新型磁性葡聚糖亲和吸附剂的制备及在尿激酶纯化中的应用

 采用反相悬浮包埋技术合成多分散的粒径在 5 0目～ 30 0目的磁性葡聚糖微球 (MDMS)。MDMS经环氧氯丙烷活化后 ,分别键合氨基乙酸、6 氨基己酸和乙二胺作为间隔臂 ,以碳二亚胺为偶联剂 ,分别偶联L 精氨酸甲酯、对氨基苯甲脒和胍基己酸配体 ,制备了 5种磁性亲和吸附剂。研究了分散介质及其粘度和密度、有机相和水相的体积比、表面活性剂的用量、搅拌速度等因素对微球制备的影响。将所制备的磁性亲和吸附剂应用于尿激酶粗品的纯化 ,并讨论了偶联试剂和配体对尿激酶纯化效果的影响。     

Recent advances in the design of dopant-free hole transporting materials for highly efficient perovskite solar cells

This review gives an overview of the latest advances in dopant-free hole transporting materials (HTMs) for perovskite solar cells and discusses the new molecular design strategies towards efficient and stable dopant-free HTMs.     

腰果酚键合硅胶固定相的制备及其色谱性能北大核心CSCD

天然产物作为一种绿色低毒、来源广泛、功能位点丰富的单体,已被广泛应用于色谱固定相的研制与开发。该文以天然可再生资源腰果酚为配体,通过一步法开环反应将其接枝到由γ-缩水甘油醚氧丙基三甲氧基硅烷(KH-560)修饰的硅胶上,制备得到腰果酚键合硅胶固定相。利用傅里叶红外光谱、元素分析、热失重分析和N_(2)吸附脱附实验对固定相进行表征,结果表明成功制备了腰果酚键合硅胶色谱固定相。采用Tanaka实验试剂、烷基苯、多环芳香烃、苯酚类化合物和芳香族位置异构体为探针评价其分离性能和保留机制,并与C_(18)柱进行对比。研究发现,腰果酚键合固定相除疏水作用外,还具有π-π和氢键作用。基于上述保留作用,腰果酚键合硅胶固定相对测试探针表现出良好的分离性能。重复进样10次,各探针保留时间的RSD为0.052%~0.079%,峰面积的RSD为0.104%~0.847%,峰高的RSD为0.081%~0.272%,表明该色谱柱具有良好的重复性和稳定性。此外,腰果酚键合硅胶色谱柱对中药喜树果和吴茱萸果的粗提物具有良好的分离性能,验证了其在实际样品分析中的巨大潜力。将天然产物腰果酚用于色谱固定相的制备,为分离纯化喜树碱和吴茱萸提供了新的方法,同时拓展了腰果酚在色谱分离材料方面的应用。     

The Role of Triazole and Glucose Moieties in Alkali Metal Cation Complexation by Lower-Rim Tertiary-Amide Calix[4]arene Derivatives

The binding of alkali metal cations with two tertiary-amide lower-rim calix[4]arenes was studied in methanol, N,N-dimethylformamide, and acetonitrile in order to explore the role of triazole and glucose functionalities in the coordination reactions. The standard thermodynamic complexation parameters were determined microcalorimetrically and spectrophotometrically. On the basis of receptor dissolution enthalpies and the literature data, the enthalpies for transfer of reactants and products between the solvents were calculated. The solvent inclusion within a calixarene hydrophobic basket was explored by means of ¹H NMR spectroscopy. Classical molecular dynamics of the calixarene ligands and their complexes were carried out as well. The affinity of receptors for cations in methanol and N,N-dimethylformamide was quite similar, irrespective of whether they contained glucose subunits or not. This indicated that sugar moieties did not participate or influence the cation binding. All studied reactions were enthalpically controlled. The peak affinity of receptors for sodium cation was noticed in all complexation media. The complex stabilities were the highest in acetonitrile, followed by methanol and N,N-dimethylformamide. The solubilities of receptors were greatly affected by the presence of sugar subunits. The medium effect on the affinities of calixarene derivatives towards cations was thoroughly discussed regarding the structural properties and solvation abilities of the investigated solvents.     

Structure elucidation of acetylation products of 2-acyl-1,3-indanediones by correlation of infrared spectral data

Summary 2-(1-Acetoxyalkylidene)- and 2-(1-acetoxybenzylidene)-1,3-indanediones (1a–1e) were proven to be the products of acetylation of 2-acyl-1,3-indanediones (2a–2e) by ketene using a detailed investigation and correlation analysis of infrared spectral data as well as¹H-NMR and¹³C-NMR spectra. Study by means of CNDO/2 and MMPI methods also demonstrates that the structure1 is more stable as the alternative one of 2-acyl-3-acetoxy-2-indene-1-ones (5). It was shown that the recently proposed general correlations v(C=O)_s vs. v(C=O)_as and v(C=O) vs. X⁺(R) as well as the mechanical anharmonicities of asymmetric C=O stretching vibration can be successfully used as a tool of structural diagnostics of cyclic 1,3-dicarbonyl compounds.

