Sugarcane Phosphoribosyl Pyrophosphate Synthetase: Molecular Characterization of a Phosphate-independent PRS

Phosphoribosyl pyrophosphate synthetase (PRS-EC:2.7.6.1) is an important enzyme present in several metabolic pathways, thus forming a complex family of isoenzymes. However, plant PRS enzymes have not been extensively investigated. In this study, a sugarcane prs gene has been characterized from the Sugar Cane Expressed Sequence Tag Genome Project. This gene contains a 984-bp open reading frame encoding a 328-amino acid protein. The predicted amino acid sequence has 77% and 78% amino acid sequence identity to Arabidopsis thaliana and Spinacia oleracea PRS4, respectively. The assignment of sugarcane PRS as a phosphate-independent PRS isoenzyme (Class II PRS) is verified following enzyme assay and phylogenetic reconstruction of PRS homologues. To gain further insight into the structural framework of the phosphate independence of sugarcane PRS, a molecular model is described. This model reveals the formation of two conserved domains elucidating the structural features involved in sugarcane PRS phosphate independence. The recombinant PRS retains secondary structure elements and a quaternary arrangement consistent with known PRS homologues, based on circular dichroism measurements.

Absolute configuration reassignment of two chromanes from Peperomia obtusifolia (Piperaceae) using VCD and DFT calculations

Previous analysis of the ECD spectra of two prenylated benzopyrans isolated from Peperomia obtusifolia, by means of the helicity rule for the chromane chromophore, resulted in the incorrect assignment of their absolute configuration, (5) instead of (R) for a deduced P-helicity of the chromane ring for the (+)-enantiomers. This was discovered by the application of DFT calculations and VCD spectroscopy. Experimental and calculated (B3LYP/6-31G(d)) VCD and IR spectra were compared, and a definitive absolute configuration of (+)-1 and (+)-2 is reassigned directly in solution as (R). The assumption of equatorial positioning of bulky groups, shown here to be invalid for the title molecules, is the underlying cause of the previous incorrect assignment of absolute configuration. Moreover, TDDFT (B3LYP/6-311++G(2d,2p)//B3LYP/6-31G(d)) calculations of ECD spectra have shown that both P- and M-helicity of the heterocyclic ring, for a given absolute configuration, lead to the same sign for the (1)L(b) ECD band, thus bringing into question the validity of the empirical ECD helicity rule for chromane molecules. (C) 2010 Elsevier Ltd. All rights reserved.

Detailed analysis of the charge transfer complex N,N-dimethylaniline-SO(2) by Raman spectroscopy and density functional theory calculations

Although the amine sulfur dioxide chemistry was well characterized in the past both experimentally and theoretically, no systematic Raman spectroscopic study describes the interaction between N,N-dimethylaniline (DMA) and sulfur dioxide (SO(2)). The formation of a deep red oil by the reaction of SO(2) with DMA is an evidence of the charge transfer (CT) nature of the DMA-SO(2) interaction. The DMA -SO(2) normal Raman spectrum shows the appearance of two intense bands at 1110 and 1151 cm(-1), which are enhanced when resonance is approached. These bands are assigned to nu(s)(SO(2)) and nu(phi-N) vibrational modes, respectively, confirming the interaction between SO(2) and the amine via the nitrogen atom. The dimethyl group steric effect favors the interaction of SO(2) with the ring pi electrons, which gives rise to a pi-pi* low-energy CT electronic transition, as confirmed by time-dependent density functional theory (TDDFT) calculations. In addition, the calculated Raman DMA-SO(2) spectrum at the B3LYP/6-311++g(3df,3pd) level shows good agreement with the experimental results (vibrational wavenumbers and relative intensities), allowing a complete assignment of the vibrational modes. A better understanding of the intermolecular interactions in this model system can be extremely useful in designing new materials to absorb, detect, or even quantify SO(2). Copyright (C) 2009 John Wiley & Sons, Ltd.

Structural Investigation of MFe(2)O(4) (M = Fe, Co) Magnetic Fluids

Ferrites of the type M(II)Fe(2)O(4) (M = Fe and Co) have been prepared by the traditional coprecipitation method. These ferrites were modified by the adsorption of fatty acids derived from soybean and castor oil and were then dispersed in cyclohexane, providing very stable magnetic fluids, readily usable in nonpolar media. The structural properties of the ferrites and modified ferrites as well as the magnetic fluids were characterized by XRD (X-ray powder diffraction), TEM (transmission electron microscopy), DRIFTS (diffusion reflectance infrared Fourier transform spectroscopy), FTMR (Fourier transform near-infrared), UV-vis, normal Raman spectroscopy, and surface-enhanced Raman scattering (SERS). XRD and TEM analysis have shown that the magnetic nanoparticles (nonmodified and modified) present diameters in the range of 10-15 nm. DRIFTS measurements have shown that the carboxylate groups of soybean and castor oil fatty acids adsorb on the ferrite surface, forming three different structures: a bridging bidentate, a bridging monodentate, and a bidentate chelate structure. The FTIR and Raman spectra of nonmodified Fe(3)O(4) and CoFe(2)O(4) nanoparticles have shown that the number of observed phonons is not compatible with the expected O(h)(7) symmetry, since IR-only active phonons were observed. in the Raman spectra and vice versa. SERS measurements of a CoFe(2)O(4) thin film on a SERS-active gold electrode at different applied potentials made possible the assignment of the signals near 550 and 630 cm(-1) to Co-O motions and the signals near 470 and 680 cm(-1) to Fe-O motions.

