Unprecedented SnCl2-mediated cyclization of nitro arenes via N-N bond formation

[reaction: see text] A mild, efficient, one-pot protocol for the cyclization of nitro-aryl substrates using SnCl(2) has been described. The mechanistic course of the reaction suggests the involvement of a hydroxylamine intermediate leading to an intramolecular cyclization via N-N bond formation. The versatility of the methodology has been demonstrated by using two nitro-aryl substrates derived from dihydroisoquinolines and dihydro-beta-carbolines. The intramolecular cyclization led to the formation of indazoles in high yields and purities.     

Construction of tricyclic enone, a common precursor for aphidicolane and stemodane B/C/D-ring system

Synthesis of a tricyclic enone (B/C/D ring system), a common key precursor for the aphidicolane- and stemodane-type diterpene, is described. The key reaction for the construction of the quaternary carbon center is allylation of epoxide at the more substituted carbon with an organotitanium reagent. Asymmetric reduction with DIP-Cl followed by stereoselective cyclization of spirocyclic ketone and the functional group modification gave the desired tricyclic enone in good yield.     

Atomistic simulation studies of magnetite surface structures and adsorption behavior in the presence of molecular and dissociated water and formic acid

Static energy minimization techniques have been used to elucidate the surface structures of magnetite crystals in pure and hydroxylated forms. Adsorption energy values in the presence of molecular water, dissociate water and simple carboxylic group molecule (formic acid) are calculated and we found that the carboxylic group do not adsorb strongly in most of the pure and hydroxylated surfaces in comparison to water. Since the associated calcium minerals are floated from magnetite using fatty acid collector, our calculations corroborate the flotation practice of removing these impurity minerals from magnetite.     

CHARMM general force field: A force field for drug‐like molecules compatible with the CHARMM all‐atom additive biological force fields

The widely used CHARMM additive all‐atom force field includes parameters for proteins, nucleic acids, lipids, and carbohydrates. In the present article, an extension of the CHARMM force field to drug‐like molecules is presented. The resulting CHARMM General Force Field (CGenFF) covers a wide range of chemical groups present in biomolecules and drug‐like molecules, including a large number of heterocyclic scaffolds. The parametrization philosophy behind the force field focuses on quality at the expense of transferability, with the implementation concentrating on an extensible force field. Statistics related to the quality of the parametrization with a focus on experimental validation are presented. Additionally, the parametrization procedure, described fully in the present article in the context of the model systems, pyrrolidine, and 3‐phenoxymethylpyrrolidine will allow users to readily extend the force field to chemical groups that are not explicitly covered in the force field as well as add functional groups to and link together molecules already available in the force field. CGenFF thus makes it possible to perform “all‐CHARMM” simulations on drug‐target interactions thereby extending the utility of CHARMM force fields to medicinally relevant systems. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

Syntheses and crystal structures of cadmium(II)X2-hexamethylenetetramine (X = Br/I/SCN) coordination polymers having different dimensionality

Four new coordination polymers of cadmium(II) with hexamethylenetetramine (htm) have been synthesized and characterized by routine physicochemical techniques as well as by X-ray single crystal structure analysis. They are [CdBr(htm)(SCN)(H₂O)₂·CH₃OH]_n (1), [CdI(htm)(SCN)(H₂O)₂·0.5(CH₃OH)]_n (2), [Cd₂(htm)₃(SCN)₄(H₂O)]_n·nH₂O (3) and [Cd₃Br₆(htm)₂(H₂O)₅·(htm)(H₂O)₆]_n (4). Complexes 1, 2 and 3 exhibit 1D polymeric structure and complex 4 shows a 2D undulated layered arrangement, containing Cd₆(htm)₆ hexagonal units as building block, which extended to a 3D supramolecular architecture through hydrogen bonding. Thorough thermal investigation suggest that as far as the thermal stability of Cd(II)-htm bond is concerned it attains the maximum in complex 1 and minimum in complex 4. In case of complex 3 the thermal study inferred that CdS end product was obtained at ∼730 °C, whereas in case of other complexes the thermally stable end product remained unidentified. Solid state fluorescence study shows that all the complexes are luminescent at room temperature except complex 3.     

Bivariate generalized exponential distribution

Recently it has been observed that the generalized exponential distribution can be used quite effectively to analyze lifetime data in one dimension. The main aim of this paper is to define a bivariate generalized exponential distribution so that the marginals have generalized exponential distributions. It is observed that the joint probability density function, the joint cumulative distribution function and the joint survival distribution function can be expressed in compact forms. Several properties of this distribution have been discussed. We suggest to use the EM algorithm to compute the maximum likelihood estimators of the unknown parameters and also obtain the observed and expected Fisher information matrices. One data set has been re-analyzed and it is observed that the bivariate generalized exponential distribution provides a better fit than the bivariate exponential distribution.     

Acoustic source localization in anisotropic plates

The conventional triangulation technique cannot locate the acoustic source in an anisotropic plate because this technique requires the wave speed to be independent of the propagation direction which is not the case for an anisotropic plate. All methods proposed so far for source localization in anisotropic plates require either the knowledge of the direction dependent velocity profile or a dense array of sensors. In this paper for the first time a technique is proposed to locate the acoustic source in large anisotropic plates with the help of only six sensors without knowing the direction dependent velocity profile in the plate. Experimental results show that the proposed technique works for both isotropic and anisotropic structures. For isotropic plates the required number of sensors can be reduced from 6 to 4.     

Morphology dependent luminescence properties of rare-earth doped lanthanum fluoride hierarchical microstructures

Here, we demonstrate an ionic liquid-assisted hydrothermal method for preparing Tb³⁺ and Eu³⁺ doped LaF₃ hierarchical microstructures and the morphology is modified by hydrothermal reaction time, temperature of heating and ionic liquid concentration. The mechanism related to morphology control is proposed and discussed. It is also found that PL intensity, decay time and quantum efficiency are sensitive to the morphology. The average decay times are 2.9 ms and 4.8 ms for Eu³⁺ doped LaF₃ microstructures prepared at 10 min and 3 h reaction time, respectively. The average decay time is increased from 4.8 ms to 5.8 ms after heating the sample at 500 °C. The quantum efficiency varies from 34% to 67% with changing morphology. Analysis suggests that morphology plays an important role on efficiency of rare-earth doped materials.