Quantum parallelism as a tool for ensemble spin dynamics calculations

Efficient simulations of quantum evolutions of spin-1/2 systems are relevant for ensemble quantum computation as well as in typical NMR experiments. We propose an efficient method to calculate the dynamics of an observable provided that the initial excitation is "local." It resorts to a single entangled pure initial state built as a superposition, with random phases, of the pure elements that compose the mixture. This ensures self-averaging of any observable, drastically reducing the calculation time. The procedure is tested for two representative systems: a spin star (cluster with random long range interactions) and a spin ladder.     

Thermal and photochemical reactivity of oxygen atoms on gold nanocluster surfaces

Reduction of oxidized gold nanoclusters by exposures to foreign gases and irradiation of UV photons has been investigated using X-ray photoelectron spectroscopy. Gold nanoclusters with narrow size distributions protected by alkanethiolate ligands were deposited on a TiO₂(1 1 0) surface with dip coating. Oxygen plasma etching was used for removal of alkanethiolate ligands and oxidization of gold clusters. The oxidized gold clusters were exposed to CO, C₂H₂, C₂H₄, H₂, and hydrogen atoms. Although, C₂H₄ and H₂ did not show any indications of reduction of oxidized gold clusters, CO, C₂H₂, and hydrogen atoms reduced the oxides on gold cluster surfaces. Among them, hydrogen atoms were most effective for reduction. Irradiation of UV photons around 400 nm could also reduce the oxidized gold clusters. The photochemical reduction mechanism was proposed as follows. The photo-reduction was initiated by electronic excitation of gold clusters and oxygen atoms activated reacted with carbon atoms at the surfaces of gold clusters. Carbon species were likely absorbed in gold clusters or remained at the boundaries between gold clusters when gold clusters agglomerated during oxygen plasma exposures. As the photochemical reduction progressed, carbon atoms segregated to the surfaces of gold clusters.     

Cochlear compression estimates from measurements of distortion-product otoacoustic emissions

Evidence of the compressive growth of basilar-membrane displacement can be seen in distortion-product otoacoustic emission (DPOAE) levels measured as a function of stimulus level. When the levels of the two stimulus tones (f1 and f2) are related by the formula L1 = 39 dB + 0.4 x L2 [Kummer et al., J. Acoust. Soc. Am. 103, 3431-3444 (1998)] the shape of the function relating DPOAE level to L2 is similar (up to an L2 of 70 dB SPL) to the classic Fletcher and Munson [J. Acoust. Soc. Am. 9, 1-10 (1933)] loudness function when plotted on a logarithmic scale. Explicit estimates of compression have been derived based on recent DPOAE measurements from the laboratory. If DPOAE growth rate is defined as the slope of the DPOAE I/O function (in dB/dB), then a cogent definition of compression is the reciprocal of the growth rate. In humans with normal hearing, compression varies from about 1 at threshold to about 4 at 70 dB SPL. With hearing loss, compression is still about 1 at threshold, but grows more slowly above threshold. Median DPOAE I/O data from ears with normal hearing, mild loss, and moderate loss are each well fit by log functions. When the I/O function is logarithmic, then the corresponding compression is a linear function of stimulus level. Evidence of cochlear compression also exists in DPOAE suppression tuning curves, which indicate the level of a third stimulus tone (f3) that reduces DPOAE level by 3 dB. All three stimulus tones generate compressive growth within the cochlea; however, only the relative compression (RC) of the primary and suppressor responses is observable in DPOAE suppression data. An RC value of 1 indicates that the cochlear responses to the primary and suppressor components grow at the same rate. In normal ears, RC rises to 4, when f3 is an octave below f2. The similarities between DPOAE and loudness compression estimates suggest the possibility of predicting loudness growth from DPOAEs; however, intersubject variability makes such predictions difficult at this time.     

NMR Studies of Drugs. Applications of Achiral and Chiral Lanthanide Shift Reagents to the Analgesic,Famprofazone: “Anomalous Shifts”

The 200 MHz ¹H NMR spectra of the analgesic, famprofazone, 1, have been studied in CDCl₃ solution at ambient temperatures with the achiral lanthanide shift reagent (LSR) tris (6, 6, 7, 7, 8, 8, 8-heptaf luoro-2, 2-dimethyl-3, 5-octanedionato) europium (III), Eu(FOD)₃, 2, for spectral simplification, and with the chiral LSR, tris [3-(heptafluoropropylhydroxymethylene) - (+) camphorato] europium (III), Eu (HFC)₃, 3. Lanthanide induced shift (LIS) magnitudes suggested predominant LSR binding at the carbonyl oxygen. Substantial enantiomeric shift differences were observed for several nuclei of 1 with added 3 which could permit direct determinations of enantiomeric excess.     