Excited states of the CaAl molecule: An MRCI study

Accurate potential energy curves, dissociation energies and spectroscopic constants for several low-lying doublet and quartet electronic states of CaAl were investigated using the CASSCF/MRCI methodology, and the cc-pVQZ basis set. Our results represent an improvement over a previous theoretical description, and also characterizes new higher excited states not previously investigated, thus confirming the assignment of four excited states investigated experimentally. With the theoretical transition moment functions, transition probabilities and radiative lifetimes were estimated via Einstein spontaneous emission coefficients. (c) 2008 Elsevier B. V. All rights reserved.

Surface-enhanced Raman study of electrochemical and photocatalytic degradation of the azo dye Janus Green B

The photocatalytic degradation of Janus Green B azo dye over silver modified titanium dioxide films was investigated by surface-enhanced Raman spectroscopy (SERS). An optimized SERS-active substrate was employed to study the photodegradation reaction of Janus Green B. Considering that photocatalytic degradation processes of organic molecules adsorbed on TiO2 might involve either their oxidation or reduction reaction, the vibrational spectroelectrochemical study of the dye was also performed, in order to clarify the transformations involved in initial steps of its photochemical decomposition. In order to understand the changes in Raman spectra of Janus Green B after photodegradation and/or electrochemical processes, a vibrational assignment of the main Raman active modes of the dye was carried out, based on a detailed resonance Raman profile. Products formed by electrochemical and photochemical degradation processes were compared. The obtained results revealed that the first steps of the degradation process of Janus Green B involve a reductive mechanism. (C) 2007 Published by Elsevier B.V.

Metabolomic assessment with CE-MS of the nutraceutical effect of Cystoseira spp extracts in an animal model

There is a need of scientific evidence of claimed nutraceutical effects, but also there is a social movement towards the use of natural products and among them algae are seen as rich resources. Within this scenario, the development of methodology for rapid and reliable assessment of markers of efficiency and security of these extracts is necessary. The rat treated with streptozotocin has been proposed as the most appropriate model of systemic oxidative stress for studying antioxidant therapies. Cystoseira is a brown alga containing fucoxanthin and other carothenes whose pressure-assisted extracts were assayed to discover a possible beneficial effect on complications related to diabetes evolution in an acute but short-term model. Urine was selected as the sample and CE-TOF-MS as the analytical technique to obtain the fingerprints in a non-target metabolomic approach. Multivariate data analysis revealed a good clustering of the groups and permitted the putative assignment of compounds statistically significant in the classification. Interestingly a group of compounds associated to lysine glycation and cleavage from proteins was found to be increased in diabetic animals receiving vehicle as compared to control animals receiving vehicle (N6, N6, N6-trimethyl-L-lysine, N-methylnicotinamide, galactosylhydroxylysine, L-carnitine, N6-acetyl-N6-hydroxylysine, fructose-lysine, pipecolic acid, urocanic acid, amino-isobutanoate, formylisoglutamine. Fructoselysine significantly decreased after the treatment changing from a 24% increase to a 19% decrease. CE-MS fingerprinting of urine has provided a group of compounds different to those detected with other techniques and therefore proves the necessity of a cross-platform analysis to obtain a broad view of biological samples.

A CASSCF/MRCI Study of the Low-Lying Electronic States of the BeS Molecule

Accurate potential energy curves, dipole moment functions, dissociation energies, and molecular constants for several low-lying singlet and triplet electronic states of BeS were investigated using the CASSCF/MRCI methodology, and the cc-pV5Z basis set for beryllium, and the aug-cc-pV(5+d) Z set for sulfur. Besides presenting improved results for the three lowest lying states, this study presents the first theoretical characterization of another set of nine excited states so far unknown experimentally. Our results are sufficiently accurate to reliably guide the experimental search and characterization of these states, and also to confirm the experimental assignment of the B(1)Sigma(+) excited state. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 111: 1694-1700, 2011

Uma coleção de história em um museu de ciências naturais: o Museu Paulista de Hermann von Ihering

Instalado em um edifício-Monumento, data de 1895 a inauguração do Museu Paulista. Seu primeiro diretor, o zoólogo Hermann Von Ihering (1895-1916), teve a tarefa de organizar suas vastas coleções, as quais possuíam objetos de diversos ramos do conhecimento, entre eles, a História. Este artigo tem a intenção de entender a dimensão, dinâmica e concepção desta coleção de História, que recebeu pouca atenção da Historiografia relativa ao tema.

