Application of glycodiversification: expedient synthesis and antibacterial evaluation of a library of kanamycin B analogues

[reaction: see text] The expedient synthesis of a library of kanamycin B analogues is reported. The revealed SAR will guide future designs in developing kanamycin-type aminoglycoside antibiotics against drug-resistant bacteria.     

Spin dynamics in the carrier-doped S=1/2 triangular lattice of NaxCoO2.yH2O

We probed the local electronic properties of the mixed-valent Co+4-x triangular lattice in NaxCoO2.yH(2)O by 59Co NMR. We observed two distinct types of Co sites for x > or =1/2, but the valence seems averaged out for x approximately 1/3. Local spin fluctuations exhibit qualitatively the same trend down to approximately 100 K regardless of the carrier concentration x, and hence the nature of the electronic ground state. A canonical Fermi-liquid behavior emerges below approximately 100 K only for x approximately 1/3.     

Complete control of the chemoselectivity in catalytic carbene transfer reactions from ethyl diazoacetate: an N-heterocyclic carbene-Cu system that suppresses diazo coupling

The complex IPrCuCl (1) catalyzes the transfer of the :CHCO2Et group from ethyl diazoacetate (EDA) to unsaturated and saturated substrates (olefins, amine, alcohols) with very high yields. In the absence of substrate, the complex 1 does not react with EDA to give the diazo coupling products (fumarate and maleate), a rare example in the field of metal-catalyzed diazocompounds decomposition.     

Subphthalocyanines: tuneable molecular scaffolds for intramolecular electron and energy transfer processes

A series of four subphthalocyanine-C(60) fullerene dyads have been prepared through axial functionalization of the macrocycle with m-hydroxybenzaldehyde and a subsequent dipolar cycloaddition reaction. The subphthalocyanine moiety has been peripherally functionalized with substituents of different electronic character, namely fluorine or iodine atoms and ether or amino groups, thus reaching a control over its electron-donating properties. This is evidenced in cyclic voltammetry experiments by a progressive shift to lower potentials, by ca. 200 mV, of the first oxidation event of the SubPc unit in the dyads. As a consequence, the energy level of the SubPc(*)(+)-C(60)(*)(-) charge-transfer state may be tuned so as to compete with energy transfer deactivation pathways upon selective excitation of the SubPc component. For instance, excitation of those systems where the level of the radical pair lies high in energy triggers a sequence of exergonic photophysical events that comprise (i) nearly quantitative singlet-singlet energy transfer to the C(60) moiety, (ii) fullerene intersystem crossing, and (iii) triplet-triplet energy transfer back to the SubPc. On the contrary, the stabilization of the SubPc(*)(+)-C(60)(*)(-) radical pair state by increasing the polarity of the medium or by lowering the donor-acceptor redox gap causes charge transfer to dominate. In the case of 1c in benzonitrile, the thus formed radical pair has a lifetime of 0.65 ns and decays via the energetically lower lying triplet excited state. Further stabilization is achieved for dyad 1d, whose charge-transfer state would lie now below both triplets. The radical pair lifetime consequently increases in more than 2 orders of magnitude with respect to 1c and presents a significant stabilization in less polar solvents, revealing a low reorganization energy for this kind of SubPc-C(60) systems.     

Elastic properties of poly(hydroxybutyrate) molecules

Elasticity of various poly(hydroxybutyrate) (PHB) molecules of regular and irregular conformational structure was examined by the molecular mechanics (MM) calculations. Force - distance functions and the Young's moduli E were computed by stretching of PHB molecules. Unwinding of the 2(1) helical conformation H is characterized at small deformations by the Young's modulus E = 1.8 GPa. The H form is transformed on stretching into the highly extended twisted form E, similar to the beta-structure observed earlier by X-ray fiber diffraction. The computations revealed that in contrast to paraffins, the planar all-trans structure of undeformed PHB is bent. Hence, a PHB molecule attains the maximum contour length in highly straightened, but slightly twisted conformations. A dependence of the single-chain moduli of regular and disordered conformations on the chain extension ratio x was found. The computed data were used to analyze elastic response of tie (bridging) molecules in the interlamellar (IL) region of a semi-crystalline PHB. A modification of the chain length distribution function of tie molecules tau(N) due to secondary crystallization of PHB was conjectured. The resulting narrow distribution tau(N) comprises the taut tie molecules of higher chain moduli prone to overstressing. The molecular model outlined is in line with the macroscopically observed increase in the modulus and brittleness of PHB with storage time.     

