Application of preparative high-speed counter-current chromatography for the separation of flavonoids from the leaves of Byrsonima crassa Niedenzu (IK)

The methanolic extract of the leaves of the medicinal plant Byrsonima crassa (Malpighiaceae) contain flavonoids with antioxidant activity. They were separated in a preparative scale using high-speed counter-current chromatography. The optimum solvent system used was composed of a mixture of ethyl acetate-n-propanol-water (140:8:80 (v/v/v)) and led to a successful separation between monoglucosilated flavonoids (quercetin-3-O-alpha-L-arabinoside, quercetin-3-O-beta-D-galactoside) and the biflavonoid amentoflavone in only 3.5 h. The purities of quercetin-3-O-alpha-L-arabinoside (95 mg), quercetin-3-O-beta-D-galactoside (16 mg) and the biflavonoid amentoflavone (114 mg) were all isolated at purity over 95%. Identification was performed by 1H NMR, 13C NMR and UV analyses.     

Synthesis and spectroscopic behavior of highly luminescent Eu(3+)-dibenzoylmethanate (DBM) complexes with sulfoxide ligands

In this paper the synthesis, characterization and photoluminescent behavior of the [RE(DBM)3L2] complexes (RE=Gd and Eu) with a variety of sulfoxide ligands; L=benzyl sulfoxide (DBSO), methyl sulfoxide (DMSO), phenyl sulfoxide (DPSO) and p-tolyl sulfoxide (PTSO) have been investigated in solid state. The emission spectra of the Eu(3+)-beta-diketonate complexes show characteristics narrow bands arising from the 5D0-->7F(J) (J=0-4) transitions, which are split according to the selection rule for C(n), C(nv) or C(s) site symmetries. The experimental Judd-Ofelt intensity parameters (Omega2 and Omega4), radiative (A(rad)) and non-radiative (A(nrad)) decay rates, and R02 for the europium complexes have been determined and compared. The highest value of Omega2 (61.9x10(-20)cm2) was obtained to the complex with PTSO ligand, indicating that Eu3+ ion is in the highly polarizable chemical environment. The higher values of the experimental quantum yield (q) and emission quantum efficiency of the emitter 5D0 level (eta) for the Eu-complexes with DMSO, DBSO and PTSO sulfoxides suggest that these complexes are promising Light Conversion Molecular Devices (LCMDs). The lower value of quantum yield (q=1%), for the hydrated complex [Eu(DBM)3H2O], indicates that the luminescence quenching occurs via multiphonon relaxation by coupling with the OH-oscillators from water molecule coordinated to rare earth ion. The pure red emission of the Eu-complexes has been confirmed by (x, y) color coordinates.     

Holo- and hemidirected lead(II) in the polymeric [Pb(4)(mu-3,4-TDTA)2(H2O)2]*4H2O complex. N,N,N',N'-tetraacetate ligands derived from o-phenylenediamines as sequestering agents for lead(II)

The coordinating ability of the ligands 3,4-toluenediamine-N,N,N',N'-tetraacetate (3,4-TDTA), o-phenylenediamine-N,N,N',N'-tetraacetate (o-PhDTA), and 4-chloro-1,2-phenylenediamine-N,N,N',N'-tetraacetate (4-Cl-o-PhDTA) (H4L acids) toward lead(II) is studied by potentiometry (25 degrees C, I = 0.5 mol x dm(-3) in NaClO4), UV-vis spectrophotometry, and 207Pb NMR spectrometry. The stability constants of the complex species formed were determined. X-ray diffraction structural analysis of the complex [Pb4(mu-3,4-TDTA)4(H2O)2]*4H2O (1) revealed that 1 has a 2-D structure. The layers are built up by the polymerization of centrosymmetric [Pb4L2(H2O)2] tetranuclear units. The neutral layers have the aromatic rings of the ligands pointing to the periphery, whereas the metallic ions are located in the central part of the layers. In compound 1, two types of six-coordinate lead(II) environments are produced. The Pb(1) is coordinated to two nitrogen atoms and four carboxylate oxygens from the ligand, whereas Pb(2) has an O6 trigonally distorted octahedral surrounding. The lead(II) ion is surrounded by five carboxylate oxygens and a water molecule. The carboxylate oxygens belong to four different ligands that are also joined to four other Pb(1) ions. The selective uptake of lead(II) was analyzed by means of chemical speciation diagrams as well as the so-called conditional or effective formation constants K(Pb)eff. The results indicate that, in competition with other ligands that are strong complexing agents for lead(II), our ligands are better sequestering agents in acidic media.     

