Investigation of homo- and heterodimer alkali metal cation complexes of resorc[4]arenes by electrospray ionization mass spectrometry

Resorc[4]arenes are compounds with interesting properties, mainly because of their ability to form host-guest complexes with the guest located inside the cavity. The size of the guest limits the complexation, as shown by a competition experiment with tetraalkylammonium ions of different size. By electroscopy ionization tandem mass spectrometric experiments on resorc[4]arene heterodimers bearing an alkali metal ion as guest, it was found that there must be two different binding mechanisms for alkali metal ions with high surface charge density (Li(+) and Na(+)) on the one hand compared with those with a lower surface charge density on the other hand (K(+), Rb(+), Cs(+)).     

卟啉—酞菁二元化合物分子内的能量传递

研究了新的以哌嗪连接的含卟啉－酞菁双发色团的分子（Ｐｒ－Ｐｃ）的时间分辨荧光光谱并对所得的结果进行了分析和讨论．在光谱数据的基础上结合分子的结构对非极性溶剂中二元化合物分子内的能量传递过程和机制进行了讨论,并算出发色团的空间相对距离为１．８７ｎｍ．     

氢键和供体－受体相互作用驱动的酰肼异体二聚体组装

A new series of hydrogen bonding-driven heterodimers have been self-assembled in chloroform from hydrazide-based monomers. Additional intermolecular donor-acceptor interaction between the electron-rich bis（p-phenylene）-34-crown-10 unit and the electron-deficient naphthalene diimide unit has been utilized to increase the stability of the dimmers, and pronounced cooperativity of the two discrete non-covalent forces to stabilize the dimer has been revealed by the quantitative ^1H （2D） NMR and UV-Vis experiments.     

Cyclodextrin as a Template for Molecular Assembly: Formation of Heterodimers Between a Polyamino- and a Polysulfonato-β-Cyclodextrin

A poly(hydroxyethylamino)- and a poly(sulfonatophenyloxy)--cyclodextrin derivative, bearing opposite ionic charges, have been shown by potentiometric titration to form stable pH-dependent heterodimers with each other in water. The formation constants of these dimers show that a very stable assembly is formed between the fully deprotonated sulfonato derivative and the fully protonated amino derivative (log K_a = 8.5), which constitutes the assembly of multiple extended atomic groupings on cyclodextrin as template.     

Density functional study of indole–pyrrole heterodimer potential energy hypersurface

A density‐functional study of indole–pyrrole heterodimer potential energy hypersurface (PES) was performed. Eight stationary points were located on the B3LYP/6‐31++G(d,p) PES, three of which correspond to real minima, all of them being characterized with an N? H … π type hydrogen bonding. In two of these minima (the local ones), pyrrole subunit acts as a hydrogen bond proton donor, while the global minimum corresponds to indole–H … π(‐pyrrole) arrangement. Besides the interaction and dissociation energies corrected for BSSE and the monomer relaxation energies and the relevant structural parameters, anharmonic N? H and N? H … π vibrational frequencies were calculated for various N? H oscillators involved in this interaction from the 1‐D DFT vibrational potentials. On the basis of anharmonic vibrational frequency analysis, it was concluded that the two types of N? H … π hydrogen bonded dimers (indole vs. pyrrole being a proton donor) should be distinguishable with spectroscopic methods. Various contributions to the overall anharmonic frequency shifts upon hydrogen bonding were calculated and discussed as well. The charge field perturbation (CFP) technique was employed to study the electrostatic + polarization influence of the proton accepting unit on the N? H(… π) vibrational potential. The second‐order perturbation theory analysis (SOPT) of the Fock matrix (i.e., its Kohn–Sham analog) within the natural bond orbital (NBO) basis, as well as various NBO deletion analyses revealed an essentially one‐directional charge transfer (CT) of a π(C? C) → σ*(N? H) type in the case of all three minima. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003     

A Novel Ratiometric Oxygen Sensor Based On a Sextuple Hydrogen‐Bonding Self‐Assembly Molecular Heterodimer