Pseudodifferential operators with C*-algebra-valued symbols: Abstract characterizations

Given a separable unital C*-algebra C with norm parallel to center dot parallel to, let E-n denote the Banach-space completion of the C-valued Schwartz space on R-n with norm parallel to f parallel to(2)=parallel to < f, f >parallel to(1/2), < f, g >=integral f(x)* g(x)dx. The assignment of the pseudodifferential operator A=a(x,D) with C-valued symbol a(x,xi) to each smooth function with bounded derivatives a is an element of B-C(R-2n) defines an injective mapping O, from B-C(R-2n) to the set H of all operators with smooth orbit under the canonical action of the Heisenberg group on the algebra of all adjointable operators on the Hilbert module E-n. In this paper, we construct a left-inverse S for O and prove that S is injective if C is commutative. This generalizes Cordes' description of H in the scalar case. Combined with previous results of the second author, our main theorem implies that, given a skew-symmetric n x n matrix J and if C is commutative, then any A is an element of H which commutes with every pseudodifferential operator with symbol F(x+J xi), F is an element of B-C(R-n), is a pseudodifferential operator with symbol G(x - J xi), for some G is an element of B-C(R-n). That was conjectured by Rieffel.

Ipolamiide and fulvoipolarniide from Stachytarpheta glabra (Verbenaceae): A structural and spectroscopic characterization

The phenylethanoid glycoside acteoside and the iridoids ipolamiide and 4-methoxycarbonyl-7-methylcyclopenta[c]pyran (fulvoipolamiide) were isolated from the leaves of Stachytarpheta glabra. The solid state structure of fulvoipolamiide was confirmed by X-ray diffraction studies. The molecules of fulvoipolamiide are displayed in layers parallel to the crystallographic axis a. This molecule is planar with electron delocalization in the fused ring system and the pyran rings of adjacent layers in the solid state structure are involved in a pi-pi stacking interaction. Raman spectroscopy has also been used to characterize the most important bands present in the spectra of fulvoipolamiide and ipolamiide, and comparison made with literature allows the assignment of some key markers, specially the bands in the 1600-1700 cm(-1) range. (C) 2007 Elsevier B.V. All rights reserved.

Azaphilones from the Endophyte Chaetomium globosum

Six new azaphilones, 5`-epichaetoviridin A (7), 4`-epichaetoviridin F (9), 12 beta-hydroxychaetoviridin C (10), and chaetoviridins G-I (11-13), and six known azaphilones, chaetoviridins A E (1-5) and 4`-epichaetoviridin A (8), were isolated from the endophytic fungus Chaetomium globosum cultivated in PDB medium for 21 days. The structure elucidation and the assignment of the relative configurations of the new natural products were based on detailed NMR and MS spectroscopic analyses. The structure of compound 1 was confirmed by single-crystal X-ray diffraction analysis. were determined using Mosher`s method. The antibiotic activity of the elegans infection model. The absolute configurations of compounds 4, 7, 8, and 12 compounds was evaluated using an in vivo Caenorhabditis elegans infection model.

Performance analysis of an optical network employing waveband and traffic grooming

This paper analyses an optical network architecture composed by an arrangement of nodes equipped with multi-granular optical cross-connects (MG-OXCs) in addition to the usual optical cross-connects (OXCs). Then, selected network nodes can perform both waveband as well as traffic grooming operations and our goal is to assess the improvement on network performance brought by these additional capabilities. Specifically, the influence of the MG-OXC multi-granularity on the blocking probability is evaluated for 16 classes of service over a network based on the NSFNet topology. A mechanism of fairness in bandwidth capacity is also added to the connection admission control to manage the blocking probabilities of all kind of bandwidth requirements. Comprehensive computational simulation are carried out to compare eight distinct node architectures, showing that an adequate combination of waveband and single-wavelength ports of the MG-OXCs and OXCs allow a more efficient operation of a WDM optical network carrying multi-rate traffic.

Hybrid Algorithms for Routing and Assignment Wavelengths in Optical Networks

This paper presents a strategy for the solution of the WDM optical networks planning. Specifically, the problem of Routing and Wavelength Allocation (RWA) in order to minimize the amount of wavelengths used. In this case, the problem is known as the Min-RWA. Two meta-heuristics (Tabu Search and Simulated Annealing) are applied to take solutions of good quality and high performance. The key point is the degradation of the maximum load on the virtual links in favor of minimization of number of wavelengths used; the objective is to find a good compromise between the metrics of virtual topology (load in Gb/s) and of the physical topology (quantity of wavelengths). The simulations suggest good results when compared to some existing in the literature.