Theoretical study on the adsorption of aromatic compounds on platinum clusters

B3 LYP hybrid functional with LACVP* pseudopotential was applied for the optimization of geometries of complexes resulting from interaction of benzene, pyridine, naphthalene, and quinoline with Pt_n (n = 4, 7) clusters. For benzene‐containing complexes, the most stable form corresponds to a bridge adsorption, with benzene undergoing considerable geometric distortions, assuming a boat‐like conformation. C? H bonds are bended upward from the plane of the cluster. C? C bonds stretch, especially when they form π‐complexes with low coordinated Pt atoms. Some arrangements for pyridine complexes involving the N atom of the organic moiety undergo further distortions, apparently preserving a formal C? N π bond. Except for that distortion, the behavior of any heteroaromatic complex is similar to that of benzene in the same arrangement. The quinoline–Pt₇ complex can suitably be used for simulation of the cinchonidine (CD) anchorage over Pt. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003     

The role of C-centered radicals on the mechanism of action of artemisinin

Artemisinin is a sesquiterpene lactone with an endoperoxide function that is essential for its antimalarial activity. Endoperoxides are supposed to act on heme leading to the reduction of the peroxide bond and production of radicals, which can be responsible for killing the parasite. The geometries of artemisinin, radical anions and neutral species generated by rearrangement after reduction of the peroxide bond were fully optimized with the AM1 and PM3 semi-empirical methods, in order to characterize the intermediates formed during the process. Among the radicals calculated along the pathway for reductive decomposition of artemisinin, the secondary radical centered on carbon C₄ has the highest stability when compared to other radicals that can be achieved either by hydrogen migration to the original O-centered radical or by homolytic break of C–C bond. This suggests that the C₄-centered radical may be the species responsible for killing the parasite, as has been indicated previously in experimental studies.     

Immobilization of protein on ferromagnetic Dacron

Ferromagnetic Dacron (polyethyleneterephthalate) is proposed as a matrix to immobilize proteins covalently. Dacron in powder was magnetized by reacting ferrous (Fe+2) and ferric (Fe+3) ions with its hydrazide form at pH 8.3. Ferromagnetic hydrazide Dacron was converted to ferromagnetic azide Dacron and amyloglucosidase (E.C. 3.2.1.3) was covalently bound through the latter group. The catalytic property of the enzyme was preserved (8% of the specific activity estimated for the soluble enzyme) and all the magnetic amyloglucosidase Dacron derivative was recovered by using a magnetic field. No activity was detected in the supernatant.     

Ground-state energy of a quantum chain with competing interactions

We show rigorously that the ground state of a quantum chain with competing ferromagnetic nearest and antiferromagnetic next nearest interactions undergoes a transition from ferromagnetic to helical type, in the isotropic case, for a certain value of the relevant ratio of coupling constants. Boundaries of the phase diagram are also determined in the anisotropic case. The stability of a special quantum state (corresponding to a classical modulated phase of =/3) is analyzed by an extension of Holstein-Primakoff arguments, along a line of constant ratio of couplings, showing in particular a sequence of (instability) gaps. Finally, a natural adaptation of a variational wave function due to Huse and Elser is used to study several portions of the phase diagram, with very good agreement with previous theoretical results.     

Spectrophotometric flow-injection determination of zinc in plant digests based on a spot test

A spot test was implemented in a flow-injection system for the spectrophotometric determination of zinc in digests of plant materials. It is based on the influence of Zn²⁺ on the oxidation rate of 1-naphthylethylenediamine (NED) by hexacyanoferrate(III) under acidic conditions. In order to control the precipitate formation and to maintain the resulting suspension, a micellar medium was established by adding Triton X-100. The proposed system handles about 65 samples per hour, meaning 72 μg NED and 9.0 mg K₃[Fe(CN)₆] per determination. Baseline drift is usually <0.01 absorbance per hour and the analytical signals for 0.5-2.5 mg l⁻¹ Zn range within ca. 0.07-0.45 absorbance. Linearity of the analytical curve is fair (r>0.999, n=6) and detection limit was estimated as 0.2 mg l⁻¹ Zn. Results are precise (R.S.D.<1%, n=10) and in agreement with flame atomic absorption spectrometry and with certified values of standard reference materials.     

Does CH prefer a C2v rather than a Cs structure?

The closely related C_s ( 1 ) and C_2v ( 3 ) structures of CH have been reinvestigated at many ab initio levels using MP2/6-31G** and MP2/6-311 + + G(2df, 2pd) geometries. The largest basis sets employed were 6-311G(3df, 2p), 6-311 + + G(3df, 3pd), and the Dunning “correlation consistent” polarized triple-split valence basis set (cc-pVTZ). Electron correlation was probed at the MP4 level, but the QCISD method was also used with the largest basis sets. While electron correlation favors 3 over 1 by about 2 kcal/mol, the correlated relative energies with all basis sets employed range from 0.36–1.03 kcal/mol in favor of 1 . The best estimate of this difference, 0.86 kcal/mol, is essentially identical with the (scaled) zero-point energy difference, 0.84 kcal/mol, favoring 3 over 1 . These results indicate that 1 and 3 have almost exactly the same energy at 0 K. Our best value for the dissociation energy of CH is 42.0 kcal/mol [QCISD(T)/6-311 + + G(3df, 3pd)//MP2(fu)/6-311 + + G(2df, 2pd), corrected to 298 K], which agrees very well with the experimental value. © 1992 by John Wiley & Sons, Inc.     

Analysis of the geometrical dependence of auxetic behavior in reentrant structures by finite elements

Materials with a negative Poisson's ratio(PR)are called auxetics;they are characterized by expansion/contraction when tensioned/compressed.Given this counterintuitive behavior,they present very particular characteristics and mechanical behavior.Geometrical models have been developed to justify and artificiall reproduce such materials' auxetic behavior.The focus of this study is the exploration of a reentrant model by analyzing the variation in the PR of reentrant structures as a function of geometrical and base material parameters.It is shown that,even in the presence of protruding ribs,there may not be auxetic behavior,and this depends on the geometry of each reentrant structure.Values determined for these parameters can be helpful as approximate reference data in the design and fabrication of auxetic lattices using reentrant geometries.     

Ion recognition properties of poly[Cu(3-MeOsalpd)] films

Poly[Cu(3-MeOsalpd)] films with good physical, chemical and electrochemical stability may be potentiodynamically electrodeposited with high deposition efficiency from acetonitrile solutions of the monomer. Comparative coulometric assays with the Ni-based analogue show that the metal in the salen motif does play a role in the electronic structure of the polymer, but that the electroactive response is ligand (not metal) based. The dynamics of redox switching are ultimately limited by coupled electron/counter ion diffusion, but this process is sufficiently rapid that it influences the voltammetric response only for thick films (Γ >420?nmol?cm^?2) at high scan rates. Redox cycling in monomer-free electrolyte shows a voltammetric signature that responds, via interaction with the pseudo-crown ether receptor sites, to the presence of Li⁺, K⁺, Mg²⁺ and Ba²⁺ ions in solution. The most prominent change is associated with the first anodic peak in the i-E signature. For each of the metal ions considered, this peak potential responds logarithmically to concentration in a manner that varies with individual complexed cation and film thickness and to an extent greater than predicted by the Nernst equation. The film characteristics offer some analytical promise, including a trade-off between sensitivity and dynamic range and signal amplification, possibly due to supramolecular effects.