Persistent carbocations from 4,4′-dimethylaminodiphenylethylenes within CaY zeolite: intrazeolite-water controls the structure of the carbocation

Inclusion of 4,4′-dimethylaminodiphenylethylene and related olefins within activated CaY results in the formation of persistent monomer carbocations. The structure of the cation, consequently the color of the zeolite, is controlled by water molecules present within zeolites. Under ‘dry’ conditions the zeolite is light yellow and under ‘wet’ conditions it is blue colored. Blue color results from the quininoidal structure adopted by 1,1-bis-(4-dimethylaminophenyl)ethyl cation through participation of the lone pair electrons present on the amino substituent at the para position.     

A phenomenological theory for polarization flop in spiral multiferroic TbMnO<Subscript>3</Subscript>

A phenomenological Landau theory has been used to explain magnetic field-driven polarization flop in TbMnO ₃. The Néel wall-like magnetic structure in spiral multiferroics induces a space-dependent internal magnetic field which exerts a torque on spins to rotate bc-spiral to ab-spiral. The external magnetic field is argued to be competing with easy axis anisotropy and the system stabilizes when anisotropy is minimum. With the help of Landau free energy with DM magnetoelectric coupling and a general ansatz for magnetization, the phenomenon of polarization flop has been explained. Relation between T_flop and critical magnetic field has been established and found to be in good agreement with the experiment. This could be an indication that anisotropy of the system is temperature- and magnetic field-dependent.     

Quantum chemical studies of peptide nucleic acid monomers and role of cyclohexyl modification on backbone flexibility

Peptide nucleic acids (PNA) bind sequence specifically to DNA/RNA and are of major interest for all fields of molecular biology and could form the basis for gene‐targeted drugs. Modifications are introduced in PNA to overcome problems associated with orientational selectivity in binding, to restrict conformational flexibility of backbone, and to discriminate binding for either DNA or RNA. The addition of geometrical isomers (1R,2S and 1S,2R) of cyclohexyl ring in the backbone of PNA could bring rigidification to PNA backbone and may impart specificity toward RNA. Therefore, quantum chemical studies are aimed to explore the conformational space, to find out preferred stable conformations of PNA and modified (1R,2S and 1S,2R) cyclohexyl PNA monomer. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009     

(4R,4aR,6S,7S,7aS)‐6‐Hydro­xy‐7‐hy­droxy­methyl‐4‐methyl­per­hydro­cyclo­penta­[c]­pyran‐1‐one chloro­form solvate from Valeriana laxiflora

The structure of an iridolactone isolated from Valeriana laxiflora was established as (4R,4aR,6S,7S,7aS)‐6‐hydroxy‐7‐hydroxy­methyl‐4‐methyl­per­hydro­cyclo­penta­[c]­pyran‐1‐one chloro­form solvate, C₁₀H₁₆O₄·CHCl₃. The two rings are cis‐fused. The δ‐lactone ring adopts a slightly twisted half‐chair conformation with approximate planarity of the lactone group and the cyclo­pentane ring adopts an envelope conformation. The hydroxy group, the hydroxymethyl group and the methyl group all have β orientations. The absolute configuration was determined using anomalous dispersion data enhanced by the adventitious inclusion of a chloro­form solvent mol­ecule. Hydro­gen bonding, crystal packing and ring conformations are discussed in detail.     

NUMERICAL SIMULATION OF THREE-DIMENSIONAL SHOCK-SHOCK INTERACTIONS ON A BLUNT BODY

A numerical study is conducted to simulate the effects of extraneous shock impingement on a blunt body in viscous hypersonic flow. The interaction of extraneous shock with the leading-edge shock results in a very complex flow field that contains local regions of high pressure and intense heating. The heating and pressure can be orders of magnitude higher than the peak values in the absence of shock impingement. The flow field is calculated by solving thin-layer Navier-Stokes equations with a finite-volume flux splitting technique developed by van Leer. For a zero or small sweep of the body, a type IV interaction occurs, which produces a lambda shock structure with a supersonic jet embedded in the otherwise subsonic flow; for a moderate sweep of about 25^°, a type V interaction occurs in which a subsonic shear layer sandwiched in supersonic flow is produced with a transmitted shock. In the present study, both type IV and type V interactions are investigated. Results of the present numerical investigation are compared with available experimental results. For the present conditions, the peak pressure is 2.2 times the unimpinged stagnation point pressure and the peak heating is 3 times the unimpinged stagnation point heating. The flow for a type IV interaction is found to be unsteady.     

Determination of 3-hydroxy pterocarpan, a novel osteogenic compound in rat plasma by liquid chromatography-tandem mass spectrometry: application to pharmacokinetics study

A rapid, sensitive and selective LC‐MS/MS method for the quantitative analysis of 3‐hydroxy pterocarpan (S006‐1709) in female rat plasma has been developed and validated. A Discovery RP₁₈ column was used for the chromatographic elution using acetonitrile and 0.1% acetic acid in water as mobile phase (80:20 v/v) at the flow rate of 0.5 mL/min. MS/MS analysis was performed using a triple quadrupole mass spectrometer with electrospray ionization in negative ion mode using biochanin as an internal standard (IS). Extraction of S006‐1709 and IS from rat plasma was done by liquid–liquid extraction method using diethyl ether. The LC‐MS/MS method was sensitive with 1.95 ng/mL as the limit of detection and 3.9 ng/mL as the lower limit of quantification. The method was linear in the concentration range of 3.9–1000 ng/mL. The percentage bias for intraday and interday accuracy was not greater than 4.2 and the %RSD for intraday and interday precision was not greater than 13.2. The recoveries of S006‐1709 and IS were 73.9–79.3 and 85.7%, respectively. S006‐1709 was found to be stable in various stability studies. The validated LC‐MS/MS method was successfully applied for the oral pharmacokinetics study of S006‐1709 at 10 mg/kg in female Sprague–Dawley rats. Copyright © 2010 John Wiley & Sons, Ltd.     