Byte structure variable length coding (BS-VLC): a new specific algorithm applied in the compression of trajectories generated by molecular dynamics

Molecular dynamics is a well-known technique very much used in the study of biomolecular systems. The trajectory files produced by molecular dynamics simulations are extensive, and the classical lossless algorithms give poor efficiencies in their compression. In this work, a new specific algorithm, named byte structure variable length coding (BS-VLC), is introduced. Trajectory files, obtained by molecular dynamics applied to trypsin and a trypsin:pancreatic trypsin inhibitor complex, were compressed using four classical lossless algorithms (Huffman, adaptive Huffman, LZW, and LZ77) as well as the BS-VLC algorithm. The results obtained show that BS-VLC nearly triplicates the compression efficiency of the best classical lossless algorithm, preserving a near lossless behavior. Compression efficiencies close to 50% can be obtained with a high degree of precision, and the maximum efficiency possible (75%), within this algorithm, can be performed with good precision.     

Observation of a continuum-continuum interference hole in ultrafast dissociating core-excited molecules

The femtosecond dissociation of HCl after core excitation has been studied through the resonant Auger decay. The spectra contain contributions from decay occurring at both "molecular" and "atomic" internuclear distances. We have observed a new interference mechanism in these spectra: An atomic spectral line develops into a negative spectral contribution, a "hole," when detuning the excitation energy from the maximum of the Cl2p(-1)sigma(*) resonance. Resonant x-ray scattering theory quantitatively explains this behavior as due to a novel destructive continuum-continuum interference between molecular and atomic contributions to the Auger decay.     

Gold adatoms and clusters on PPV: An ab initio investigation

We have performed an ab initio investigation of the energetic, structural, electronic, and vibrational properties of Au atoms and clusters adsorbed on poly-p-phenylene vinylene (PPV) chains, Au(n)/PPV (with n =?1, 2, 6, 7, 10, and 12). We find that the Au(n)/PPV systems are energetically stable by 0.5 eV, compared with the isolated systems, viz., PPV chain and Au(n) clusters, thus supporting the formation of Au(n)/PPV nanocomposites. Further support to the formation of Au(n)/PPV has been provided by examining the vibrational properties of pristine PPV and Au(n)/PPV systems. In agreement with experimental measurements, we find a reduction on the in-plane vibrational frequency of C-C bonds of Au(n)/PPV, when compared with the same vibrational modes of pristine PPV. The electronic properties of isolated Au(n) clusters are modified when adsorbed on PPV. The highest occupied states of Au(n)/PPV are mostly concentrated on the Au(n) cluster, while the lowest unoccupied states are mainly localized along the PPV chain. The HOMO-LUMO energy gap of the Au(n)/PPV systems are smaller than the energy gap of the isolated systems, Au(n) clusters, and pristime PPV chains.     

In situ microbial fuel cell-based biosensor for organic carbon

The biological oxygen demand (BOD) may be the most used test to assess the amount of pollutant organic matter in water; however, it is time and labor consuming, and is done ex-situ. A BOD biosensor based on the microbial fuel cell principle was tested for online and in situ monitoring of biodegradable organic content of domestic wastewater. A stable current density of 282±23mA/m(2) was obtained with domestic wastewater containing a BOD(5) of 317±15mg O(2)/L at 22±2°C, 1.53±0.04mS/cm and pH 6.9±0.1. The current density showed a linear relationship with BOD(5) concentration ranging from 17±0.5mg O(2)/L to 78±7.6mg O(2)/L. The current generation from the BOD biosensor was dependent on the measurement conditions such as temperature, conductivity, and pH. Thus, a correction factor should be applied to measurements done under different environmental conditions from the ones used in the calibration. These results provide useful information for the development of a biosensor for real-time in situ monitoring of wastewater quality.     