A vector radiative transfer model for coupled atmosphere and ocean systems with a rough interface

We report on an exact vector (polarized) radiative transfer (VRT) model for coupled atmosphere and ocean systems. This VRT model is based on the successive order of scattering (SOS) method, which virtually takes all the multiple scattering processes into account, including atmospheric scattering, oceanic scattering, reflection and transmission through the rough ocean surface. The isotropic Cox–Munk wave model is used to derive the ref and transmission matrices for the rough ocean surface. Shadowing effects are included by the shadowing function. We validated the SOS results by comparing them with those calculated by two independent codes based on the doubling/adding and Monte Carlo methods. Two error analyses related to the ocean color remote sensing are performed in the coupled atmosphere and ocean systems. One is the scalar error caused by ignoring the polarization in the whole system. The other is the error introduced by ignoring the polarization of the light transmitted through the ocean interface. Both errors are significant for the cases studied. This code fits for the next generation of ocean color study because it converges fast for absorbing medium as, for instance, ocean.     

A Synthesis of Fused Butenoudes

It has been shown that tert-butyldimethylsilylated (Z) 2-carboethoxymethylene cycloalkanols are readily desilylated with concomitant cyclization to give the corresponding butenolides. The (E) isomers are desilylated, but not cyclized under these conditions.     

Synthesis of 3,4-Dihydro-2H-Pyrroles from Ketones,Aldehydes, and Nitro Alkanes via Hydrogenative Cyclization

Syntheses of N-heterocyclic compounds that permit a flexible introduction of various substitution patterns by using inexpensive and diversely available starting materials are highly desirable. Easy to handle and reusable catalysts based on earth-abundant metals are especially attractive for these syntheses. We report here on the synthesis of 3,4-dihydro-2H-pyrroles via the hydrogenation and cyclization of nitro ketones. The latter are easily accessible from three components: a ketone, an aldehyde and a nitroalkane. Our reaction has a broad scope and 23 of the 33 products synthesized are compounds which have not yet been reported. The key to the general hydrogenation/cyclization reaction is a highly active, selective and reusable nickel catalyst, which was identified from a library of 24 earth-abundant metal catalysts.     

Structural insight into exosite binding and discovery of novel exosite inhibitors of botulinum neurotoxin serotype A through in silico screening

Botulinum neurotoxin serotype A (BoNT/A) is the most lethal toxin among the Tier 1 Select Agents. Development of potent and selective small molecule inhibitors against BoNT/A zinc metalloprotease remains a challenging problem due to its exceptionally large substrate binding surface and conformational plasticity. The exosites of the catalytic domain of BoNT/A are intriguing alternative sites for small molecule intervention, but their suitability for inhibitor design remains largely unexplored. In this study, we employed two recently identified exosite inhibitors, D-chicoric acid and lomofungin, to probe the structural features of the exosites and molecular mechanisms of synergistic inhibition. The results showed that D-chicoric acid favors binding at the α-exosite, whereas lomofungin preferentially binds at the β-exosite by mimicking the substrate β-sheet binding interaction. Molecular dynamics simulations and binding interaction analysis of the exosite inhibitors with BoNT/A revealed key elements and hotspots that likely contribute to the inhibitor binding and synergistic inhibition. Finally, we performed database virtual screening for novel inhibitors of BoNT/A targeting the exosites. Hits C1 and C2 showed non-competitive inhibition and likely target the α- and β-exosites, respectively. The identified exosite inhibitors may provide novel candidates for structure-based development of therapeutics against BoNT/A intoxication.     

Coordinating ability of the heterocycles 1,3-dithia-2-arsa- and stiba-cyclopentanes. Part III. Dithioacid and dithiocarbamate complexes containing a free functional group. Crystal structure of 2-pyrrolidonedithiocarbamate of 1,3-dithia-arsa-cyclopentane

Three 1,1-dithioacids containing an additional functional group, 2-pyrrolidone-1-carbodithioic acid, 2-hydroxycyclopentene-1-carbodithioic acid, and 2-pyrrolidone-1,3-bis(carbodithioic) acid, were reacted with the Group 15 heterocycles 2-chloro-1,3-dithia-2-arsa- and stiba-cyclopentanes (CIMS₂C₂H₄; M = As, Sb). The dithiocomplexes obtained were characterized by spectroscopic methods and elemental analyses. The X-ray structure determination of the 2-pyrrolidonedithiocarbamate of 1,3-dithia-arsacyclopentane shows a monodentate behavior of the dithiocarbamate entity and the absence of participation of the carbonyl oxygen in the coordination.     

Recent Analytical Approaches for the Study of Bioavailability and Metabolism of Bioactive Phenolic Compounds

The study of the bioavailability of bioactive compounds is a fundamental step for the development of applications based on them, such as nutraceuticals, functional foods or cosmeceuticals. It is well-known that these compounds can undergo metabolic reactions before reaching therapeutic targets, which may also affect their bioactivity and possible applications. All recent studies that have focused on bioavailability and metabolism of phenolic and terpenoid compounds have been developed because of the advances in analytical chemistry and metabolomics approaches. The purpose of this review is to show the role of analytical chemistry and metabolomics in this field of knowledge. In this context, the different steps of the analytical chemistry workflow (design study, sample treatment, analytical techniques and data processing) applied in bioavailability and metabolism in vivo studies are detailed, as well as the most relevant results obtained from them.