The sugar conformation governs (6-4) photoproduct formation at the dinucleotide level

The LNA dinucleotide mimic of TpT whose two-sugar puckers are locked in the C3'-endo conformation selectively produces the corresponding cyclobutane pyrimidine dimer under 254 nm irradiation. In the natural series (TpT) the sugar puckers are in a major C2'-endo sugar conformation and the (6-4) photoproduct is also produced. Consequently, this study demonstrates that the C2'-endo conformation of the sugar pucker is necessary for (6-4) photoproduct formation.     

Self-assembly of ligands designed for the building of a new type of [2 x 2] metallic grid. anion encapsulation and diffusion NMR spectroscopy

The ligands 4,6-bis(pyrazol-1-yl)pyrimidine (bpzpm), 4,6-bis(3,5-dimethylpyrazol-1-yl)pyrimidine (bpz(*)pm), 4,6-bis(4-methylpyrazol-1-yl)pyrimidine (Mebpzpm), and 3,6-bis(3,5-dimethylpyrazol-1-yl)pyridazine (ppdMe) were synthesized and were made to react with Cu(I) centers in the presence of different counteranions. Different [2 x 2] metallic grids were obtained. With ligands bpzpm, bpz*pm, and Mebpzpm, a new type of grid was obtained where the facing ligands were divergent and two counteranions (BF(4-) or PF(6-)) were hosted in the resulting cavities and exhibit C-H...F and anion...pi interactions in the solid state. The presence of methyl groups on the pyrazolyl rings induced several distortions in the structure. In complexes with the ligand ppdMe, there were found two groups of parallel ligands in the grid, and the cavities generated were smaller. The counteranions were situated outside the grid, and the facing ligands exhibited aromatic pi-pi stacking interactions. Anion-pi interactions involving the pyridazine ring were found. The behavior in solution of the new derivatives with a special emphasis on the cation-anion interactions was studied by UV-vis and NMR spectroscopy. Diffusion NMR experiments performed for some complexes allowed us to conclude that weak cation-anion interactions exist in solution, with the counteranions undergoing fast exchange on the diffusion time scale between the free and ion-paired states.     

A new multiresponse optimization approach in combination with a D-Optimal experimental design for the determination of biogenic amines in fish by HPLC-FLD

A new strategy to approach multiresponse optimization in conjunction to a D-optimal design for simultaneously optimizing a large number of experimental factors is proposed. The procedure is applied to the determination of biogenic amines (histamine, putrescine, cadaverine, tyramine, tryptamine, 2-phenylethylamine, spermine and spermidine) in swordfish by HPLC-FLD after extraction with an acid and subsequent derivatization with dansyl chloride. Firstly, the extraction from a solid matrix and the derivatization of the extract are optimized. Ten experimental factors involved in both stages are studied, seven of them at two levels and the remaining at three levels; the use of a D-optimal design leads to optimize the ten experimental variables, significantly reducing by a factor of 67 the experimental effort needed but guaranteeing the quality of the estimates. A model with 19 coefficients, which includes those corresponding to the main effects and two possible interactions, is fitted to the peak area of each amine. Then, the validated models are used to predict the response (peak area) of the 3456 experiments of the complete factorial design. The variability among peak areas ranges from 13.5 for 2-phenylethylamine to 122.5 for spermine, which shows, to a certain extent, the high and different effect of the pretreatment on the responses. Then the percentiles are calculated from the peak areas of each amine. As the experimental conditions are in conflict, the optimal solution for the multiresponse optimization is chosen from among those which have all the responses greater than a certain percentile for all the amines. The developed procedure reaches decision limits down to 2.5 μg L⁻¹ for cadaverine or 497 μg L⁻¹ for histamine in solvent and 0.07 mg kg⁻¹ and 14.81 mg kg⁻¹ in fish (probability of false positive equal to 0.05), respectively.     

