HPLC separation,NMR and QTOF/MS/MS structure elucidation of a prominent nitric oxide donor agent based on an isomeric composition of a nitrosyl ruthenium complex

A new and promising nitrosyl ruthenium complex, [Ru(NO)(bdqi-COOH)(terpy)](PF₆)₃, bdqi-COOH is 3,4-diiminebenzoic acid and terpy is 2,2′-terpyridine, has been synthesized as a NO donor agent. The procedure used for [Ru(NO)(bdqi-COOH)(terpy)](PF₆)₃ synthesis has, apparently, yielded the formation of two isomers in which the ligand bdqi-COOH appears to be coordinated in its reduced form (bdcat-COOH), which could have differences in their pharmacological properties. Therefore, it was intended to separate the two possible isomers by high-performance liquid chromatography (HPLC) and to characterize them by high resolution mass spectrometry (QTOF MS) and by magnetic nuclear resonance spectroscopy (NMR). The results obtained by MS showed that the ESI-MS mass spectra of both HPLC column fractions, e.g. peak 1 and peak 2, are essentially equal, showing that both isomers display nearly identical gas-phase behavior with clusters of isotopologue ions centered at m/z 573, m/z 543 and m/z 513. Regarding the NMR analysis, the results showed that the positional isomerism is located in the bdqi-COOH ligand. From the observed results it can be concluded that the synthesis procedure that has been used results in the formation of two [Ru(terpy)(bdqi-COOH)NO](PF₆)₃ isomers.     

An Application of Wavelets in Tomography

A method of tomographic inversion using wavelets is described which relies on the “diagonalization” property of wavelets for the derivative of the Hilber transform. Error bounds are given for reconstruction using the technique and an optimal wavelet which minimizes the error is presented. The method is well suited for inversion of from local data.     

Inhibition of HSP90 with Pochoximes: SAR and Structure‐Based Insights

The pochoximes, based on the radicicol pharmacophore, are potent inhibitors of heat shock protein 90 (HSP90) that retain their activity in vivo. Herein we report an extended library that broadly explores the structure–activity relationship (SAR) of the pochoximes with four points of diversity. Several modifications were identified that afford improved cellular efficacy, new opportunities for conjugation, and further diversifications. Cocrystal structures of pochoximes A and B with HSP90 show that pochoximes bind to a different conformation of HSP90 than radicicol and provide a rationale for the enhanced affinity of the pochoximes relative to radicicol and the pochonins.     

Novel approach for measuring the effective shear modulus of porous materials

A new approach is proposed for the experimental study of the effective shear modulus of porous elastic materials using the uniaxial tension test. The idea is to measure strains at a few points surrounding a cluster of holes that represents the structure of the material. The representative cluster is placed in the material with the same elastic properties as those of the matrix. The measured strains lead to the properties of the equivalent circular inhomogeneity, which would produce the same elastic fields as from the cluster. An aluminum plate containing a cluster of seven circular or hexagonal holes was used. The effective shear modulus obtained from the strain data was compared with theoretical predictions and various bounds, and it was shown that the laboratory estimated values are quite accurate. The experimental technique can be used for the determination of the effective Poisson’s ratio of porous media and/or cellular solids if more detailed strain data are obtained.     

Engineering design approaches for minimum fouling in submerged MBR

A contributor to success in managing membrane operations is to be able to identify suitable engineering design approaches to slow down the membrane fouling rate. Two such approaches were discussed in this study, namely: (1) offsite chemical and mechanical cleaning, and (2) air scouring. A longer subsequent operation time was observed after a membrane was cleaned chemically compared with mechanically. For air scouring during membrane operation, the investigation aimed at determining the crossflow velocity induced by coarse and fine bubble diffusers. Higher crossflow velocities were obtained with the latter. Uniformly distributed fine air bubbling might possibly have caused less uplift resistance and induced higher crossflow velocities. Such air scouring, at critical aeration intensity, was able to prolong the membrane operation for up to 8 months without needing chemical or mechanical cleaning.     

