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Spectroscopic Measurements (spectroscopic + measurement)
Selected AbstractsSpectroscopic Diagnostics of Pulsed arc Plasmas for Particle GenerationCONTRIBUTIONS TO PLASMA PHYSICS, Issue 8 2008K. Behringer Abstract Pulsed arc plasmas were diagnosed by means of emission spectroscopy. A capacitor was discharged through argon and hydrogen leading to a few cycles of damped current oscillation with ,120 ,s period and 5-12 kA maximum current. Spectroscopic measurements in the visible range were carried out in order to characterise the electron temperature and density in the arc channel as well as electron and gas temperatures in the afterglow plasmas. Spectra were integrated over 10 ,s time windows and shifted in time from pulse to pulse. The plasmas also contained substantial fractions of electrode material (brass), namely copper and zinc. The electron density was measured in the conventional way from the broadening of H, or from the Ar I Stark width. In the arc channel, it ranged from about 3 · 1022 to 2 · 1023 m,3. The broadening of Zn II lines could also be used. Ratios of Ar I to Ar II and of Zn I to Zn II line intensities were analysed for the electron temperature. Line pairs were found which lay conveniently close in one frame of the spectrometer allowing automatic on-line analysis without relying on reproducibility. Atomic physics models including opacity were developed for Ar II and Zn II in order to check the existence of a Boltzmann distribution of their excited states. These calculations showed that the observed levels were in fact close to thermodynamic equilibrium, in particular, if the resonance lines were optically thick. Electron temperature measurements yielded values between 14000 K and 21000 K. The gas temperature in the afterglow, where particles should have formed, was derived from the rotational and vibrational temperatures of C2 molecular bands. Ratios between Cu I line intensities yielded the electron temperatures. Both were found to be a few 1000 K. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Chiral interaction in Gly-capped N-terminal motif of 310 -helix and domino-type induction in helix senseBIOPOLYMERS, Issue 4 2006Naoki Ousaka Abstract Chiral interaction of helical peptide with chiral molecule, and concomitant induction in its helix sense have been demonstrated in optically inactive nonapeptide (1) possessing Gly at its N-terminus: H,Gly,(,ZPhe,Aib)4,OCH3 (1: ,ZPhe = Z-dehydrophenylalanine; Aib = ,-aminoisobutyric acid). Spectroscopic measurements [mainly nuclear magnetic resonance (NMR) and circular diochroism (CD)] as well as theoretical simulation have been carried out for that purpose. Peptide 1 in the 310 -helix tends to adopt preferentially a right-handed screw sense by chiral Boc- L -amino acid (Boc: t -butoxycarbonyl). Induction in the helix sense through the noncovalent chiral domino effect should be derived primarily from the complex supported by the three-point coordination on the N-terminal sequence. Thus the 310 -helical terminus consisting of only ,-amino acid residues enables chiral recognition of the Boc-amino acid molecule, leading to modulation of the original chain asymmetry. Dynamics in the helix-sense induction also have been discussed on the basis of a low-temperature NMR study. Furthermore, the inversion of induced helix sense has been achieved through solvent effects. © 2006 Wiley Periodicals, Inc. Biopolymers 83:337,351, 2006 This article was originally published online as an accepted preprint. The "Published Online" date corresponds to the preprint version. You can request a copy of the preprint by emailing the Biopolymers editorial office at biopolymers@wiley.com [source] Use of local rank-based spatial information for resolution of spectroscopic images,,JOURNAL OF CHEMOMETRICS, Issue 5 2008Anna de Juan Abstract Spectroscopic images are singular chemical measurements that enclose chemical and spatial information about samples. Resolution of spectroscopic images is focused on the recovery of the pure spectra and distribution maps of the image constituents from the sole raw spectroscopic measurement. In image resolution, constraints are generally limited to non-negativity and the spatial information is generally not used. Local rank analysis methods have been adapted to describe the local spatial complexity of an image, providing specific pixel information. This local rank information combined with reference spectral information allows the identification of absent