electrophoretic run. The inter‐plug distance is regulated by applying an electrical field over the capillary for a predetermined time period (t_PE). The migration time of an analyte being exposed to the partial electrophoresis was calculated from the partial migration time (t_mig(p)) as described in this paper. The identification is based on the closeness of agreement between the calculated migration time (t_mig(c)) and observed migration time (t_mig) of the reference standard. The validity of the derived equations was checked by analyzing several substances such as caffeine, melamine, acetyl salicylic acid, paracetamol, ibuprofen, metoprolol, naproxen, somatropin, several insulin analogs, as well as different pharmaceutical and natural products. The migration time ratios for the identified solutes varied between 0.996 and 1.006 (i.e., 1.001 ± 0.005), indicating good agreement between the observed and calculated migration times.     

Determination of six polyynes in Oplopanax horridus and Oplopanax elatus using polyethylene glycol modified reversed migration microemulsion electrokinetic chromatography

A PEG‐modified reversed migration MEEKC method was developed for simultaneous determination of six polyynes, including oplopandiol, falcarindiol, oplopandiol acetate, (11S, 16S, 9Z)‐9,17‐octadecadiene‐12,14‐diyne‐1,11,16‐triol,1‐acetate, oplopantriol B, and oplopantriol A, in Oplopanax horridus and Oplopanax elatus. The running buffer containing 0.8% v/v ethyl acetate, 3.8% w/v SDS, 6.6% v/v n‐butanol in 20 mM phosphate buffer (pH 2.5), followed by mixing with propan‐2‐ol at 30% v/v and PEG‐1000 at 15% w/v, was applied in the analysis. The proposed method was successfully applied to determine the six polyynes in five samples of Oplopanax horridus and one of O. elatus. The result showed that the types and amounts of polyynes present were obviously different when comparing the two herbs. Besides, the developed PEG‐modified reversed MEEKC method might be suitable for the analysis of hydrophobic analytes in herbal medicines.     

An evidence of contact ion pair in β-(acyloxy)alkyl radical heterolysis during copper(I)-mediated synthesis of trisubstituted alkenes

The first evidence for a unified mechanism of heterolysis in β-(acyloxy)alkyl radical involving contact ion pair (CIP) is presented for both fragmentation and rearrangement of the acyloxy group in the reaction of 1-alkoxy-2,2,2-trichloroethyl acetate with 2 mol equiv each of CuCl and bpy in refluxing DCE under a N₂ atmosphere and availed this reaction for the synthesis of Z-stereoselective trisubstituted alkenes. The stereochemistry of the trisubstituted alkenes was assigned by the uniform pattern of the chemical shift values of some relevant signals in ¹H and ¹³C NMR spectra. This assignment was further supported by the X-ray diffraction spectroscopy of Z-1-chloro-2-(4-nitrobenzyloxy)vinyl acetates.     

Fibril Structure Demonstrates the Role of Iodine Labelling on a Pentapeptide Self-Assembly

Iodination has long been employed as a successful labelling strategy to gain structural insights into proteins and other biomolecules via several techniques, including Small Angle X-ray Scattering, Inductively Coupled Plasma Mass Spectrometer (ICP-MS), and single-crystal crystallography. However, when dealing with smaller biomolecular systems, interactions driven by iodine may significantly alter their self-assembly behaviour. The engineering of amyloidogenic peptides for the development of ordered nanomaterials has greatly benefitted from this possibility. Still, to date, iodination has exclusively been applied to aromatic residues. In this work, an aliphatic bis-iodinated amino acid was synthesized and included into a custom pentapeptide, which showed enhanced fibrillogenic behaviour. Peptide single crystal X-ray structure and powder X-ray diffraction on its dried water solution demonstrated the key role of iodine atoms in promoting intermolecular interactions that drive the peptide self-assembly into amyloid fibrils. These findings enlarge the library of halogenated moieties available for directing and engineering the self-assembly of amyloidogenic peptides.     

