Resonance Raman and surface-enhanced resonance Raman studies of polymer-modified electrodes which mimic heme enzymes

Iron-5,10,15,20-tetraphenylporphyrin (FeTPP) has been incorporated into films of a coordinating hydrogel polymer support medium, poly(gamma-ethyl-L-glutamate) (PEG) functionalised with imidazole pendant arms (PEG-Im), and studied in situ on silver electrodes using a combination of both resonance Raman (RR) and surface-enhanced resonance Raman (SERR) spectroscopy. The SERR spectra give information on the portion of the film close to the electrode surface while RR spectra probe the

SURFACE-ENHANCED RAMAN-SCATTERING STUDIES OF METALLOPORPHYRINS ON SILVER SOLS, MELLFS, AND ELECTRODES - EVIDENCE FOR REVERSIBLE PHOTOINDUCED DEMETALATION OF A SILVER(II) PORPHYRIN

A series of metalloporphyrins of the type M(TMPyP) (where M = Ag(II), Zn(II), Cu(II) and TMPyP = meso-tetrakis(4-N-methylpyridyl)porphyrin) have been investigated in solution and on the surface of silver sols, electrodes, and MELLFs (metal liquidlike films). Similar spectra were recorded on all three surfaces but significant differences in detailed behavior were found. In particular, a novel, reversible, and rapid photoinduced demetalation reaction has been observed for the AgII(TMPyP)/MELLF system. An apparently similar demetalation reaction for the same metalloporphyrin was observed on Ag electrodes but this reversed at a very much slower rate. No demetalation of Ag(II)(TMPyP) was observed with Ag sols nor with any of the other metalloporphyrins at any of the surfaces investigated. The implications of the findings in relation to the nature of the MELLF environment are briefly considered.

RAMAN-SCATTERING AND SCANNING ELECTRON-TUNNELING STUDIES OF METAL LIQUID-LIKE FILMS PRODUCED FROM SILVER AND GOLD SOLS

Surface-enhanced Raman scattering (SERS) excited at several visible wavelengths and recorded using a cooled charged-coupled device detector is reported from the mobile, interfacial, liquid-like metal films (MELLFs) formed when solutions of metal complexes or pyridine in chlorocarbon solvents are mixed with aqueous sols of silver or gold. MELLF formation has not previously been reported for gold sols or for pyridine as stabilizer. Comparison of the spectra for the MELLFs formed from individual metal complexes and from 50:50 mixtures show that the spectral patterns observed for the latter are distinctive and are not generally equivalent to the sum of the spectra associated with the individual complexes, in contrast to the situation observed for sols where the individual spectra do appear to be additive. Raman scattering from both gold and silver MELLFs is readily observed at excitation wavelengths in the red, around 750 nm, but at 514 nm only that from silver films is detectable. These findings are considered in terms of particle size and absorption band intensities. A preliminary study of the film surface topography and particle size was carried out by scanning tunnelling electron microscopy (STM) of Ag MELLFs deposited on gold-coated mica substrates. Computer-processed images of the STM data show the presence on the film surface of finger-like bars, 200-400 nm long with approximately square cross-section, 40-60 nm side, together with other smaller cuboid features. The implications of these findings in relation to SERS are briefly considered.

Limiting withdrawal rate and maximum film thickness during dip-coating of titania sols onto a Si substrate

The article highlights new insights into production of thin titania films widely used as catalyst support in many modern reactors including capillary microreactors, microstructured fixed-bed reactors and falling film microreactors. Dip-coating of a Mania sol onto a Si substrate has been studied in the range of the sol viscosities of 1.5-2.5 mPa s and the sol withdrawal rates of 0.2-18 mm/s. Different viscosities of sols were created by addition of desired amounts of nitric acid to the synthesis mixture of titanium isopropoxide and Plutonic F127 in ethanol which allowed to control the rate of the condensation reactions. Uniform inesoporous titania coatings were obtained at the solvent withdrawal rates below 10 mm/s at sol viscosities in the range from 1.6 mPa s to 2.5 mPa s. There exists a limiting withdrawal rate corresponding to a capillary number of ca. 0.01 beyond which uniform titania films cannot be obtained. Below the limiting withdrawal rate, the coating thickness is a power function of the sol viscosity and withdrawal rate, both with an exponent of 2/3. The limiting withdrawal rate increases as the solvent evaporation rate increases and it decreases as the sol viscosity increases. Crown Copyright (C) 2011 Published by Elsevier B.V. All rights reserved.

Overcoming Equilibrium Issues with Carbonyl Reductase Enzymes

We report herein the screening, optimisation and scale up to 100 g of a bioreduction process that employs an in situ product removal (ISPR) technique to overcome the inherent equilibrium problem associated with the coupled-substrate approach to biocatalytic carbonyl reduction. This technique allowed the valuable chiral alcohol, (S)-2-bromo-2-cyclohexen-1-ol, to be isolated in 88% yield and 99.8% ee without the need for further purification, validating the general applicability of this experimental setup.

An in vitro screen of bacterial lipopolysaccharide biosynthetic enzymes identifies an inhibitor of ADP-heptose biosynthesis

The lipopolysaccharide (LPS)-rich outer membrane of gram-negative bacteria provides a protective barrier that insulates these organisms from the action of numerous antibiotics. Breach of the LPS layer can therefore provide access to the cell interior to otherwise impermeant toxic molecules and can expose vulnerable binding sites for immune system components such as complement. Inhibition of LPS biosynthesis, leading to a truncated LPS molecule, is an alternative strategy for antibacterial drug development in which this vital cellular structure is weakened. A significant challenge for in vitro screens of small molecules for inhibition of LPS biosynthesis is the difficulty in accessing the complex carbohydrate substrates. We have optimized an assay of the enzymes required for LPS heptose biosynthesis that simultaneously surveys five enzyme activities by using commercially available substrates and report its use in a small-molecule screen that identifies an inhibitor of heptose synthesis.