compounds in pixels with low compound overlap. The introduction of this information in the resolution process under the form of constraints helps to increase the performance of the resolution method and to decrease the ambiguity linked to the final solutions. Copyright © 2008 John Wiley & Sons, Ltd. [source] In vivo spectroscopy in dermatology: methods and new fields of applicationJOURNAL OF THE EUROPEAN ACADEMY OF DERMATOLOGY & VENEREOLOGY, Issue 1 2000K Liebold Abstract Background,The human skin is an easily accessible organ on which non-invasive examination methods can be applied. Remittance spectroscopy uses registration of the proportion of reflected light from the skin surface. Optical characteristics of skin are determined by scattering, reflection and absorption. The remittance is influenced by various test conditions and topography. Spectroscopic methods are applied for determination of microcirculation, measuring of erythema and pigmentation and in pharmacology and toxicology of applied drugs. Conclusion,The standardization of spectroscopic measurement of human skin is essential to reduce error sources. In future a better investigation of skin structures and molecules, which are responsible for optical characteristics of skin and a more precise evaluation of spectroscopic signals are necessary to get more information about the state of skin and to develop new fields of applications, such as early diagnosis of skin diseases or monitoring of metabolic processes. [source] Spectroscopy of solar neutrinosASTRONOMISCHE NACHRICHTEN, Issue 5 2010M. Wurm Abstract In the last years, liquid-scintillator detectors have opened a new window for the observation of low-energetic astrophysical neutrino sources. In 2007, the solar neutrino experiment Borexino began its data-taking in the Gran Sasso underground laboratory. High energy resolution and excellent radioactive background conditions in the detector allow the first-time spectroscopic measurement of solar neutrinos in the sub-MeV energy regime. The experimental results of the Beryllium 7 neutrino flux measurements (Arpesella et al. 2008b) as well as the prospects for the detection of solar Boron 8, pep and CNO neutrinos are presented in the context of the currently discussed ambiguities in solar metallicity. In addition, the potential of the future SNO+ and LENA experiments for high-precision solar neutrino spectroscopy will be outlined (© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] An in vivo model to evaluate the efficacy of barrier creams on the level of skin penetration of chemicalsCONTACT DERMATITIS, Issue 1 2006Alexa Teichmann The reservoir function and the barrier function are important properties of the skin. The reservoir function is dependent on the barrier function which, however, needs support by protective measures, in particular under working conditions. Barrier creams represent a possibility to protect the skin. In the present study, a method was developed to investigate the effectiveness of reservoir closure by different formulations. Patent Blue V in water was used as a model penetrant. Its penetration, with and without barrier cream treatment, was analyzed by tape stripping in combination with UV/VIS spectroscopic measurements. The investigations showed that the stratum corneum represents a reservoir for topically applied Patent Blue V in water. Furthermore, the barrier investigations showed that vaseline and bees wax form a 100% barrier on the skin surface. The third barrier cream, containing waxes and surfactant, only partially showed a protective effect against the penetration of Patent Blue V in water. Strong interindividual differences were observed for this barrier product. In conclusion, it was assumed that the application of barrier creams cannot replace other protective measures and should be maximally used to inhibit low-grade irritants or in combination with other protectants or in body areas where other protective measures are not applicable. [source] Studies on multiphased mixed crystals of NaCl, KCl and KICRYSTAL RESEARCH AND TECHNOLOGY, Issue 1 2009M. Priya Abstract Multiphased mixed crystals of NaCl, KCl and KI were grown by the melt method, for the first time. Densities and refractive indices of all the grown crystals were determined and used for the estimation of the composition in the crystal. Atomic absorption spectroscopic measurements were done to estimate the metal atom contents in the crystal. Lattice parameters and thermal parameters (Debye-Waller factor, mean square amplitude