On the irregularity strength of trees

For any graph G, let n_i be the number of vertices of degree i, and . This is a general lower bound on the irregularity strength of graph G. All known facts suggest that for connected graphs, this is the actual irregularity strength up to an additive constant. In fact, this was conjectured to be the truth for regular graphs and for trees. Here we find an infinite sequence of trees with λ(T) = n₁ but strength converging to . © 2004 Wiley Periodicals, Inc. J Graph Theory 45: 241–254, 2004     

Determining the hydrographic parameters of the surface of water from the image sequences of a CCD camera

Water surface fluctuations were analyzed using image sequences from a CCD (charge coupled device) camera. Both regular and irregular waves were used for the study. A transfer function is obtained by comparing the gray scales of the image and results of in-situ wave gauge array measurements. The effects of non-uniform illumination within the wave basin are imbedded in the transfer function. Thus, the obtained transfer function is directly applicable to all other areas of interests within the wave basin. Estimated wave heights are all in qualitative agreement with those obtained through direct measurements. It is shown that the averaged relative error between these two wave heights is less than 16%.     

Alternating layer and island growth of Pb on Si by spontaneous quantum phase separation

Real-time in situ x-ray studies of continuous Pb deposition on Si(111)-(7x7) at 180 K reveal an unusual growth behavior. A wetting layer forms first to cover the entire surface. Then islands of a fairly uniform height of about five monolayers form on top of the wetting layer and grow to fill the surface. The growth then switches to a layer-by-layer mode upon further deposition. This behavior of alternating layer and island growth can be attributed to spontaneous quantum phase separation based on a first-principles calculation of the system energy.     

Improved direct measurement of the parity-violation parameter Ab using a mass tag and momentum-weighted track charge

We present an improved direct measurement of the parity-violation parameter A(b) in the Z boson-b-quark coupling using a self-calibrating track-charge technique applied to a sample enriched in Z-->bb events via the topological reconstruction of the B hadron mass. Manipulation of the Stanford Linear Collider electron-beam polarization permits the measurement of A(b) to be made independently of other Z-pole coupling parameters. From the 1996-1998 sample of 400,000 hadronic Z decays, produced with an average beam polarization of 73.4%, we find A(b)=0.906+/-0.022(stat)+/-0.023(syst).     

Intraoperative contrast-enhanced MR-imaging as predictor of tissue damage during cryoablation of porcine liver

This study evaluate intraoperative Magnetic Resonance Imaging (MRI) as predictor of tissue damage following cryoablation of porcine liver with and without concomitant hepatic vascular inflow occlusion.Inflow occlusion was used during freezing in 6 of 12 pigs included. The volumes of the procedural ice-balls were estimated from MR images. Immediately after thawing contrast (MnDPDP) enhanced MRI was performed to estimate the volume of the cryolesion. Four days after ablation MRI was repeated of the in-vivo and the ex-vivo liver. Photography was performed of the sliced liver specimens to estimate the volumes of the lesions. The intraoperative volume of the cryolesion as shown by contrast enhanced MRI corresponded well to the ice-ball volume for lesions made without vascular occlusion (difference 0.3 +/- 0.9 cm(3), p = 0.239). For lesions made during occlusion the volume of the intraoperative cryolesion was larger than the corresponding ice-ball (difference 7.5 +/- 3.3 cm(3), p = 0.003). The volume of the cryolesions as estimated from histopathology four days after freezing and contrast enhanced MRI immediately after freezing corresponded well for lesions made with (difference -2.6 +/- 4.5 cm(3), p = 0.110) and without vascular occlusion (difference -0.5 +/- 2.3 cm(3), p = 0.695).Intraoperative MnDPDP-enhanced MRI of the cryolesion is predictive of the tissue damage induced during cryoablation of porcine liver. The procedural ice-ball is not, if induced during inflow occlusion.