Performance evaluation of a wave-front displacement system for vectorial shearing interferometer

We describe a wave-front displacement system using a novel configuration of a pair of wedge prisms. The wave-front propagation, through the displacement system, is analyzed using the exact ray trace. The main advantage, of this configuration, is that the shearing (direction and magnitude) is constant from the displacement system to the image plane. The direction of the shearing depends on the relative orientation of the prisms. The magnitude of the shearing is proportional to the distance between prisms. The proportionality constant depends on the wedge angle and the material of fabrication of the prisms, and it gives the sensitivity to the displacement of the system. The deviation of the shearing due to the difference between the wedge angles is larger than that the produced by the oblique incidence of the wave-front. The experimental results confirm the theoretical data.     

Erratum to: Solution behavior of aqueous mixtures of low and high molecular weight hydrophobic amphiphiles

Mixtures of a hydrophobic triblock copolymer (L121, PEO₅PPO₆₈PEO₅) and a hydrophobic anionic surfactant (AOT, Sodium bis(2-ethylhexyl)sulfosuccinate), each alone forming turbid vesicular solutions in water, aggregate to produce a thermodynamically stable, transparent and isotropic solution. Mixed AOT/L121 aggregates could be confirmed by fluorescence, surface tension, differential scanning calorimetry (DSC) and isothermal titration calorimetry (ITC). In an isotropic region, where mixed aggregates are formed, there is a synergistic interaction between monomers of AOT and L121 in the mixture. In addition, Small Angle Neutron Scattering (SANS) experiments provided evidence that mixed aggregates have the shape of either spheres (with a certain polydispersity) or very short ellipsoids (axial ratio below 2), confirming a transition from giant multilamellar vesicles to small aggregates upon mixing the two hydrophobic amphiphiles. Upon dilution, the morphology changes to disk-like. From an examination of the results of all the methods the peculiar behavior of the mixed AOT/L121 system is explained.     

Development and optimization of the SPE procedure for determination of pharmaceuticals in water samples by HPLC‐diode array detection

This paper focuses on the investigation of different types of SPE sorbents for the preconcentration of eight veterinary pharmaceuticals from water samples. The pharmaceuticals studied were sulfamethazine, sulfadiazine, sulfaguanidine, trimethoprim, oxytetracycline, enrofloxacin, norfloxacin and penicillin G/procaine. Five different SPE materials (Strata‐X, Strata‐X‐C, Strata SDB‐L, Strata C8 and Strata C18) from Phenomenex were compared with Oasis HLB with a view to obtaining the best cartridges for all pharmaceuticals investigated. Extraction efficiency was determined by HPLC with diode array detection (DAD). HPLC‐DAD separation and quantification of the selected pharmaceuticals were carried out under gradient elution by a binary mixture of 0.01 M oxalic acid and ACN based on cyano modified column (LiChrosphere 100 CN) from Merck. Strata‐X provided the best results in the preconcentration of 100 mL water samples, yielding average pharmaceutical recoveries of higher than 90%, except for sulfaguanidine (76.1%). The developed Strata‐X‐HLPC‐DAD method was validated and applied, for the efficient investigation of reverse osmosis/nanofiltration membranes and for the removal of these eight pharmaceuticals from the production wastewater samples. NF90 and XLE membranes were shown to be the best for the rejection of all investigated pharmaceuticals.     

Complete biosynthesis of erythromycin A and designed analogs using E. coli as a heterologous host

Erythromycin A is a potent antibiotic long-recognized as a therapeutic option for bacterial infections. The soil-dwelling bacterium Saccharopolyspora erythraea natively produces erythromycin A from a 55 kb gene cluster composed of three large polyketide synthase genes (each ~10 kb) and 17 additional genes responsible for deoxysugar biosynthesis, macrolide tailoring, and resistance. In this study, the erythromycin A gene cluster was systematically transferred from S. erythraea to E. coli for reconstituted biosynthesis, with titers reaching 10 mg/l. Polyketide biosynthesis was then modified to allow the production of two erythromycin analogs. Success establishes E. coli as a viable option for the heterologous production of erythromycin A and more broadly as a platform for the directed production of erythromycin analogs.     