Optimization of transfer of laser-cooled atom cloud to a quadrupole magnetic trap

We present here our experimental results on transfer of laser-cooled atom cloud to a quadrupole magnetic trap. We show that by choosing appropriately the ratio of potential energy in magnetic trap to kinetic energy of cloud in molasses, we can obtain the maximum phase-space density in the magnetic trap. These results guide us to choose the value of current to be switched in the quadrupole coils used for magnetic trapping for a given temperature of the cloud after molasses. This study is also useful to set the initial phase-space density of the cloud before evaporative cooling.     

腙基席夫碱配体铜(Ⅱ)配合物的合成、结构表征、生物活性和密度泛函理论计算

以甲醇为介质,合成了3种新的席夫碱配体HL¹(2-hydroxybenzaldehyde2-(2-oxo-1,2-diphenylethylidene)hydrazone)、HL²(4-hydroxybenzaldehyde2 -(2 - oxo- 1,2 -diphenylethylidene)hydrazone)和 L³(2 -methoxybenzaldehyde2-(2-oxo-1,2-diphenylethylidene)hydrazone)的Cu(Ⅱ)配合物1~3。通过元素分析、光谱方法、磁化率测量和密度泛函理论(DFT)计算对配合物进行了表征。通过单晶X射线衍射研究对合成的配体进行了结构表征。通过DFT计算确定了配合物的优化结构。通过紫外可见吸收光谱和荧光发射光谱研究了配合物与小牛胸腺DNA(CT-DNA)的结合能力。吸收光谱研究揭示了增色效应,并提出了与CT-DNA相互作用的可能模式。溴化乙锭(EB)竞争结合研究表明,配合物可以取代 DNA-EB 加合物中的 DNA,且配合物可能以嵌入模式与 CT-DNA结合。配合物对革兰氏阴性肺炎克雷伯菌、大肠杆菌、鲍氏志贺菌和革兰氏阳性金黄色葡萄球菌的体外抗菌活性研究表明,配合物2对肺炎克雷伯菌和鲍氏志贺菌具有明显抗菌活性,但配合物1和3没有表现出任何显著的抗菌活性。     

Structural and spectral studies of palladium(II) and platinum(II) complexes derived from N,N,N,N-tetradentate macrocyclic ligands

Palladium(II) and platinum(II) complexes having the general composition [M(L)] X2 (where M=Pd(II) and Pt(II), L=3,4,12,13-tetraphenyl-2,5,11,14,19,20-hexaaza tricyclo [13.3.1.1.(6-10)] cosa-1(19), 2,4,6,8,10,(20),11,13,15,17-decaene (L1); 3,4,13,14-tetraphenyl-2,5,12,15-tetraaza tricyclo [11,0,0,(6-11)] cosa-1(16),2,4,7,9,6(11),12,14,17, 19-decaene (L2); 2,3,8,9-tetraphenyl-1,4,7,10-tetraaza cyclododeca-1,3,7,9-tetraene (L3) and X=Cl(-)) have been synthesized. The ligands were characterized on the basis of elemental analyses, IR, 1H NMR and EI mass spectral studies while that of the complexes were characterized on the basis of elemental analyses, molar conductance measurements, magnetic susceptibility measurements, IR, and electronic spectral techniques. All the complexes were found to be diamagnetic. The structures consist of monomeric units in which the Pd(II) and Pt(II) atoms exhibit square planar geometry.     

Optical excitations in carbon architectures based on dodecadehydrotribenzo[18]annulene

The origin of excitations in multi-chromophore carbon network substructures based on dodecadehydrotribenzo[18]annulene has been investigated by steady-state and photon echo spectroscopy, configuration interaction (CIS and CIS(D)), and time-dependent density functional theory (TD-DFT). 1,4-diphenylbutadiyne, the simplest structural subunit within the annulene, was used in modeling the spectroscopic studies to explain the origin of excitations in the macrocycles. The optical excitations in longer linear systems were found to be similar to its diphenylacetylene analogue. However, the results from dodecadehydrotribenzo[18]annulene and other multichromophore networks systems illustrate the possibility of strong intramolecular interactions and the formation of delocalized excited states. Calculations were carried out to explain the basic similarities and differences in excitations of the model compounds such as diphenylbutadiyne and the macrocycles. The fundamental excitation in these systems can be primarily described as a pi --> pi* transition. Two low-energy resonances were observed from experiment for the annulene systems, and possible explanations for these low-energy resonances in the macrocycles are explored. The significant difference found in the calculated oscillator strength of the two low-energy bands for the macrocycles as well as the dynamics of solvent interactions was further investigated by three-pulse photon echo measurements. A simple exciton model was developed to discuss the excitations in the larger macrocycles. The results from this model were found to be in good agreement with the TD-DFT calculations.