Structure and spectroscopic aspects of water‐halide ion clusters: A study based on a conjunction of stochastic and quantum chemical methods

In this article, we propose a stochastic search based method, namely genetic algorithm in conjunction with density functional theory to evaluate structures of water‐halide microclusters, with the halide ion being Cl^?, Br^?, and I^?. Once the structures are established, we evaluate the infrared spectroscopic modes, vertical detachment energies and natural population analysis based charges. We compare our results with available experimental and theoretical results. © 2012 Wiley Periodicals, Inc.     

A family of mixed-ligand oxovanadium(V) complexes incorporating tridentate ONO donor hydrazone ligands derived from acetylhydrazide and 2-hydroxybenzaldehyde/2-hydroxyacetophenone

In the title family the tridentate ONO donor ligands are the fully deprotonated forms of acetylhydrazones of 2-hydroxybenzaldehyde (H₂L¹) and 2-hydroxyacetophenone (H₂L²) (general abbreviation H₂L), while bidentate mononegative OO donor ligands are the deprotonated salicylaldehyde (Hsal), vanillin (Hvan) and monodeprotonated 1,2-ethanediol (H₂ed) (general abbreviation HB). The reaction of V^IVO(acac)₂ with H₂L and Hsal or Hvan in equimolar ratio in MeOH afforded the complexes of the type [V^VO(L)(B)], (1)–(4). The reaction of V^IVO(acac)₂ with H₂L¹ (in an equimolar ratio) and an excess of H₂ed in MeOH yielded the complex [V^VO(L¹)(Hed)], (5) but the similar reaction with H₂L² ligand failed to produce such a type of complex. Complexes have been characterized by elemental analyses and by i.r., n.m.r. and u.v.-vis. spectroscopies. All the complexes are diamagnetic and display only LMCT bands. ¹H-n.m.r. spectral data indicate that complexes (1)–(4) exist in two isomeric forms [(1A), (1B); (2A), (2B); (3A), (3B) and (4A), (4B)] in different ratios in CDCI₃ solution. Complexes (1)–(4) display a quasi-reversible one electron reduction peak in the −0.06 to +0.05 V versuss.c.e. region in CH₂CI₂ solution and (5) displays an irreversible reduction peak at −0.46 V versuss.c.e. in DMF solution. The trend in the redox potential values has been correlated with the basicity of both the primary and auxiliary ligands.     

Honeycomb nets with interpenetrating frameworks involving iminodiacetato-copper(II) blocks and bipyridine spacers: syntheses, characterization, and magnetic studies

Three coordination polymers of copper(II), viz. ([Cu(ida)(4,4'-bipyH)]ClO(4))( proportional, variant ) (1), ([Cu(2)(ida)(2)(micro-4,4'-bipy)].2H(2)O)( proportional, variant ) (2), and [Cu(2)(ida)(2)(bpa)]( proportional, variant ) (3) have been synthesized by the process of self-assembly using Cu(ida) [ida = iminodiacetate(2-)] as the building block and 4,4'-bipyridyl and 1,2-bis(4-pyridyl)ethane (bpa) as linkers. Crystals of 1 are orthorhombic, of space group Pna2(1), with a = 13.8956(12) A, b = 16.3362(16) A, c = 7.3340(12), and Z = 4. Both compounds 2 and 3 crystallize in monoclinic space group P2(1)/a with a = 10.1887(8) A (9.6779(10) A for 3), b = 8.0008(11) A (9.1718(10) A), c = 11.6684(9) A (12.9144(12) A), beta = 98.307(11) degrees (102.796(18) degrees ), and Z = 2 (2). Compound 1 has a zigzag chain structure with an extensive hydrogen-bonded network while compounds 2 and 3 are honeycomb (6,3) nets with interpenetrating structures. Variable temperature (2-300 K) magnetic study indicates the presence of weak antiferromagnetic interactions (J = 0.82 +/- 0.01 cm(-)(1)) in 1 and ferromagnetic in 2 (J = -0.45 +/- 0.05 cm(-)(1)) and 3 (J = -0.21 +/- 0.02 cm(-)(1)). The extent of planarity of the bridging "Cu-O-C-O-Cu" moiety, acting as the super-exchange pathway between the neighboring copper centers, probably controls the sign of the magnetic exchange coupling in these compounds.     

Contact angle hysteresis, adhesion, and marine biofouling

Adhesive and marine biofouling release properties of coatings containing surface-oriented perfluoroalkyl groups were investigated. These coatings were prepared by cross-linking a copolymer of 1H,1H,2H,2H-heptadecafluorodecyl acrylate and acrylic acid with a copolymer of poly(2-isopropenyl-2-oxazoline) and methyl methacrylate at different molar ratios. The relationships between contact angle, contact angle hysteresis, adhesion, and marine biofouling were studied. Adhesion was determined by peel tests using pressure-sensitive adhesives. The chemical nature of the surfaces was studied by using X-ray photoelectron spectroscopy. Resistance to marine biofouling of an optimized coating was studied by immersion in seawater and compared to previous, less optimized coatings. The adhesive release properties of the coatings did not correlate well with the surface energies of the coatings estimated from the static and advancing contact angles nor with the amount of fluorine present on the surface. The adhesive properties of the surfaces, however, show a correlation with water receding contact angles and contact angle hysteresis (or wetting hysteresis) resulting from surface penetration and surface reconstruction. Coatings having the best release properties had both the highest cross-link density and the lowest contact angle hysteresis. An optimized coating exhibited unprecedented resistance to marine biofouling. Water contact angle hysteresis appears to correlate with marine biofouling resistance.     