Estimation of the degree of asphericity of a glass sphere using a vectorial shearing interferometer

The degree of asphericity is estimated by determining the average radius of curvature in different sections, at various points on the surface of a sphere, and the deviation from it. We employ the vectorial shearing interferometer (VSI) as the instrument to determine the radius of curvature from two subapertures of the transparent glass sphere. We incorporate the sphere as a thick lens into the interferometric setup, illuminating it with an expanded beam. The spherical aberration, introduced by the sphere in the wave front, depends on the local sphere radius, on the refraction index of the glass, and on the cone angle of the source. The wave front aberrated by the sphere impinges on the VSI. Here, the wave front is divided in two in amplitude, it is sheared vectorially, and it is superimposed with itself. The fringe pattern is formed in the intersection of the wave fronts. The shape of the resulting fringe pattern is directly related to spherical aberration. We estimate qualitatively the degree of asphericity, comparing the phase gradients in different sections of the sphere. Here, we report on the experimental setup to test the asphericity, the results with different vectorial shearing (magnitude and direction). Finally, we perform a comparison with the theoretical predictions.     

Spin-label saturation-recovery EPR at W-band: applications to eye lens lipid membranes

Saturation-recovery (SR) EPR at W-band (94 GHz) to obtain profiles of the membrane fluidity and profiles of the oxygen transport parameter is demonstrated for lens lipid membranes using phosphatidylcholine (n-PC), stearic acid (n-SASL), and cholesterol analog (ASL and CSL) spin labels, and compared with results obtained in parallel experiments at X-band (9.4 GHz). Membranes were derived from the total lipids extracted from 2-year-old porcine lens cortex and nucleus. Two findings are especially significant. First, measurements of the spin-lattice relaxation times T1 for n-PCs allowed T1 profiles across the membrane to be obtained. These profiles reflect local membrane properties differently than profiles of the order parameter. Profiles obtained at W-band are, however, shifted to longer T1 values compared to those obtained at X-band. Second, using cholesterol analog spin labels and relaxation agents (hydrophobic oxygen and water-soluble NiEDDA), the cholesterol bilayer domain was discriminated in membranes made from lipids of the lens nucleus. However, membranes made from cortical lipids show a single homogeneous environment. Profiles of the oxygen transport parameter obtained from W-band measurements are practically identical to those obtained from X-band measurements, and are very similar to those obtained earlier at X-band for membranes made of 2-year-old bovine cortical and nuclear lens lipids (M. Raguz, J. Widomska, J. Dillon, E.R. Gaillard, W.K. Subczynski, Biochim. Biophys. Acta 1788 (2009) 2380-2388). Results demonstrate that SR EPR at W-band has the potential to be a powerful tool for studying samples of small volume, ～30 nL, compared with the sample volume of ～3 μL at X-band.     

Hydrolysis and retro‐aldol cleavage of ethyl threo‐2‐(1‐adamantyl)‐3‐hydroxybutyrate: competing reactions

The hydrolysis of ethyl threo‐2‐(1‐adamantyl)‐3‐hydroxybutyrate ( 1 ) and the parent ester ethyl 3‐hydroxybutyrate ( 4 ) has been studied experimentally and computationally. In the hydrolysis of threo‐ester 1 with 2 M NaOH, predominantly retro‐aldol product was observed, whereas the hydrolyzed product was present in a minor amount. When the reaction is carried out under the same conditions with the parent ester ethyl 3‐hydroxybutyrate ( 4 ), hydrolyzed product is exclusively observed. The competitive pathways, namely hydrolysis and the retro‐aldol reaction for 1 and 4 were investigated using DFT calculations in the both gas and solvent phase. The calculated results in the solvent phase at B3LYP/6–31 + G* level revealed that the formation of retro‐aldol products is kinetically preferred over the hydrolysis of threo‐ester 1 in the presence of a base. However, the parent ester 4 showed that the retro‐aldol process is less favored than the hydrolysis process under similar conditions. The steric effect imposed by the bulky adamantyl group to enhance the activation barriers for the hydrolysis of the ethyl threo‐2‐(1‐adamantyl)‐3‐hydroxybutyrate ( 1 ) was further supported by the calculations performed with tert‐butyl group at the α‐carbon atom of ethyl 3‐hydroxybutyrate ( 7 ). Copyright © 2010 John Wiley & Sons, Ltd.