Study of H/D exchange rates to derive the strength of intramolecular hydrogen bonds in halo substituted organic building blocks: An NMR spectroscopic investigation

Rates of hydrogen/deuterium (H/D) exchange determined by H-1 NMR spectroscopy are utilized to derive the strength of hydrogen bonds and to monitor the electronic effects in the site-specific halogen substituted benzamides and anilines. The theoretical fitting of the time dependent variation of the integral areas of H-1 NMR resonances to the first order decay function permitted the determination of HID exchange rate constants (k) and their precise half-lives (t(1/2)) with high degree of reproducibility. The comparative study also permitted the unambiguous determination of relative strength of hydrogen bonds and the contribution from electronic effects on the HID exchange rate. (C) 2015 Elsevier B.V. All rights reserved.

Conformation-selective coordination-driven self-assembly of a ditopic donor with Pd-II acceptors

Coordination-driven self-assembly of 3-(5-(pyridin-3-yl)-1H-1,2,4-triazol-3-yl)pyridine (L) was investigated with 90 degrees cis-blocked Pd(II) acceptors and tetratopic Pd(NO3)(2). Although the ligand is capable of binding in several different conformations (acting as a ditopic donor through the pyridyl nitrogens), the experimental results (including X-ray structures) showed that it adopts a particular conformation when it binds with 90 degrees cis-blocked Pd(II) acceptors (two available sites) to yield 2 + 2] self-assembled macrocycles. On the other hand, with Pd(NO3)(2) (where four available sites are present) a different conformer of the same donor was selectively bound to form a molecular cubic cage. The experimental findings were corroborated well with the density functional theory (B3LYP) calculations. The tetratopic Pd(NO3)(2) yielded a 6 + 12] self-assembled Pd6L12 molecular cube, which contains a potential void occupied by nitrate and perchlorate ions. Being a triazole based ligand, the free space inside the cage is enriched with several sp(2) hybridised nitrogen atoms with lone pairs of electrons to act as Lewis basic sites. Knoevenagel condensation reactions of several aromatic aldehydes with active methylene compounds were successfully performed in reasonably high yields in the presence of the cage.

Evaporation-Condensation Synthesis and Optical Property of In(2)O(3)Octahedrons

Synthesis of In2O3 octahedrons is carried out successfully by heating Indium metal pieces in air ambient. The sample is characterized by scanning electron microscopy (SEM), Energy dispersive X-ray spectroscope (EDS), X-ray diffraction (XRD) and Raman spectroscopy. The as-prepared In2O3 octahedrons are highly crystalline and exhibit body centered cubic structure. Room temperature and temperature (293-453K) dependence photoluminescence reveals a deep levelbroad emission of yellowish-orange spectra centered around 605 nm. The emission is due to the presence of defect levels in the band gap of materials.

HOMOGENIZATION OF A HYPERBOLIC EQUATION WITH HIGHLY CONTRASTING DIFFUSIVITY COEFFICIENTS

We study a hyperbolic problem in the framework of periodic homogenization assuming a high contrast between the diffusivity coefficients of the two components M-epsilon and B-epsilon of the heterogeneous medium. There are three regimes depending on the ratio between the size of the period and the amplitude a, of the diffusivity in B-epsilon. For the critical regime alpha(epsilon) similar or equal to epsilon, the limit problem is a strongly coupled system involving both the macroscopic and the microscopic variables. We also include the results in the non critical case.