of vibration, Debye temperature and Debye frequency) were determined from the X-ray powder diffraction data. DC and AC electrical measurements were done at various temperatures ranging from 40 to 150°C. Activation energies were also estimated. The observed lattice parameters showed that the system exhibits three phases each nearly corresponds to NaCl, KCl and KI. The thermal and electrical parameters show a highly nonlinear bulk composition dependence. Results are reported. (© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Growth of big single crystals of a new magnetic superconducting double perovskite Ba2PrRu1,xCuxO6CRYSTAL RESEARCH AND TECHNOLOGY, Issue 2 2006S. M. Rao Abstract Single crystals of Ba2PrRu1,xCuxO6 with x = 0 to 0.2, have been grown from high temperature solutions of a mixture of PbO-PbF2 in the temperature range 1100,1200 °C. Thin crystals with mostly a hexagonal and triangular plate like habit measuring up to 1,2 mm across and 0.1,0.2 mm thick were obtained. The size, quality and morphology of the crystals were improved by varying the solution volume as well as additives like B2O3. Large crystals measuring up to 3 mm across and 0.3 to 0.5 mm thick were obtained with 5,7 wt% solute concentration and 0.51 wt% of B2O3. The ZFC curves exhibit a spin glass like behavior with x = 0 and a superconducting transition at 8 to 11 K depending on x = 0.05 to 0.1. The transition was also influenced by the growth temperature and post growth annealing. Powder x-ray diffraction, EDS and Raman spectroscopic measurements confirm the presence of Cu in the crystals. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Prussian Blue Dispersed Sphere Catalytic Labels for Amplified Electronic Detection of DNAELECTROANALYSIS, Issue 3 2008Siriwan Suwansa-ard Abstract A highly sensitive electrochemical DNA hybridization assay using Prussian blue (PB)-modified polymeric spheres as the oligonculeotide labeling tag is described. The sandwich assay relies on a secondary nucleic-acid probe functionalized with polystyrene beads loaded with numerous Prussian blue nanoparticles. The very strong catalytic activity of the captured PB ,artificial peroxidase' tag towards the reduction of hydrogen peroxide, along with the encapsulation of numerous catalytic particles onto polymeric beads, allows amperometric detection of the DNA target down to the 50,fM level (2.5,amol). Imaging and spectroscopic measurements are used to characterize the PB-tagged polystyrene beads. Such coupling of PB catalytic labels with polymeric carrier beads offers great promise for amplified transduction of different biomolecular interactions. [source] Recent Advances in Electrochemical Enzyme ImmunoassaysELECTROANALYSIS, Issue 21 2005María Díaz-González Abstract Enzyme immunoassays (EIAs) are currently the predominant analytical technique for the quantitative determination of a broad variety of analytes in clinical, medical, biotechnological, and environmental significance. Although the most common detection methods for EIAs are based on spectroscopic measurements, electrochemical techniques, due to their high sensitivity, selectivity, simplicity and low cost, have emerged as a very attractive alternative to carry out the detection step in this kind of assays. The intention of this review is to cover the progress and development in integrating electrochemical detection methods with EIAs, over the past five years. [source] Heavy Metals in Matrices of Food Interest: Sequential Voltammetric Determination at Trace and Ultratrace Level of Copper, Lead, Cadmium, Zinc, Arsenic, Selenium, Manganese and Iron in MealsELECTROANALYSIS, Issue 18 2004Clinio Locatelli Abstract The voltammetric methods are very suitable and versatile techniques for the simultaneous metal determination in complex matrices. The present work, regarding the sequential determination of Cu(II), Pb(II), Cd(II), Zn(II) by square-wave anodic stripping voltammetry (SWASV), As(III), Se(IV) by square-wave cathodic stripping voltammetry (SWCSV) and Mn(II), Fe(III) by square-wave voltammetry (SWV) in matrices involved in foods and food chain as wholemeal, wheat and maize meal, are an interesting example of the possibility to sequentially determine each single element in real samples. Besides the set up of the analytical method, particular attention is aimed either at the problem of possible signal interference or to show that, using the peak area Ap as instrumental datum, it is possible to achieve lower limits of detection. The analytical procedure was verified