Free field measurements of the absorption coefficient for nonlocally reacting sound absorbing porous layers

A simple asymptotic approximation with two parameters (the plane wave reflection coefficient and a correction factor) has been derived by Brekhovskikh and Godin [Acoustics of Layered Media II. Point Sources and Bounded Beams (Springer, New York, 1992)], for the spherical field reflected by nonlocally reacting surfaces. In the present work, an expression for the correction factor is obtained for the case of a homogeneous and isotropic porous layer. A free field method for evaluating reflection and absorption coefficients with this approximation is presented. The evaluation of the absorption coefficient at normal incidence is performed on a porous layer on a rigid backing, and compared to measurements performed using a two microphone technique and an impedance tube.     

The structure of NADH in the enzyme dTDP-d-glucose dehydratase (RmlB)

The structure of Streptococcus suis serotype type 2 dTDP-d-glucose 4,6-dehydratase (RmlB) has been determined to 1.5 A resolution with its nicotinamide coenzyme and substrate analogue dTDP-xylose bound in an abortive complex. During enzyme turnover, NAD(+) abstracts a hydride from the C4' atom of dTDP-glucose-forming NADH. After elimination of water, hydride is then transferred back to the C6' atom of dTDP-4-keto-5,6-glucosene-regenerating NAD(+). Single-crystal spectroscopic studies unambiguously show that the coenzyme has been trapped as NADH in the crystal. Electron density clearly demonstrates that in contrast to native structures of RmlB where a flat nicotinamide ring is observed, the dihydropyridine ring of the reduced cofactor in this complex is found as a boat. The si face, from which the pro-S hydride is transferred, has a concave surface. Ab initio electronic structure calculations demonstrate that the presence of an internal hydrogen bond, between the amide NH on the nicotinamide ring and one of the oxygen atoms on a phosphate group, stabilizes this distorted conformation. Additionally, calculations show that the hydride donor ability of NADH is influenced by the degree of bending in the ring and may be influenced by an active-site tyrosine residue (Tyr 161). These results demonstrate the ability of dehydratase enzymes to fine-tune the redox potential of NADH through conformational changes in the nicotinamide ring.     

Reduced charge transfer exciton recombination in organic semiconductor heterojunctions by molecular doping

We investigate the effect of molecular doping on the recombination of electrons and holes localized at conjugated-polymer-fullerene interfaces. We demonstrate that a low concentration of p-type dopant molecules (<4% weight) reduces the interfacial recombination via charge transfer excitons and results in a favored formation of separated carriers. This is observed by the ultrafast quenching of photoluminescence from charge transfer excitons and the increase in photoinduced polaron density by ~70%. The results are consistent with a reduced formation of emissive charge transfer excitons, induced by state filling of tail states.     

Control of light transmission through opaque scattering media in space and time

We report the first experimental demonstration of combined spatial and temporal control of light transmission through opaque media. This control is achieved by solely manipulating spatial degrees of freedom of the incident wave front. As an application, we demonstrate that the present approach is capable of forming bandwidth-limited ultrashort pulses from the otherwise randomly transmitted light with a controllable interaction time of the pulses with the medium. Our approach provides a new tool for fundamental studies of light propagation in complex media and has the potential for applications for coherent control, sensing and imaging in nano- and biophotonics.     

Laser cutting of silicon with the liquid jet guided laser using a chlorine-containing jet media

In this paper results for liquid media are presented, which are used the first time as liquid jet for cutting of silicon with laser chemical processing (LCP). The liquids contain a perfluoro-carbon compound as solvent and elemental chlorine as etching agent for silicon. Experiments were performed to investigate its influence on groove form and maximum achieved groove depth. It is shown that with the addition of low-concentration chlorine, the groove depth can already be significantly increased. The groove shape could be changed from a V-profile to a U-profile. Furthermore, an about four times greater groove depth was achieved by applying a saturated chlorine solution compared to groove depths without using chlorine. Finally, a theory is given and discussed to describe the phenomena observed.     

Characterization of low energy charge transfer transitions in (terpyridine)(bipyridine)ruthenium(II) complexes and their cyanide-bridged bi- and tri-metallic analogues

The lowest energy metal-to-ligand charge transfer (MLCT) absorption bands found in ambient solutions of a series of [Ru(tpy)(bpy)X](m+) complexes (tpy = 2,2':3',2'-terpyridine; bpy = 2,2'-bipyridine; and X = a monodentate ancillary ligand) feature one or two partly resolved weak absorptions (bands I and/or II) on the low energy side of their absorption envelopes. Similar features are found for the related cyanide-bridged bi- and trimetallic complexes. However, the weak absorption band I of [(bpy)(2)Ru{CNRu(tpy)(bpy)}(2)](4+) is missing in its [(bpy)(2)Ru{NCRu(tpy)(bpy)}(2)](4+) linkage isomer demonstrating that this feature arises from a Ru(II)/tpy MLCT absorption. The energies of the MLCT band I components of the [Ru(tpy)(bpy)X](m+) complexes are proportional to the differences between the potentials for the first oxidation and the first reduction waves of the complexes. Time-dependent density functional theory (TD-DFT) computational modeling indicates that these band I components correspond to the highest occupied molecular orbital (HOMO) to lowest unoccupied molecular orbital (LUMO) transition, with the HOMO being largely ruthenium-centered and the LUMO largely tpy-centered. The most intense contribution to a lowest energy MLCT absorption envelope (band III) of these complexes corresponds to the convolution of several orbitally different components, and its absorption maximum has an energy that is about 5000 cm(-1) higher than that of band I. The multimetallic complexes that contain Ru(II) centers linked by cyanide have mixed valence excited states in which more than 10% of electronic density is delocalized between the nearest neighbor ruthenium centers, and the corresponding stabilization energy contributions in the excited states are indistinguishable from those of the corresponding ground states. Single crystal X-ray structures and computational modeling indicate that the Ru-(C≡N)-Ru linkage is quite flexible and that there is not an appreciable variation in electronic structure or energy among the conformational isomers.     

Identification of epidermal L‐tryptophan and its oxidation products by in vivo FT‐Raman Spectroscopy further supports oxidative stress in patients with vitiligo

In the past, non‐invasive in vivo FT‐Raman spectroscopy has been used to detect H₂O₂‐mediated oxidation of methionine to methionine sulfoxide and methionine sulfone, as well as cysteine to cysteic acid, in the sequence of proteins in the epidermis of patients with vitiligo. L ‐tryptophan (Trp) is another potential target for this oxidation. Owing to the presence of 10⁻³M epidermal albumin which contains one Trp residue, it was tempting to follow the oxidation of this amino acid. Using in vivo and in vitro FT‐Raman spectroscopy, we show for the first time that epidermal Trp is oxidised in patients with vitiligo, yielding 5‐OH‐Trp at 930 cm⁻¹ and other oxidation products (i.e. N‐formyl kynurenine and kynurenine) from indole ring oxidation peaking at 1050 cm⁻¹. On the basis of detailed in vitro results, we could conclude that 5‐OH‐Trp as well as formyl kynurenine and kynurenine are formed via H₂O₂‐mediated Fenton chemistry. These results once again bring out the strength of non‐invasive in vivo FT‐Raman Spectroscopy in dermatology to follow the effect of oxidative stress in the skin of patients with vitiligo. Copyright © 2008 John Wiley & Sons, Ltd.