A novel sextuple hydrogen‐bonding (HB) self‐assembly molecular heterodimer bearing an iridium complex as the indicator dye and two carbazoles as the reference dye, namely 6HB‐Irbt‐Cz , was synthesized, and its molecular structure was confirmed by ¹H NMR, ¹³CNMR, TOF‐MS and 2D NMR. Because of the inefficient energy transfer process between the carbazole and iridium complex units, 6HB‐Irbt‐Cz exhibits distinct ?uorescence/phosphorescence dual emission in neat film state. More importantly, the neat film sample of 6HB‐Irbt‐Cz could display linear ratiometric optical response toward oxygen in the full oxygen concentration range from 0 to 100 vol%, together with good stability, reversibility and rapid response‐recovery times. Note that this represents the first discovery of neat‐film‐based oxygen sensor capable of showing strictly linear ratiometric Stern‐Volmer behavior in the oxygen concentration of 0–100 vol%.     

Ag-Al纳米球二聚体的光学性质研究

金属纳米材料因其表面等离子体共振特性而备受关注。异质结构的金属纳米材料的光学特性相比于同质结构因其材料的不同破坏了原有结构的对称性,对称性的破坏将引起光学性质的改变,相邻两个颗粒之间的相互作用会产生Fano共振。Fano共振是由异质纳米结构的表面等离子体共振耦合引起的,通过合理地调控表面等离子体共振的耦合,将进一步调控Fano共振的强度同时促使异质结构的电场增强特性和辐射特性得到进一步优化。受金银等贵金属的带间跃迁影响,金属铝纳米材料成为研究紫外-近紫外光区的表面等离子体共振研究最佳选择。采用有限时域差分方法研究了Ag-Al纳米球二聚体的光学特性。研究了Ag和Al纳米球组成的二聚体的吸收光谱与入射光偏振方向、纳米球半径、颗粒间距和介质折射率等几何结构及物理参数的关系,并深入讨论了二聚体的局域场分布规律;讨论了获取更高效的Fano共振光谱的方法。由于材料的对称性被破坏,异质二聚体的光学性质与同质二聚体明显不同,Ag-Al异质纳米球二聚体呈现出在紫外和可见光区的双Fano共振现象。Ag-Al二聚体表面等离子体互相耦合引起Fano共振从而导致表面等离子体的共振抑制和增强。研究结果对在紫外-可见光区的表面等离子体应用、纳米光学器件的设计与开发及基于表面等离子体共振的表面增强光谱、生物传感和检测研究等有一定参考价值。     

具有相反电荷取代基的卟啉和酞菁异聚体荧光光谱的研究

用荧光光谱的方法研究了由水溶性的中位-四-[对-(N,N,N-三甲基苯基)铵基]卟啉的碘化物和2,6,9,15-四(4'-磺酸基)镓酞菁形成的超分子体系,在水溶液中阴离子酞菁与阳离子卟啉能形成杂聚集体。荧光光谱滴定的结果表明:聚集体为杂二聚体,形成平衡常数为1.17×10⁸L/mol。说明了卟啉-酞菁杂二聚体是非常稳定的。没有观察到聚集体的荧光发射。     

Crystallographic Studies of Cephalosporin Acylase from Pseudomonas sp. Strain 130

The cephalosporin acylases are a group of enzymes that hydrolyze cephalosporin C and/or glutaryl 7-aminocephalosporanic acid to produce ?-aminocephalosporanic acid. The cephalosporin acylase from Pseudomonas sp. strain 130 was crystallized in two different forms suitable for structural studies. A tetragonal crystal form diffracted to 0.24 nm belonged to the space group P41212. There was one αβ heterodimer per asymmetric unit. A second crystal form diffracted to 0.21nm belonged to the space group P21. There was four αβ heterodimers per asymmetric unit. The tetragonal crystal structure of CA-130 was determined using the multiwavelength anomalous diffraction method and the P21 crystal structure was then determined using the molecular replacement method.