Stereochemistry of new nitrogen containing heterocyclic aldehyde. IX. Spectroscopic studies on novel mixed-ligand complexes of Rh(III)

Mono, bis and tris complexes of rhodium(III) oxine (systematic name 8-hydroxy-7-quinolinecarboxaldehyde) and mixed ligand have been prepared. The amine exchange reaction of coordinated Schiff base in these complexes has also been carried out, which gives symmetrical tetradentate Schiff base complexes. The complexes are characterized by elemental and thermal analysis, IR, magnetic and electronic spectral analysis methods were also employed as well as conductivity measurements. An octahedral structure is proposed for all the new complexes in which chloride is attached to the metal ion in 1:1; 1:2 (metal:ligand) ratio. The spectral data were utilized to compute the important ligand field parameter B, beta and Dq. The B-values suggest a strong covalency in the metal-ligand sigma-bond and the Dq-values indicate a medium strong ligand field. 1H NMR spectra show that the tris (ligand) complex is cis isomer. IR spectra show that the ligand is mono-basic bidentate.     

Finite perturbation theory-density functional theory calculation of the spin-dipolar contribution to NMR spin-spin coupling constants

In this work an implementation of the FPT-DFT approach for calculating the spin-dipolar contribution to NMR spin-spin coupling constants is presented. This method was tested in a set of small molecules, giving results in excellent agreement when comparing them with values taken from the literature, which were obtained with state-of-the-art calculations. To obtain an insight into the relative importance of the spin-dipolar contribution in unsaturated compounds, calculations of J(F,C), J(F,F) and J(F,H) couplings in 1,2-, 1,3-, and 1,4-difluorobenzenes were performed. An important spin-dipolar contribution to ³ J(F, F) and ⁵ J(F,F) was found, suggesting that this term might be important in some cases. When performing DFT calculations the non-singlet instabilities usually found in unsaturated compounds are overcome.     

Orbital contributions to relativistic corrections of the NMR nuclear magnetic shielding tensor originated in scalar field-dependent operators

In this work relativistic corrections to the magnetic shielding constant (σM), which arise from scalar field-dependent operators (both linear and bilinear), are calculated and decomposed into contributions from molecular orbitals (MOs). Numerical results for the magnetic shielding constant of the heavy nucleus X in closed shell atomic ions X^? and HX compounds (X = F, Cl, Br, I) are presented. The relative importance of inner-shell and valence electrons in the definition of each one of these terms is thus assessed and its relation with their sensitivity to changes in a chemical environment is discussed.     

Experimental, Theoretical and Biological Activity Study on the Acyl-Substituted Benzo-18-crown-6, Dibenzo-18-crown-6 and Dibenzo-24-crown-8

Hexadecanoyl, dihexadecanoyl, dioctadecaneoyl, di-10-undecenoyl, and dicis-9-octadecenoyl derivatives of benzo[18]crown-6, dibenzo[18]crown-6 and dibenzo[24]-8 were synthesized by the condensation of carboxylic acids (palmitic, stearic, oleic and undecenoic acid) with benzo and dibenzo crown ethers in the presence of zinc chloride. The extraction equilibrium constants of such macrocyclic ethers with long side chains were estimated using chloroform/water and dichloromethane/water membranes transfer of Na-PAR (4-(2-pyridylazo)-resorcinol mono sodium monohydrate) with UV–Vis spectroscopy. It was found that they were in the range of 10.88–11.71 in dichloromethane and 8.04–11.77 in chloroform. These results actually show that the Na+ binding effect of macrocyclic ethers depends on the type and the length of side chains. The geometrical properties of the molecules were studied employing semi-empirical calculations by simulated annealing technique. The frontier molecular orbital energies and dipole moments were also examined. The biological activity results showed that the synthesized crown ethers have no activity against the studied microorganisms.     

FLUSHING TIME IN THE CIENFUEGOS BAY,CUBA

We use a high‐resolution numerical model to analyze the hydrodynamical exchange processes of the Cienfuegos Bay with the Caribbean Sea. Results show that freshwater inputs and wind are the main factors controlling the water exchange in the bay. Nine simulation case studies with three wind conditions and three freshwater inputs were carried out. The main conclusion is that the Cienfuegos Bay system has a slow exchange rate, with an average flushing time of 39 days during the rainy period and 50 days during the dry one, for the most probable wind direction. Two new temporary scales for Cienfuegos Bay are discussed: the local e‐flushing time and the flushing lag. The results obtained for these new variables validate the slow exchange capacity of the bay.     

Molecular Interactions and Thermodynamic Aspects of the Complexation Reaction between Gentian Violet and Several Cyclodextrins

The complexation process between gentian violet (CV+) and four different cyclodextrins (-, -, -, and HP--CDs) has been investigated under different reaction conditions (pH, solvent, and temperature) by electronic absorption and 1H NMR (NOE and NOESY) spectroscopies. All the binding constants were determined by the direct spectroscopic method. The H and S complexation values have been evaluated and discussed according to the diverse factors that affect the chemical interactions in these systems. A simple association takes place between the secondary hydroxyl or the hydroxypropyl groups of and HP--cycloamyloses, respectively, with the amine group of the gentian violet, while the binding between CV+ and - or -CDs corresponds to a real inclusion. Also, a CV22+ dimmeric species within the -CD cavity was detected in aqueous solution, while two molecules of -CD react with one molecule of gentian violet in DMSO at 294 K. In all the reaction media the -CD forms 1 : 1 complexes, but in the buffered aqueous solution at pH 7.5 the inclusion is deeper than in the other solvents. It is important to point out that the solvophobic effect is the most important binding factor in the complexation of the CV+ with the - and HP--CDs, while the complexes with -, and -cyclodextrins are mainly stabilized by van der Waals interactions between the guest and the host cavity. In all cases, the inclusion orientation is probably determined by the ion-dipole interactions between gentian violet and the solvent.     

半导体纳米激光

半导体纳米激光的研究是目前纳米技术（或纳米光子学）和半导体激光交汇产生的研究前沿。本文将综述这一领域最近一些最激动人心的进展。我们将集中讨论两种半导体纳米结构的纳米激光：自下而上生长而成的纳米线和自上而下刻蚀制成的纳米柱状结构。本文将综述这些纳米激光器的特殊特征,特别是利用表面等离子效应而成制成的金属{半导体等离子体激光,即目前世界上最小激光器的最新进展。由于这些纳米激光器的微小的尺寸以及对光在空间限制增强,我们必须重新检验半导体激光器中某些熟悉的概念在纳米尺度上的正确性和含义,例如模式增益和光限制因子（CF）的概念。本文将从统一的观点解释光限制因子在电介质和等离子体纳米激光器中的某些似乎反常的行为。在本文的通篇论述中,我们将尝试回答究竟激光器的尺寸能够小到什么程度,或者激光器的尺寸是否存在一个最小极限等基本问题。