by the analysis of the standard reference materials: Wholemeal BCR-CRM 189, Wheat Flour NIST-SRM 1567a and Rice Flour NIST-SRM 1568a. Precision, as repeatability, and accuracy, expressed as relative standard deviation and relative error, respectively, were lower than 6% in all cases. In the presence of reciprocal interference, the standard addition method considerably improved the resolution of the voltammetric technique. Once set up on the standard reference materials, the analytical procedure was transferred and applied to commercial meals sampled on market for sale. A critical comparison with spectroscopic measurements is also discussed. [source] Immobilized Cytochrome c Sensor in Organic/Aqueous Media for the Characterization of Hydrophilic and Hydrophobic AntioxidantsELECTROANALYSIS, Issue 18 2003Moritz Beissenhirtz Abstract A method for the characterization of antioxidants is introduced, which allows the measurement of pure hydrophilic and hydrophobic substances as well as complex cosmetic creams. The sensor is based on cytochrome c covalently immobilized on a gold wire electrode working in mixtures of phosphate buffer and organic solvents. It is combined with a superoxide generating enzyme system. The decrease of the superoxide concentration in the test solution by the added antioxidants is detected and used for the quantification of their antioxidative efficiency. Electrochemical properties of immobilized cytochrome c, such as formal potential and heterogeneous electron transfer rate constant, have been investigated in mixtures of aqueous buffer and DMSO, methanol, butanediol, and THF. The maximum organic solvent content for quasi-reversible electrode behavior was correlated to spectroscopic measurements. The activity of the radical producing enzyme in such media was determined and the radical generation characterized. The antioxidative properties of pure substance such as ascorbic acid and Biochanin A as well as of five anti-ageing cosmetic creams were studied. This showed also the influence of matrix composition on the efficiency of antioxidative supplements. [source] Optical, Magnetic and Structural Properties of the Spin-Crossover Complex [Fe(btr)2(NCS)2]·H2O in the Light-Induced and Thermally Quenched Metastable StatesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 36 2007Vincent Legrand Abstract [Fe(btr)2(NCS)2]·H2O [btr = 4,4,-bis(1,2,4-triazole)] is thearchetype of highly cooperative and low-dimensional spin-crossover complexes, which exhibit low-spin (LS) to high-spin (HS) light-induced conversion at very low temperature. The structural reorganizations related to the light-induced and thermally induced LS,HS transitions were characterized by single-crystal X-ray diffraction below the relaxation temperature (T = 15 K < TLIESST) and at 130 K within the thermal hysteresis loop. We show that the LIESST and thermal spin transitions lead to the same structural variations, namely an elongation of the Fe,N bonds by 0.18 Å (Fe,NNCS) and 0.20 Å (Fe,Nbtr), on going from LS to HS, together with a reorientation of the NCS group by nearly 13°. The atomic displacement amplitudes, derived from the crystal structures, indicate lattice vibration modes of larger amplitudes and correlatively lower vibration frequencies in the HS state. The deformation of the crystal lattice as a function of temperature and laser excitation was quantitatively analyzed in terms of the HS and LS thermal-expansion (,HS and ,LS) and spin-transition spontaneous-strain (,) tensors. The eigendirections and eigenvalues of the , and , tensors correlate well with the weak and strong interactions in the solid and are responsible for the high cooperativity and low-dimensional behaviour. Magnetic and spectroscopic measurements were performed in all the different spin states and related to the structural findings. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] A Series of Lithium Rare Earth Polyphosphates [LiLn(PO3)4] (Ln = La, Eu, Gd) and Their Structural, Optical, and Electronic PropertiesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 2 2007Jing Zhu Abstract The structural, optical, and electronic properties of a series of lithium rare earth polyphosphates [LiLn(PO3)4] [Ln = La (1), Eu (2), Gd (3)] have been investigated by means of single-crystal X-ray diffraction, elemental analyses, and spectroscopic measurements, as well as calculations of energy-band structures, density of states, and optical response functions by density functional methods. These LiLn(PO3)4 systems are monoclinic with space group C2/c and Z = 4. Their unit-cell parameters decrease as the ionic radius of Ln3+ decreases (La3+ > Eu3+ > Gd3+). Both (PO4)3, zig-zag chains and infinite chains formed by the alternate connection of LnO8 polyhedra and LiO4 tetrahedra run parallel to the b -axis in the structure. The energy-band structures, density of states, the chemical bonds, and optical properties have been investigated by density functional methods for some of the title compounds. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Exchange Interactions at the Supramolecular Level , Synthesis, Crystal Structure, Magnetic Properties, and EPR Spectra of [Mn(MAC)(TCNQ)2] (MAC = Pentaaza Macrocyclic Ligand; TCNQ·, = Radical Anion of 7,7,8,8-Tetracyano- p -quinodimethane)EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 10 2003Augustin M. Madalan Abstract The reaction between [Mn(MAC)(H2O)2]Cl2·4H2O and LiTCNQ (MAC = 2,13-dimethyl-3,6,9,12,18-pentaazabicyclo[12.3.1]octadeca-1(18),2,12,14,16-pentaene) affords a complex with the formula [Mn(MAC)(TCNQ)2] (1), whose crystal structure has been determined. Its structure consists of neutral mononuclear entities. The manganese(II) ion is heptacoordinated, with a pentagonal bipyramidal geometry. The apical positions are occupied by the TCNQ·, radicals, while the macrocyclic ligand is coordinated at the equatorial positions. The seven Mn,N distances range from 2.273(3) to 2.301(6) Å. The strong intermolecular ,,, stacking interactions between the TCNQ radicals (3.2 Å) leads to weave-like infinite chains, which propagate along the crystallographic c axis. The cryomagnetic investigation of 1 revealed a weak intermolecular antiferromagnetic coupling of the Mn2+ ions (J = ,0.18 cm,1), which is mediated by the diamagnetic (TCNQ)22, pairs resulting from the stacking interactions in the crystal. The intermolecular exchange interaction between the Mn2+ ions was further confirmed by variable temperature EPR spectroscopic measurements [|J| = 0.15(5) cm,1], which have been carried out in both the X and Q bands. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Close Proximity Dibenzo[a,c]phenazine,Fullerene Dyad: Synthesis and Photoinduced Singlet Energy TransferEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 18 2010Rajeev K. Dubey Abstract A dibenzo[a,c]phenazine,fullerene (DBPZ-C60) dyad in which two chromophores are linked in close proximity to each other has been synthesized and studied in detail by optical spectroscopy to explore a new energy donor,acceptor system. The dyad was prepared by Prato reaction between 11-formyldibenzo[a,c]phenazine and fullerene. 3,5-Di- tert -butylbenzyl group was introduced onto the fulleropyrrolidine unit to achieve adequate solubility of the dyad. A thorough study of the photophysical properties of the dyad and relevant reference compounds, performed by means of steady state and time resolved spectroscopic measurements, has revealed the presence of highly efficient (ca. 98,%) and extremely fast (ken = 5,×,1011 s,1) intramolecular photoinduced singlet,singlet energy-transfer process from singlet excited state of the DBPZ moiety to fullerene. In both polar and nonpolar environment transduction of singlet excited state energy governs the excited state deactivation, but the efficiency and rate of energy transfer were found to be higher in nonpolar solvents in comparison to polar. The DBPZ singlet excited state decays within 2 and 4.7 ps in toluene andbenzonitrile, respectively, via singlet,singlet energy transfer to produce a fullerene singlet excited state which decays with a life time of 1.5 ns to give a very long-lived fullerene triplet state as final populated excited state. [source] The Origin of the High Voltage in DPM12/P3HT Organic Solar CellsADVANCED FUNCTIONAL MATERIALS, Issue 16 2010Antonio Sánchez-Díaz Abstract Organic solar cells made using a blend of DPM12 and P3HT are studied. The results show that higher Voc can be obtained when using DPM12 in comparison to the usual mono-substituted PCBM electron acceptor. Moreover, better device performances are also registered when the cells are irradiated with sun-simulated light of 10,50 mW cm,2 intensity. Electrochemical and time-resolved spectroscopic measurements are compared for both devices and a 100-mV shift in the density of states (DOS) is observed for DPM12/P3HT devices with respect to PCBM/P3HT solar cells and slow polaron-recombination dynamics are found for the DPM12/P3HT devices. These observations can be directly correlated with the observed increase