紫外光辐照下CH3NH3PbI3基钙钛矿太阳能电池失效机制

随着光伏产业的不断发展,有机无机杂化钙钛矿太阳能电池的研发成为科学与工业界广泛关注的焦点。到目前为止,其光电转换效率已经提高到了25.2%,成为替代硅基太阳能电池的核心方案之一。然而,钙钛矿太阳能电池的稳定性较差,容易受到环境中氧气、水分、温度甚至光照的影响,这严重制约了其大规模推广与应用。大量科学研究表明,如何避免紫外辐照下有机无机杂化钙钛矿太阳能电池的性能衰减,对于提高钙钛矿太阳能电池的光照稳定性至关重要。然而到目前为止,仍然没有系统的工作来对紫外辐照下钙钛矿太阳能电池性能以及微结构演化过程进行详细的表征与分析。本文中,我们利用聚焦离子束-扫描电子显微分析(FIB-SEM)以及球差校正透射电子显微分析(TEM)等技术,全面地研究了紫外辐照过程中有机无机杂化钙钛矿太阳能电池性能变化规律以及电池微结构演化特征。实验结果表明,紫外辐照过程中太阳能电池内部会形成0.5–0.6 V的内建电场,钙钛矿中的I^-离子在电场的驱动下向金属Au电极和空穴传输层2, 2’, 7, 7’-四[N, N-二(4-甲氧基苯基)氨基]-9, 9'-螺二芴(Spiro-OMeTAD)一侧迁移;随后,空穴传输层与金电极的界面处,碘离子与光生空穴一起与金电极发生反应,将金属态Au氧化成离子态Au⁺。而Au⁺离子则在内建电场的驱动下反向迁移穿过钙钛矿MAPbI₃层,直接被SnO₂和MAPbI₃界面处的电子还原形成金属Au纳米团簇。除此之外,紫外辐照过程中钙钛矿太阳能电池性能降低的同时,往往伴随着Spiro-OMeTAD与钙钛矿界面处物质迁移、钙钛矿薄膜内晶界展宽以及Au纳米颗粒周围MAPbI₃物相分解等现象。以上各种因素的协同作用,共同导致了紫外光照下有机无机杂化钙钛矿太阳能电池光电转换性能(PCE)、开路电压(V_oc)以及短路电流(J_sc)等性能参数的急剧下降。     

Acyl Group Migration in Pyranosides as Studied by Experimental and Computational Methods

Acyl group migration affects the synthesis, isolation, manipulation and purification of all acylated organic compounds containing free hydroxyl groups, in particular carbohydrates. While several isolated studies on the migration phenomenon in different buffers have been reported, comprehensive insights into the overall migration process in different monosaccharides under similar conditions have been lacking. Here, we have studied the acyl migration in different monosaccharides using five different acyl groups by a combination of experimental, kinetic and theoretical tools. The results show that the anomeric configuration in the monosaccharide has a major influence on the migration rate, together with the relative configurations of the other hydroxyl groups and the nature of the migrating acyl group. Full mechanistic model, based on computations, demonstrates that the acyl migration proceeds through an anionic stepwise mechanism with linear dependence on the [OH⁻] and the pK_a of the hydroxyl group toward which the acyl group is migrating.     

锰氧化物中氧空位的构建及其催化氧化苯系物作用机制研究进展

作为一种过渡金属氧化物,锰氧化物以其多晶型、储/释氧能力强、蕴含丰富氧物种、结构缺陷可控等优点被广泛应用于苯系物的热催化氧化。其中,具有众多特性的氧空位能有效促进苯系物的完全催化氧化,因而成为各界研究的焦点。我们综述了常见的氧空位构建方法及表征技术,并总结了在苯系物催化氧化过程中,锰氧化物中氧空位的几种重要作用机制对催化活性和抗水性能的积极影响。最后文章对氧空位构建新方法、形成机理、具体过程及其在锰氧化物热催化氧化苯系物领域中的应用进行了总结和展望。