Urea-Functionalized Self-Assembled Molecular Prism for Heterogeneous Catalysis in Water

Reaction of a ditopic urea ``strut'' (L-1) with cis-(tmen)Pd(NO3)(2) yielded a 3+3] self-assembled molecular triangle (T)L-1 = 1,4-di(4-pyridylureido)benzene; tmen = N,N,N',N'-tetrame-thylethane-1,2-diamine]. Replacing cis-(tmen)Pd(NO3)(2) in the above reaction with an equimolar mixture of Pd(NO3)(2) and a clip-type donor (L-2) yielded a template-free multicomponent 3D trigonal prism (P) decorated with multiple urea moieties L-2 = 3,3'-(1H-1,2,4-triazole-3,5-diyl)dipyridine]. This prism (P) was characterized by NMR. spectroscopy, and the structure was confirmed by X-ray crystallography. The P was employed as an effective hydrogen-bond-donor catalyst for Michael reactions of a series of water-insoluble nitro-olefins in an aqueous medium. The P showed better catalytic activity compared to the urea based ligand L-1 and the triangle T. Moreover, the confined nanospace of P in addition to large product outlet windows makes this 3D architecture a perfect molecular vessel to catalyze Diels-Alder reactions of 9-hydroxymethylanthracene with N-substituted maleimide in the aqueous medium. The present results demonstrate new observations on catalytic aqueous Diels-Alder and Michael reactions in heterogeneous fashion employing a discrete 3D architecture of Pd(II). The prism was recycled by simple filtration and reused several tithes without significant loss of activity.

HOMOGENIZATION OF A HYPERBOLIC EQUATION WITH HIGHLY CONTRASTING DIFFUSIVITY COEFFICIENTS

We study a hyperbolic problem in the framework of periodic homogenization assuming a high contrast between the diffusivity coefficients of the two components M-epsilon and B-epsilon of the heterogeneous medium. There are three regimes depending on the ratio between the size of the period and the amplitude a, of the diffusivity in B-epsilon. For the critical regime alpha(epsilon) similar or equal to epsilon, the limit problem is a strongly coupled system involving both the macroscopic and the microscopic variables. We also include the results in the non critical case.

Primary and rechargeable zinc-air batteries using ceramic and highly stable TiCN as an oxygen reduction reaction electrocatalyst

Primary and secondary zinc-air batteries based on ceramic, stable, one dimensional titanium carbonitride (TiCN) nanostructures are reported. The optimized titanium carbonitride composition by density functional theory reveals their good activity towards the oxygen reduction reaction (ORR). Electrochemical measurements show their superior performance for the ORR in alkaline media coupled with favourable kinetics. The nanostructured TiCN lends itself amenable to be used as an air cathode material in primary and rechargeable zinc-air batteries. The battery performance and cyclability are found to be good. Further, we have demonstrated a gel-based electrolyte for rechargeable zinc-air batteries based on a TiCN cathode under ambient, atmospheric conditions without any oxygen supply from a cylinder. The present cell can work at current densities of 10-20 mA cm(2) (app. 10 000 mA g(-1) of TiCN) for several hours (63 h in the case of 10 mA cm(-2)) with a charge retention of 98%. The low cost, noble metal-free, mechanically stable and corrosion resistant TiCN is a very good alternative to Pt for metal-air battery chemistry.

Investigation on a simulation model of floating half zone convection .2. Experiment

A simulation model of floating half zone with non-uniform temperature distribution at the upper rod and uniform temperature distribution at lower rod was discussed by numerical investigation in a previous paper. In the present paper, the experimental investigation of the simulation model is given generally. The results of the present model show that the temperature profile is quite different and the critical applied temperature difference is lower than the one of usual model with same geometrical parameters in most cases. The features of critical Marangoni number depending on the liquid bridge volume are also different from the ones of usual model.