Synthesis and optical properties of luminescent core-shell structured silicate and phosphate nanoparticles

Monodisperse, luminescent core-shell structured inorganic nanoparticles were synthesized by sol-gel technology. They exhibit an amorphous SiO₂ core and a crystalline luminescent shell. Zn₂SiO₄:Mn²⁺ and Ca₁₀(PO₄)₆OH:Eu³⁺ shell materials are investigated. The influence of the doping concentration on optical and structural properties was studied. The resulting nanoparticles were characterized by X-ray diffraction analysis, transmission electron microscopy, inductively coupled plasma optical emission spectrometry, and photoluminescence spectroscopy.     

Zeolitic materials with hierarchical porous structures

During the past several years, different kinds of hierarchical structured zeolitic materials have been synthesized due to their highly attractive properties, such as superior mass/heat transfer characteristics, lower restriction of the diffusion of reactants in the mesopores, and low pressure drop. Our contribution provides general information regarding types and preparation methods of hierarchical zeolitic materials and their relative advantages and disadvantages. Thereafter, recent advances in the preparation and characterization of hierarchical zeolitic structures within the crystallites by post-synthetic treatment methods, such as dealumination or desilication; and structured devices by in situ and ex situ zeolite coatings on open-cellular ceramic foams as (non-reactive as well as reactive) supports are highlighted. Specific advantages of using hierarchical zeolitic catalysts/structures in selected catalytic reactions, such as benzene to phenol (BTOP) and methanol to olefins (MTO) are presented.     

Bacterial attachment to RO membranes surface-modified by concentration-polarization-enhanced graft polymerization

Concentration polarization-enhanced radical graft polymerization, a facile surface modification technique, was examined as an approach to reduce bacterial deposition onto RO membranes and thus contribute to mitigation of biofouling. For this purpose an RO membrane ESPA-1 was surface-grafted with a zwitterionic and negatively and positively charged monomers. The low monomer concentrations and low degrees of grafting employed in modifications moderately reduced flux (by 20-40%) and did not affect salt rejection, yet produced substantial changes in surface chemistry, charge and hydrophilicity. The propensity to bacterial attachment of original and modified membranes was assessed using bacterial deposition tests carried out in a parallel plate flow setup using a fluorescent strain of Pseudomonas fluorescens. Compared to unmodified ESPA-1 the deposition (mass transfer) coefficient was significantly increased for modification with the positively charged monomer. On the other hand, a substantial reduction in bacterial deposition rates was observed for membranes modified with zwitterionic monomer and, still more, with very hydrophilic negatively charged monomers. This trend is well explained by the effects of surface charge (as measured by ζ-potential) and hydrophilicity (contact angle). It also well correlated with force distance measurements by AFM using surrogate spherical probes with a negative surface charge mimicking the bacterial surface. The positively charged surface showed a strong hysteresis with a large adhesion force, which was weaker for unmodified ESPA-1 and still weaker for zwitterionic surface, while negatively charged surface showed a long-range repulsion and negligible hysteresis. These results demonstrate the potential of using the proposed surface- modification approach for varying surface characteristics, charge and hydrophilicity, and thus minimizing bacterial deposition and potentially reducing propensity biofouling.     

Differentiation of lactococci from 2 Greek cheeses with protected designation of origin by phenotypic criteria and RAPD-PCR

Abstract: Seventy‐six lactococci isolates from 2 protected designation of origin (PDO) cheeses were studied for their acidification ability, proteolytic activity, and inhibitory activities as well as their intraspecies characterization by randomly amplified polymorphic DNA‐polymerase chain reaction (RAPD‐PCR). Fifty‐two of them were characterized as Lactococcus lactis subsp. lactis by the SDS‐PAGE of whole‐cell proteins. The test strains increased the amount of acid in milk from 6 to 24 h as well as the quantities of amino acids on incubation for 4 d. The majority of the isolates degraded preferentially α_s‐casein. The isolates from Feta differed from those of Graviera Kritis in respect of β‐casein degradation. This fragment was either not degraded or underwent a small degradation by lactococci from Feta. A stronger intensity of acidification for the isolates from Feta and a higher casein breakdown ability for those from Graviera Kritis were also recorded. Lactococci from Feta and Graviera Kritis inhibited, preferentially, the growth of Escherichia coli O157:H7, and Yersinia enterocolitica, respectively. A high heterogeneity among the isolates according to RAPD‐PCR was determined, as well as grouping of the isolates according to their source of isolation. Selected isolates from each cheese could be used as starters to make either Feta or Graviera Kritis.