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Strukturaufklärung von Acetylierungsprodukten von 2-Acyl-1,3-indandionen mittels Korrelation von Infrarot-Daten

Zusammenfassung 2-(1-Acetoxyalkyliden)- und 2-(1-Acetoxybenzyliden)-1,3-indandione (1a–1e) wurden mittels einer detaillierten infrarot-spektroskopischen Untersuchung (IR-Korrelation) und¹H-NMR und¹³C-NMR Spektroskopie als Acetylierungsprodukte von 2-Acyl-1,3-indandionen (2a–2e) mit Keten nachgewiesen. CNDO/2- und MMPI-Rechnungen zeigten auch, daß Struktur1 stabiler ist, als die der alternativen 2-Acyl-3-acetoxy-2-inden-1-one5. Es wird gezeigt, daß die kürzlich vorgeschlagenen allgemeinen Korrelationen v(C=O)_s gengen v(C=O)_as und v(C=O) gegen X ⁺(R) und auch die mechanischen Anharmonizitäten der asymmetrischen C=O Streckschwingung erfolgreich als Werkzeug zur Strukturaufklärung cyclischer 1,3-Dicarbonyl-Verbindungen eingesetzt werden können.

     

Torsion of chiral Cosserat elastic rods

This paper is concerned with the torsion of isotropic chiral Cosserat elastic cylinders. First, the generalized plane strain problem is defined and an existence result is presented. Then, the three-dimensional problem is reduced to the study of some generalized plane strain problems. In general, the torsion of the cylinder is accompanied by bending and extension. The method is applied to study the torsion of a circular cylinder.     

A novel selective fluorescent chemosensor for Fe 3+ ions based on phthalonitrile dimer: synthesis,analysis, and theoretical studies

Phenyl-4,4-di(3,6-dibutoxyphthalonitrile) ( 3 ) was synthesized by the reaction of 1,4-phenylenebisboronic acid ( 1 ) and 4-bromo-3,6-dibutoxyphthalonitrile ( 2 ), using Suzuki cross-coupling reaction. The newly synthesized compound ( 3 ) was characterized by FT-IR, MALDI-MS, ESI-MS, ¹ H-NMR, ¹³ C-NMR, and ¹³ C-DEPT-135-NMR. The fluorescence property of phenyl-4,4-di(3,6-dibutoxyphthalonitrile) ( 3 ) towards various metal ions was investigated by fluorescence spectroscopy, and it was observed thatthe compound ( 3 ) displayed a significantly ‘turn-off’ response to Fe ³⁺ , which was referred to 1:2 complex formation between ligand ( 3 ) and Fe ³⁺ . The compound was also studied via density functional theory calculations revealing the interaction mechanism of the molecule with Fe ³⁺ ions.     

Stacking of Metal Chelates with Benzene: Can Dispersion‐Corrected DFT Be Used to Calculate Organic–Inorganic Stacking?

CCSD(T)/CBS energies for stacking of nickel and copper chelates are calculated and used as benchmark data for evaluating the performance of dispersion‐corrected density functionals for calculating the interaction energies. The best functionals for modeling the stacking of benzene with the nickel chelate are M06HF‐D3 with the def2‐TZVP basis set, and B3LYP‐D3 with either def2‐TZVP or aug‐cc‐pVDZ basis set, whereas for copper chelate the PBE0‐D3 with def2‐TZVP basis set yielded the best results. M06L‐D3 with aug‐cc‐pVDZ gives satisfying results for both chelates. Most of the tested dispersion‐corrected density functionals do not reproduce the benchmark data for stacking of benzene with both nickel (no unpaired electrons) and copper chelate (one unpaired electron), whereas a number of these functionals perform well for interactions of organic molecules.     

Synthesis of Cyclic Alkenyl Triflates by a Cationic Cyclization Reaction and its Application in Biomimetic Polycyclizations and Synthesis of Terpenes

Cyclic alkenyl triflates are useful intermediates in organic synthesis usually synthesized from ketones through a reaction involving enolization and trapping with a triflating agent. This sequence suffers from some stereochemical drawbacks owing to the basic conditions required. Herein, we describe a new acid‐mediated cationic cyclization reaction of enyne derivatives (or alkynols) to access cyclic alkenyl triflates. This new atom‐economical process is high yielding, scalable, technically very simple, proceeds without the need of any metallic reagent or catalyst, and more importantly, it complements and challenges conventional methodologies. We have also developed new biomimetic cationic cyclization reactions to yield interesting polycyclic compounds. As a demonstration of the potential of this method in the context of total synthesis, we have synthesized two terpenes: austrodoral and pallescensin A. Using the cationic cyclization in the key step of the synthetic routes allowed the synthesis of these natural products in a very simple, concise, scalable, and efficient way.