Dissociative photoionization of adenine following valence excitation

We present results on the valence level excitation, ionization and dissociation of adenine, using time-of-flight mass spectrometry and synchrotron radiation, in the vacuum ultraviolet (VUV) range of 12-21 eV. The measurements were performed using a gas-phase (Ne) harmonics filter in order to eliminate contributions from higher-order harmonics. Mass spectra were obtained using the photoelectron-photoion coincidence technique (PEPICO). The relative abundances for each ionic fragment and their mean kinetic energy release have been determined from the analysis of the corresponding peak shapes in the mass spectra. Comparison with the available photoelectron spectra and previous measurements allowed the assignment of the main features in the spectra. A discussion on the dissociative photoionization channels of this molecule has also been included. Due to our harmonics-free incident photon beam we were able to propose new appearance energy (AE) for the most important ionic channels in this energy range. The precursor ion, C(5)H(5)N(5)+, is the most abundant species (40% at 15 eV and 20% at 20 eV), which confirms the high stability of adenine upon absorption of VUV photons. We have observed other intense fragment ions such as: C(4)H(4)N(4)+, C(3)H(3)N(3) (+), C(2)H(2)N(2)+ and HCNH+. The production of the neutral HCN fragment represents up to 40% of the dissociative channels for this molecule as induced by VUV photons.     

Effect of low intensity helium-neon (HeNe) laser irradiation on experimental paracoccidioidomycotic wound healing dynamics

The effect of HeNe laser on the extracellular matrix deposition, chemokine expression and angiogenesis in experimental paracoccidioidomycotic lesions was investigated. At days 7, 8 and 9 postinfection the wound of each animal was treated with a 632.8 nm HeNe laser at a dose of 3 J cm(-2). At day 10 postinfection, the wounds were examined by using histologic and immunohistochemical methods. Results revealed that laser-treated lesions were lesser extensive than untreated ones, and composed mainly by macrophages and lymphocytes. High IL-1beta expression was shown in the untreated group whereas in laser-treated animals the expression was scarce. On the other hand, the expression of CXCL-10 was found to be reduced in untreated animals and quite intensive and well distributed in the laser-treated ones. Also, untreated lesions presented vascular endothelial growth factor (VEGF) in a small area near the center of the lesion and high immunoreactivity for hypoxia-inducible factor-1 (HIF-1), whereas laser-treated lesions expressed VEGF surrounding blood vessels and little immunoreactivity for HIF-1. Laser-treated lesions presented much more reticular fibers and collagen deposition when compared with the untreated lesion. Our results show that laser was efficient in minimizing the local effects observed in paracoccidioidomycosis and can be an efficient tool in the treatment of this infection, accelerating the healing process.     

Determination of contact angles, silane coverage, and hydrophobicity heterogeneity of methylated quartz surfaces using ToF-SIMS

Methylated quartz surfaces are extensively used in colloid science for wettability studies and the control and impact of hydrophobicity in key physicochemical processes. In this study, time-of-flight secondary ion mass spectrometry (ToF-SIMS) has been used to correlate the surface chemistry of trimethylchlorosilane-methylated quartz surfaces with the contact angle. Models have been developed for the calculation of both advancing and receding contact angles based on measurements of the ToF-SIMS signals for SiC(3)H(9)(+) (TMCS) and Si(+) (quartz). These models enable the contact angle across surfaces and, more importantly, that of individual particles to be determined on a micrometer scale. Distributions of contact angles in large ensembles of particles, therefore, can now be determined. In addition, from the ToF-SIMS analysis, the surface coverage of the methylated species can be quantitatively determined, in line with the Cassie equation. Moreover, advancing and receding contact angle maps can be calculated from ToF-SIMS images, and hence the variation in microscopic hydrophobicity (e.g., at the particle level) can be extracted directly from the images.