Highly stable Ag nanoparticles in agar-agar matrix as inorganic–organic hybrid

A novel synthesis of inorganic–organic hybrid films containing well dispersed and almost uniform size Ag nanoparticles in agar-agar matrix has been reported. The films are found to be highly stable for more than a year. The colloidal particles of Ag can be obtained in large quantities in the form of a film or in the gel form when dispersed in agar-agar or by dissolving in a suitable solvent as solution. Characterization has been done by UV–visible spectroscopy and TEM. The hybrid may be of interest to study third-order non-linear susceptibility.     

Pes study of spin-state transitions in d6 transition metal complexes and oxides

Transitions from the low-to the high-spin state in Fe²⁺ and Co³⁺ compounds have been examined by X-ray and UV photoelectron spectroscopy. It has been shown that the core-level bands in XPES, in particular the metal 3s band, as well as the valence bands, are diagnosis in the study of spin-state transitions.     

Agonistic and antagonistic properties of a Rhizobium sin-1 lipid A modified by an ether-linked lipid

LPS from Rhizobium sin-1 (R. sin-1) can antagonize the production of tumor necrosis factor alpha (TNF-alpha) by E. coli LPS in human monocytic cells. Therefore these compounds provide interesting leads for the development of therapeutics for the prevention or treatment of septic shock. Detailed structure activity relationship studies have, however, been hampered by the propensity of these compounds to undergo beta-elimination to give biological inactive enone derivatives. To address this problem, we have chemically synthesized in a convergent manner a R. sin-1 lipid A derivative in which the beta-hydroxy ester at C-3 of the proximal sugar unit has been replaced by an ether linked moiety. As expected, this derivative exhibited a much-improved chemical stability. Furthermore, its ability to antagonize TNF-alpha production induced by enteric LPS was only slightly smaller than that of the parent ester modified derivative demonstrating that the ether-linked lipids affect biological activities only marginally. Furthermore, it has been shown for the first time that R. sin-1 LPS and the ether modified lipid A are also able to antagonize the production of the cytokine interferon-inducible protein 10, which arises from the TRIF-dependent pathway. The latter pathway was somewhat more potently inhibited than the MyD88-dependent pathway. Furthermore, it was observed that the natural LPS possesses much greater activity than the synthetic and isolated lipid As, which indicates that di-KDO moiety is important for optimal biological activity. It has also been found that isolated R. sin-1 LPS and lipid A agonize a mouse macrophage cell line to induce the production of TNF-alpha and interferon beta in a Toll-like receptor 4-dependent manner demonstrating species specific properties.     

A note on overpotential dependence of AC impedance data

Charge-transfer resistance [R _ct = (dη/di)_{η = 0}] and Tafel plots of current density (i) versus overpotential (η) data are generally known to yield values of the energy-transfer coefficient (α) and exchange current density (i _o) of an electrochemical reaction. In the present investigation, the resistance (dη/di)_η≠0 that could be calculated by differentiating a wide range of i−η curves was also shown to provide the values of α and i _o, by plotting ln(dη/di)_η≠0 against η. Since α and i _o could also be evaluated directly from the experimental DC polarization data, the procedure was not of significant importance. Nevertheless, it was considered important in evaluating α and i _o from AC impedance data, because the procedure was based on data analysis, which was much simpler than that reported in the literature. A cobalt electrode prepared from fine metal powder was used in 1 M KOH electrolyte and the hydrogen evolution reaction was studied by AC impedance at several potentials. The resistance values measured from the complex plane impedance diagram were plotted against the potential, and the values of α and i _o were evaluated. Received: 8 October 1998 / Accepted: 11 January 1999     

Rationalizing the generation of broad spectrum antibiotics with the addition of a positive charge

Antibiotic resistance of Gram-negative bacteria is largely attributed to the low permeability of their outer membrane (OM). Recently, we disclosed the eNTRy rules, a key lesson of which is that the introduction of a primary amine enhances OM permeation in certain contexts. To understand the molecular basis for this finding, we perform an extensive set of molecular dynamics (MD) simulations and free energy calculations comparing the permeation of aminated and amine-free antibiotic derivatives through the most abundant OM porin of E. coli, OmpF. To improve sampling of conformationally flexible drugs in MD simulations, we developed a novel, Monte Carlo and graph theory based algorithm to probe more efficiently the rotational and translational degrees of freedom visited during the permeation of the antibiotic molecule through OmpF. The resulting pathways were then used for free-energy calculations, revealing a lower barrier against the permeation of the aminated compound, substantiating its greater OM permeability. Further analysis revealed that the amine facilitates permeation by enabling the antibiotic to align its dipole to the luminal electric field of the porin and form favorable electrostatic interactions with specific, highly-conserved charged residues. The importance of these interactions in permeation was further validated with experimental mutagenesis and whole cell accumulation assays. Overall, this study provides insights on the importance of the primary amine for antibiotic permeation into Gram-negative pathogens that could help the design of future antibiotics. We also offer a new computational approach for calculating free-energy of processes where relevant molecular conformations cannot be efficiently captured.

A rapid pathway sampling method combining Monte Carlo and graph theory, developed to describe permeation pathways through outer membrane porins, can distinguish between structurally similar analogs with different permeabilities.     

Estimating optical properties in layered tissues by use of the Born approximation of the radiative transport equation

We use the Born approximation of the radiative transport equation to recover simultaneously the absorption and scattering coefficients in a single layer of a two-layer tissue sample from reflectance data. This method reduces the estimation of both optical properties to a single linear, least-squares problem. It is valid over length scales smaller than a transport mean free path and hence is useful for epithelial tissue layers. We demonstrate the accuracy of this method by using spatially resolved reflectance data computed with Monte Carlo simulations.     

The Coulomb Green’s function revisited

It is demonstrated how the energy-dependent Green’s function for the Schrödinger-Coulomb problem can be deduced from a knowledge of the harmonic oscillator time-propagator. All the known results of the Coulomb system are shown to be elegantly derivable from such a connection.     

Exact energy eigenvalues by summation of thejwkb series

For the potentialV(x)=V ₀ tan² x, the corrections to the lowest orderjwkb (Bohr-Sommerfeld) energy quantization rule are non-zero. These higher order corrections are explicitly computed using the formalism of Dunham. The resultingjwkb series for the energy eigenvalues is summable, and yields the exact bound state spectrum.     

Accurate and efficient Monte Carlo solutions to the radiative transport equation in the spatial frequency domain

We present an approach to solving the radiative transport equation (RTE) for layered media in the spatial frequency domain (SFD) using Monte Carlo (MC) simulations. This is done by obtaining a complex photon weight from analysis of the Fourier transform of the RTE. We also develop a modified shortcut method that enables a single MC simulation to efficiently provide RTE solutions in the SFD for any number of spatial frequencies. We provide comparisons between the modified shortcut method and conventional discrete transform methods for SFD reflectance. Further results for oblique illumination illustrate the potential diagnostic utility of the SFD phase-shifts for analysis of layered media.     

Relation between Green’s functions for different potentials

A general relation between the energy-dependent Green’s functions for different potentials is derived in a simple and direct manner. This interesting connection enables the eigenstates of one physical system to be deduced from those of a related system. The derivation is based on the Schrödinger equation and provides an independent justification for the technique of path-dependent time transformation used in path integration.