Removing electrons can increase the electron density: a computational study of negative Fukui functions

Ab initio and density-functional theory calculations for a family of substituted acetylenes show that removing electrons from these molecules causes the electron density along the C-C bond to increase. This result contradicts the predictions of simple frontier molecular orbital theory, but it is easily explained using the nucleophilic Fukui function-provided that one is willing to allow for the Fukui function to be negative. Negative Fukui functions emerge as key indicators of redox-induced electron rearrangements, where oxidation of an entire molecule (acetylene) leads to reduction of a specific region of the molecule (along the bond axis, between the carbon atoms). Remarkably, further oxidization of these substituted acetylenes (one can remove as many as four electrons!) causes the electron density along the C-C bond to increase even more. This work provides substantial evidence that the molecular Fukui function is sometimes negative and reveals that this is due to orbital relaxation.     

Synthesis of alpha- and beta-glycosyl isothiocyanates via oxazoline intermediates

A practical synthesis of acylated glycosyl isothiocyanates from sugar oxazolines, by reaction with thiophosgene, is reported. In the absence of any additive, the reaction is governed by the reverse anomeric effect, leading to the equatorially oriented isothiocyanate. However, in the presence of copper(II) chloride, the reaction proceeds preferentially with retention of the configuration at the anomeric center, providing the axial anomer as the major product. Noteworthy, this strategy allows accessing per-O-acetylated glycopyranosyl isothiocyanates with 1,2-cis relative configuration (e.g., the alpha-anomer in the D-gluco and D-galacto series), a problem that was outside the scope of previous methodologies.     

A Model for Kidney Tissue Damage under High Speed Loading

In a medical procedure to comminute kidney stones the patient is subjected to hypersonic waves focused at the stone. Unfortunately such shock waves also damage the surrounding kidney tissue. We present here a model for the mechanical response of the soft tissue to such a high speed loading regime. The material model combines shear induced plasticity with irreversible volumetric expansion as induced, e.g., by cavitating bubbles. The theory is based on a multiplicative decomposition of the deformation gradient and on an internal variable formulation of continuum thermodynamics. By the use of logarithmic and exponential mappings the stress update algorithms are extended from small‐strain to the finite deformation range. In that way the time‐discretized version of the porous‐viscoplastic constitutive updates is described in a fully variational manner. By numerical experiments we study the shock‐wave propagation into the tissue and analyze the resulting stress states. A first finite element simulation shows localized damage in the human kidney. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Transfer measurements for the Ti+Ni systems at near barrier energies

Large enhancements have been observed in the sub-barrier fusion cross sections for Ti+Ni systems in our previous studies. Coupled channel calculations incorporating couplings to 2⁺ and 3⁻ states failed to explain these enhancements completely. A possibilty of transfer channels contributing to the residual enhancements had been suggested. In order to investigate the role of relevant transfer channels, measurements of one- and two-nucleon transfer were carried out for ^46,48Ti+⁶¹Ni systems. The present paper gives the results of these studies.     

Experimental search for solar axions

A new technique has been used to search for solar axions using a single crystal germanium detector. It exploits the coherent conversion of axions into photons when their angle of incidence satisfies a Bragg condition with a crystalline plane. The analysis of approximately 1.94 kg.yr of data from the 1 kg DEMOS detector in Sierra Grande, Argentina, yields a new laboratory bound on axion-photon coupling of g_αγγ < 2.7 × 10⁻⁹GeV⁻¹, independent of axion mass up to 1 keV.     

Persistence Length of Cartilage Aggrecan Macromolecules Measured via Atomic Force Microscopy

Tapping mode atomic force microscopy (TMAFM) was employed to directly calculate the persistence length of individual fetal bovine epiphyseal and mature nasal cartilage aggrecan monomers, as well as their constituent chondroitin sulfate glycosaminoglycan chains.     

Second-order shakeup terms in electron propagator calculations on F2 and H2O2

A new approximation of the electron propagator includes second-order terms in the superoperator Hamiltonian matrix that are not present in the nondiagonal, renormalized method (NR2) of J. Chem. Phys. 108 , 1008 (1998). These terms are not difficult to calculate and resemble expressions obtained with various propagator and coupled-cluster formalisms. Their inclusion produces larger, more accurate vertical ionization energies of F₂ and H₂O₂. Cancellations between the second-order terms considered here and the first-order terms present in the NR2 method reduce the importance of shakeup operators in describing the first few cationic states of these molecules. Dyson orbitals for ²A final states of H₂O₂ exhibit qualitatively important mixings between canonical orbitals. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 69: 175–182, 1998