in Voc, which is in contrast with previous results that correlated the higher Voc with different ideality factors obtained using dark-diode measurements. The origin for the shift in the DOS can be correlated to the crystallinity of the blend that is influenced by the properties of the included fullerene. [source] Functional Chromium Wheel-Based Hybrid Organic,Inorganic Materials for Dielectric ApplicationsADVANCED FUNCTIONAL MATERIALS, Issue 20 2009Vito Di Noto Abstract The first example of organic,inorganic hybrid materials based on the embedding of a chromium,nickel wheel cluster {[(n-C3H7)2NH2]- [Cr7NiF8(O2C4H5)16]} (Cr7Ni) into poly(methyl methacrylate) (PMMA) and the characterization of the dielectric properties of the obtained material is described. By an optimized copolymerization of the methacrylate-functionalized chromium,nickel wheel with methyl methacrylate in a cluster/monomer 1:200 molar mixture, a homogeneous hybrid material CrNi_MMA200 is obtained. The electrical responses of the non-doped PMMA and of the hybrid material were studied by broadband dielectric spectroscopy (BDS) from 0.01,Hz to 10,MHz and over the temperature range of 5,115,°C. The permittivity profiles reveal two relaxation peaks in the materials, which correspond to the , and , relaxation modes of the PMMA matrix. The position of these modes shifts toward higher frequencies as temperature increases. BDS is a powerful tool revealing the intimate miscibility of the various components of the hybrid material, thus indicating that, on a molecular scale, the material proposed is a homogeneous system. Finally, a value of the dielectric constant of 2.9 at 25,°C and 1,kHz is determined. This value is noticeably lower than the value of 3.2 obtained for pristine PMMA prepared following the same synthesis protocol. Thus, these results classify the hybrid CrNi_MMA200 as an appealing starting material for the development of dielectric polymeric layers for the development of innovative capacitors, transistors, and other microelectronic devices. The vibrational properties of the hybrid materials are investigated by Fourier-transform infrared (FT-IR) and Raman spectroscopy, whereas the thermal behavior is analyzed by thermogravimetric analysis (TGA). Swelling experiments are used to qualitatively evaluate the crosslinking density of the hybrid materials. The integrity of the wheels once embedded in the macromolecular backbone is confirmed by extended X-ray absorption fine structure (EXAFS) and electron spin resonance (EPR) spectroscopic measurements. [source] Quantum Confinement in Self-Assembled Bioinspired Peptide HydrogelsADVANCED MATERIALS, Issue 21 2010Nadav Amdursky The self-assembly process of peptide fibrils is followed by spectroscopic measurements, which show that a quantum confinement (QC) nanocrystal structure is formed within the peptide fibrils as they assemble into a hydrogel. The optical and electronic properties of this first bioorganic-inspired QC structure (see figure) are demonstrated to be related to the QC effect. [source] Study of association thermodynamics between crystal violet and sodium bis(2-ethylhexyl)sulfosuccinate and kinetics of basic fading of crystal violet in microemulsionsINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 6 2008Zhi Yun Chen The thermodynamics of the association between 4,4,,4,-tris(dimethyl-amino)triphenylmethyl chloride (crystal violet or CV) and sodium bis(2-ethylhexyl)-sulfosuccinate (aerosol OT or AOT) in water/AOT/n -decane microemulsion and the kinetics of the basic hydrolysis of CV in a water-in-oil microemulsion were investigated by UV,vis spectroscopic measurements. An association model of CV and AOT was used to analyze the experimental data to obtain the association constants at various temperatures. By taking the association into account, the "actual" rate constants and the activation energies of the basic hydrolysis of CV in the media of water/AOT/oil were obtained. The difference in thermodynamics and kinetics between the two media of water/AOT/n -decane and water/AOT/isooctane is discussed. