Complexation and extraction behavior of trivalent indium with multiple proton ionizable p�Ct-butylcalix[5]arene pentacaarboxylic acid derivative: a new efficient solvent extraction reagent for indium

Complexation behavior of plural ion-exchangeable p?Ct-butylcalix[5]arene pentacarboxylic acid derivative towards trivalent indium has been investigated along with its monomeric analog from weakly acidic media into chloroform. The cyclic structure of calixarene ligand providing certain cavity and cooperativity of functional groups significantly affect the complexation behavior and calixarene derivative is an excellent extractant over monomeric analog. The extraction mechanism is ion exchange and carboxylic acid groups are adequate functional sites for extraction. Mononuclear and/or polynuclear species of indium and monomeric or bridged dimeric species of calixarene are involved in complexation and the composition of extracted complex varied with solution pH. One mole of calix[5]arene derivative tend to extract 3.5 mol of indium. The loaded indium was quantitatively back extracted with 1 mol dm^?3 hydrochloric acid solution.     

Quantification of binding affinities of essential sugars with a tryptophan analogue and the ubiquitous role of C-H···π interactions

The role of noncovalent interactions in carbohydrate recognition by aromatic amino acids has long been reported. To develop a molecular understanding of noncovalent interactions in the recognition process, we have examined a series of binary complexes between 3-methylindole (3-MeIn) and sugars. In particular, the geometries and binding affinities of 3-MeIn with α/β-D-glucose, β-D-galactose, α-D-mannose and α/β-L-fucose are obtained using the MP2(full)/6-31G(d,p) and the M06/TZV2D//MP2/6-31G(d,p) level of theories. The conventional hydrogen bonding such as N-H···O and C-H···O as well as nonconventional O-H···π and C-H···π type of interactions is, in general, identified as responsible for the moderately strong interaction energies. Large variations in the position-orientations of 3-MeIn with respect to saccharide are noticed, within the same sugar family, as well as across different sugar series. Furthermore, complexes with large differences in their geometries are recognized as capable of exhibiting very similar interaction energies, underscoring the significance of exhaustive conformation sampling, as carried out in the present study. These observations are readily attributed to the differences in the efficiency of the type of interactions enlisted above. The highest and lowest interaction energies, upon inclusion of 50% BSSE correction, are found to be -16.02 and -6.22 kcal mol(-1), respectively, for α-D-glucose (1a) and α-L-fucose (5j). While more number of prominent conventional hydrogen bonding contacts remains as a characteristic feature of the strongly bound complexes, the lower end of the interaction energy spectrum is dominated by multiple C-H···π interactions. The complexes exhibiting as many as four C-H···π contacts are identified in the case of α/β-D-glucose, β-D-galactose, and α/β-L-fucose with an interaction energy hovering around -8 kcal mol(-1). The presence of effective C-H···π interactions is found to be dependent on the saccharide configuration as well as the area of the apolar patch constituted by the C-H groups. The study offers a comprehensive set of binary complexes, across different saccharides, which serves as an illustration of the significance and ubiquitous nature of C-H···π interactions in carbohydrate binding in saccharide-protein complexes.     

Synthesis of chalcone precursor via Cu(I) catalyzed 1,3-dipolar reaction of functionalized acetylene and pyrazole embedded dipole

A new class of functionalized pyrazole bearing 1,2,3-triazole has been synthesized via Cu(I) mediated 1,3-dipolar cycloaddition of pyrazole bearing azide with various aromatic/heteroaromatic bearing terminal dipolarophile (acetylene). Structures of the newly synthesized compounds were explicated by analytical and spectral analysis. All the newly synthesized compounds were evaluated for their in-vitro antibacterial and antioxidant activity. Among the synthesized compound, triazole bearing 2,5-thiazolidinone 5b (20 ± 0.70) and triazole bearing thiocarboamide 5e (19 ± 0.70) showed good antibacterial activity against Escherichia coli and Pseudomonas aeruginosa, respectively. The newly synthesized compounds further tested for their ability to bleach DPPH radical using DPPH scavenging assay. Among the synthesized compounds 1,2,3-triazole bearing 2,5-thiazolidinone 5b (58.81%) exhibited good DPPH scavenging activity compared to the rest of the compounds. From the X-ray and Hirshfield analysis, it was observed that compound 3 , crystallizes in a triclinic crystal system with a P-1 space group. The major intercontacts present in these molecules are H…H (39.7%), C…H (23.9%), N…H (20.3%).     

An Expeditious Study of the Nature of Halogen(S) at γ-Positions in Carbonyl Compounds

The detailed study, of the behaviour of di/tri halo carbonyls to act as the synthetic equivalents of corresponding mono γ-halo carbonyls, is carried out.     