Internal resonance of an L-shaped beam with a limit stop .2. Forced vibration

A limit stop is placed at the elbow of an L-shaped beam whose linear natural frequencies are nearly commensurable. As a result of this hardening device the non-linear system exhibits multiple internal resonances, which involve various degree of coupling between the first five modes of the beam in free vibration. A point load is so placed as to excite several modes and the resulting forced vibration is examined. In the undamped case, three in-phase and two out-of-phase solution branches have been found. The resonance curve is extremely complicated, with multiple branches and interactions between the first four modes. The amplitudes of the higher harmonics are highly influenced by damping, the presence of which can effectively attenuate internal resonances. Consequently parts of the resonance curve may be eliminated, with the resulting response comprising different distinctive branches. (C) 1996 Academic Press Limited

Influence of liquid bridge volume on the onset of oscillation in floating-zone convection .2. Numerical-simulation

The onset of oscillation in the floating zone convection driven by the gradient of surface tension was studied numerically for an unsteady and two-dimensional model, and studies were concentrated on the influence of liquid bridge volume on the onset of oscillation in comparison with the experimental results in the Paper I. The numerical results agree with the experimental ones presented in the previous paper, in which the distributions of critical applied temperature difference depending on the volume of liquid bridge and a gap range of liquid volume in marginal stability curve were obtained.

The influence of fluctuation fields on the force-free field .2. The local expansion

In Paper I (Hu, 1982), we discussed the the influence of fluctuation fields on the force-free field for the case of conventional turbulence and demonstrated the general relationships. In the present paper, by using the approach of local expansion, the equation of average force-free field is obtained as (1+b)×B 0=(#x002B;a)B 0#x002B;a (1)×B 0#x002B;K. The average coefficientsa,a (1),b, andK show the influence of the fluctuation fields in small scale on the configurations of magnetic field in large scale. As the average magnetic field is no longer parallel to the average electric current, the average configurations of force-free fields are more general and complex than the usual ones. From the view point of physics, the energy and momentum of the turbulent structures should have influence on the equilibrium of the average fields. Several examples are discussed, and they show the basic features of the fluctuation fields and the influence of fluctuation fields on the average configurations of magnetic fields. The astrophysical environments are often in the turbulent state, the results of the present paper may be applied to the turbulent plasma where the magnetic field is strong.

Post-cyclic Strength Degradation of Undisturbed and Remolded Marine Silty Clay

A series of static and cyclic-static tri-axial compression tests under consolidated-undrained conditions are carried out to study the characteristics of post-cyclic strength of the undisturbed and the remolded samples of marine silty clay. It is found that the post-cyclic monotonic strength decreases if the cyclic strain or pore pressure is over a certain value. The maximum degradation is 10% for undisturbed samples while 70% for remolded ones. The relationship between normalized undrained shear strength and apparent overconsolidation ratio, which is determined by the excess pore pressure induced by cyclic loading, is also established. Static consolidated-undrained tests on overconsolidated remolded samples are also performed. It is proposed that the static consolidated-undrained tests may be substituted for the cyclic-static consolidated-undrained tests if the post-cyclic strength degradation of remolded silty clay is needed to be evaluated simply.

Activación de aldehídos a,b-insaturados mediante aminocatálisis en procesos enantioselectivos. Cicloadiciones (3+2) y reacciones en cascada Michael/Henry

During the research that it is summarized in the present memory, the activation of enals via iminium ion catalysis in different transformations has been studied. Firstly, a 1,3-dipolar cycloaddition between stable azomethine ylides and a,b-unsaturated aldehydes catalyzed by a chiral imidazolidinone derivative has been optimized. Employing this methodology we have synthesized a large range of densely substituted pyrroloisoquinolines and pyrrolophthalazines with good yields and high values of diastereo- and enantioselectivity. Moreover, a mechanistic study has been carried out based on DFT calculations and experimental data which have allowed us to propose that the (3+2) cycloaddition reaction follows a sequential Michael addition/Mannich cyclization pathway. The formation of the iminium ion as a result of the condensation between the a,b-unsaturated aldehyde and the catalyst plays an essential role, regarding both reactivity and stereoselectivity. On the other hand we have developed a methodology to carry out a cascade Michael/Henry reaction followed by a sequential dehydration. Starting from simple substrates (2-nitromethylacrilates and a,b-unsaturated aldehydes) and employing a prolinol-derivative catalyst a series of quiral nitrocyclohexadienes have been synthesized.