Failure of elastomeric polymers due to rate dependent bond rupture

A new cohesive zone model is developed in order to study the mechanisms of adhesive and cohesive failures of soft rubbery materials. The fracture energy is estimated here using a strategy similar to that of Lake and Thomas (LT) by considering the dissipation of stored elastic energy followed by the extension and relaxation of polymer chains. The current model, however, departs from that of LT in that the force needed to break an interfacial bond does not have a fixed value; instead, it depends on the thermal state of the system and the rate at which the force is transmitted to the bond. While the force required to rupture a chain is set by the rules of thermomechanically activated bond dissociation kinetics, extension of a polymer chain is modeled within both the linear and nonlinear models of chain elasticity. Closed form asymptotic solutions are obtained for the dependence of crack propagation speed on the energy release rate, which are valid in two regimes: (I) slow crack velocity or short relaxation time for bond dissociation; (II) fast crack velocity or long relaxation time for bond dissociation. The rate independent and the zero temperature limit of this theory correctly reduces to the fracture model of LT. Detailed comparisons are made with a previous work by Chaudhury et al. which carried out an approximate analysis of the same problem.     

Measuring the work of adhesion between a soft confined film and a flexible plate

We present a theoretical and experimental study of a method for the determination of the adhesion strength between a thin elastomeric film bonded to a rigid substrate and a flexible plate in a geometry common in the peel test. In particular, we characterize the work of adhesion in terms of the length of an equilibrium crack, generated by a spacer of known thickness wedged between the flexible plate and adhesive film, and the elastic and geometric properties of the film and the plate. We treat both the limit of perfect bonding and that of perfect slippage at the interface of the adhesive film and the flexible plate. A series of experiments allow us to verify the theory quantitatively and thus validate our method, which ought to be of value in many technological situations.     

Targeted synthesis of mu-oxo divanadium(V) compounds with asymmetry in coordination environments

Isovalent mu-oxo divanadium(V) compounds [L1VO(mu-O)VO(salen)] (1) and its bromo derivative [L2VO(mu-O)VO(salen)].CH3CN (2) (both H2L1 and H2L2 are tridentate dithiocarbazate-based ONS ligands) with ligands providing donor set and coordination number asymmetry in tandem have been synthesized for the first time; confirmations in favor of these unsymmetrical molecular structures have come from single-crystal X-ray diffraction analysis, as well as from NMR (both 1H and 51V) spectroscopy.     

Structure-Based Design,Synthesis, and Biological Evaluation of Hsp90β-Selective Inhibitors

The 90 kDa heat shock proteins (Hsp90) are molecular chaperones that are responsible for the folding and/or trafficking of ∼400 client proteins, many of which are directly associated with cancer progression. Consequently, inhibition of Hsp90 can exhibit similar activity as combination therapy as multiple signaling nodes can be targeted simultaneously. In fact, seventeen small-molecule inhibitors that bind the Hsp90 N-terminus entered clinical trials for the treatment of cancer, all of which exhibited pan-inhibitory activity against all four Hsp90 isoforms. Unfortunately, most demonstrated undesired effects alongside induction of the pro-survival heat shock response. As a result, isoform-selective inhibitors have been sought to overcome these detriments. Described herein is a structure-based approach to design Hsp90β-selective inhibitors along with preliminary SAR. In the end, compound 5 was shown to manifest ∼370-fold selectivity for Hsp90β versus Hsp90α, and induced the degradation of select Hsp90β-dependent clients. These data support the development of Hsp90β-selective inhibitors as a new paradigm to overcome the detriments associated with pan-inhibition of Hsp90.     

Accessing C2-Functionalized 1,3-(Benz)azoles through Transition Metal-Catalyzed C−H Activation

The skeletal presence of 1,3-azoles in a variety of bioactive natural products, pharmacophores, and organic materials demands the derivatization of such heteroarenes regioselectively. Plenty of cross-coupling as well as cyclocondensation reactions have been performed to build up these skeletons but remained commercially unrealizable. A couple of severe drawbacks are faced by these traditional protocols that require a more straightforward strategy to obviate them. Transition metal-catalyzed C−H functionalization has emerged as a superior alternative in that context. 1,3-Azoles and their benzo counterparts have been extensively functionalized exploiting both noble and earth-abundant transition metals. Lately, C-2 functionalization have gained much traction due to the ease of attaining high regioselectivity and installation of synthetically manipulative functionalities. This critical review presents a bird‘s eye view of all major C-2 functionalization of (benz)azoles catalyzed by a diverse set of metals performed over the past 15 years.     

Working group report: Neutrino and astroparticle physics

This is the report of neutrino and astroparticle physics working group at WHEPP-7. Discussions and work on CP violation in long baseline neutrino experiments, ultra high energy neutrinos, supernova neutrinos and water Cerenkov detectors are discussed.