The Primitive Idempotents of a Cyclic Group Algebra

Explicit expressions are obtained for the 2n + 1 primitive idempotents in FG, the semisimple group algebra of the cyclic group G of order pⁿ (p an odd prime, n ≥ 1) over the finite field F of prime power order q, when q has order φ(pⁿ)/2 modulo pⁿ.AMS Mathematical Subject Classification (2000): 20C05, 94B05, 12E20, 16S34.     

Sustainability screw: role of relative production and abatement time scales

We postulate that reasonable notions of sustainability must include a time-scale synchronization of both the processes of human development and those of the natural environment. We perform our analysis within a simple system of five differential equations where non-renewable and renewable resources are coupled with production capacities, abatement and human capital as functions of time. A ‘sustainability screw’ phenomenon is demonstrated describing a spiral like trajectory of three key variables—the non-renewable resources, the renewable resources and the production capital. This spiral may tend to an undesirable steady state, however, by adjusting a ratio of intensity parameters, time scales of production and natural recovery processes can be altered to produce more sustainable trajectories.     

Simulative investigations of power penalty for DWDM link in the presence of FWM

In this paper, the eight channels dense wavelength division multiplexing (DWDM) optical communication system has been simulated, and power penalty introduced due to neighboring channels required to compensate the crosstalk has been calculated. It has been observed that the intermediate channels are more affected as compared to the boundary channels and more power is required to compensate the loss of information due to crosstalk.     

Silver-halide/organic-composite structures: Toward materials with multiple photographic functionalities

We report the synthesis and structure of the novel silver-halide-based organic-inorganic hybrids Ag₂Br₆(PPD)₂, Ag₂Br₆(CD-2)₂·H₂O, Ag₂Br₄(TMBD), and Ag₂I₆(CD-2)₂·H₂O. 1,4-phenylenediammonium hexabromodiargentate(I) [Ag₂Br₆(PPD)₂] crystals are monoclinic (P2₁/n), with unit-cell dimensions, , , and β=93.109(1)°. N,N-diethyl-2-methyl-1,4-benzenediammonium hexabromodiargentate(I) monohydrate [Ag₂Br₆(CD-2)₂·H₂O] crystals are monoclinic (space group P2₁/c) with , , , and β=96.153(1)°. N,N,N′,N′-tetramethyl-1,4-benzenediammonium tetrabromodiargentate(I) [Ag₂Br₄(TMBD)] crystals are orthorhombic (space group Pbcn) with , , and . N,N-diethyl-2-methyl-1,4-benzenediammonium hexaiododiargentate(I) monohydrate, [Ag₂I₆(CD-2)₂·H₂O], are monoclinic (C2/c), with unit-cell dimensions, , , , and β=98.657(1)°. The novel structures are members of a class of silver-halide-based organic-inorganic hybrids based upon the assembly of [Ag_aX_b]ⁿ⁻ clusters and protonated organoamines in aqueous mineral acids. The clusters display short intracluster Ag-Ag distances, and computational methods are used to evaluate intracluster Ag-Ag bonding. The diverse stoichiometries and cluster connectivities observed suggest a rich compositional and structural chemistry based upon the general assembly method. We have extended the methodology to include a silver-halide-organoamonium chemistry in which the organic moiety is chosen to serve a specific photographic function and demonstrate the first examples of such materials. The methodology allows for the direct assembly of [Ag_aX_b]ⁿ⁻ clusters with commercial photographic color developer molecules, and we show that development is repressed but can later be “switched on” in a unique photographic scheme. The photographic properties of Ag₂Br₆(PPD)₂ are examined and show an extremely facile development rate owing to the fact that the developer molecules are within molecular proximity to the clusters. As a result of their molecular nature, we anticipate that such materials could enable conventional or completely new imaging technologies with very fast image access rates and very high resolution.     

beta-acylvinyl anion and dianion equivalents: lithiation of 1-[(2EZ)-3-chloroprop-2-enyl]-1H-1,2,3-benzotriazole: preparation and elaboration of 1-(2-oxiranylvinyl)-1H-benzotriazoles

The allyllithium generated from 1-[(2EZ)-3-chloroprop-2-enyl]-1H-1,2,3-benzotriazole (5) and LDA, in the presence of HMPA, reacts with enolizable and nonenolizable carbonyls solely at the CCl terminus to give 1-(2-oxiranylvinyl)benzotriazoles 6a-g in 61-82% yields. Allyllithiums generated from 6a,c reacted exclusively at the CBt terminus to give 10a-d in 68-88% yields. Acidic hydrolysis of (oxiranylvinyl)benzotriazoles 6a-g and 10a-d provided 4-hydroxyalk-2-en-1-one derivatives 12a,b,c,e,g, 13a-d, and furan 14 in 54-86% yields.