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 294,300, 2008 [source] The kinetics of complex formation between Ti(IV) and hydrogen peroxideINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 8 2007Daniel W. O'Sullivan The kinetics of the formation of the titanium-peroxide [TiO2+2] complex from the reaction of Ti(IV)OSO4 with hydrogen peroxide and the hydrolysis of hydroxymethyl hydroperoxide (HMHP) were examined to determine whether Ti(IV)OSO4 could be used to distinguish between hydrogen peroxide and HMHP in mixed solutions. Stopped-flow analysis coupled to UV-vis spectroscopy was used to examine the reaction kinetics at various temperatures. The molar absorptivity (,) of the [TiO2+2] complex was found to be 679.5 ± 20.8 L mol,1 cm,1 at 405 nm. The reaction between hydrogen peroxide and Ti(IV)OSO4 was first order with respect to both Ti(IV)OSO4 and H2O2 with a rate constant of 5.70 ± 0.18 × 104 M,1 s,1 at 25°C, and an activation energy, Ea = 40.5 ± 1.9 kJ mol,1. The rate constant for the hydrolysis of HMHP was 4.3 × 10,3 s,1 at pH 8.5. Since the rate of complex formation between Ti(IV)OSO4 and hydrogen peroxide is much faster than the rate of hydrolysis of HMHP, the Ti(IV)OSO4 reaction coupled to time-dependent UV-vis spectroscopic measurements can be used to distinguish between hydrogen peroxide and HMHP in solution. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 457,461, 2007 [source] Preparation and study of cellulose acetate membranes modified with linear polymers covalently bonded to Starburst polyamidoamine dendrimersJOURNAL OF APPLIED POLYMER SCIENCE, Issue 5 2008J. Ledesma-García Abstract Novel ion-selective membranes were prepared by means of the noncovalent modification of a cellulose acetate (CA) polymer with either poly(ethylene- alt -maleic anhydride) or poly(allylamine hydrochloride) chains covalently linked to Starburst amine-terminated polyamidoamine (PAMAM) dendrimers generations 4 and 3.5, respectively. Linear polymer incorporation within the porous CA membrane was performed with mechanical forces, which resulted in modified substrates susceptible to covalent adsorption of the relevant dendritic materials via the formation of amide bonds with a carbodiimide activation agent. The membranes thus prepared were characterized by chemical, physical, and spectroscopic measurements, and the results indicate that the dendrimer peripheral functional groups were the species that participated in the ion-exchange events. The prepared materials were also evaluated for their ion-exchange permeability with sampled current voltammetry experiments involving cationic and anionic species {[Ru(NH3)6]3+ and [Fe(CN6)]3,, respectively} as redox probe molecules under different pH conditions. As expected, although permeability was favored by opposite charges between the dendrimer and the electroactive probe, a clear blocking effect took place when the charge in the dendritic polymer and the electroactive complex was the same. Electrochemical impedance spectroscopy measurements, on the other hand, showed that the PAMAM-modified membranes were characterized by good selectivity and low resistance values for multivalent ions compared to a couple of commercial ion-exchange membranes. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] Influence of carbohydrates on stability of papain in aqueous tetrahydrofuran mixtureJOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 1 2009András Szabó Abstract BACKGROUND: The use of enzymes in organic solvents has extended the scale of their practical applications. Papain has been widely used in chemical syntheses because of its broad substrate specificity. The aim of the present study was to improve the stability of papain in aqueous tetrahydrofuran (THF) by using different saccharides. The effects of these carbohydrates on the structure of papain were followed by means of circular dichroism (CD) and fluorescence spectroscopic measurements. RESULTS: In contrast with most organic solvents, 60% (i.e. 600 mL L,1) THF practically inactivated the enzyme within 30 min. Sugars protected papain from THF-induced inactivation in the sequence D -ribose > D -fructose > D -glucose > D -saccharose > D -raffinose. Ribose at 1.6 mol L,1 proved the most effective stabiliser: in 60% THF in the presence of ribose, papain preserved about 55% of its initial activity after 2 h. Fluorescence and near-UV CD spectroscopic measurements revealed local changes in the papain conformation. With decrease in the free amino group content of the enzyme, protein-carbohydrate interactions (Schiff base formation) were detected. CONCLUSION: These results demonstrate that the catalytic activity and stability of papain may be increased in aqueous THF by using different carbohydrates, when a more compact structure of the enzyme is formed. Copyright © 2008 Society of Chemical Industry [source] Empirical preprocessing methods and their impact on NIR calibrations: a simulation studyJOURNAL OF CHEMOMETRICS, Issue 2 2005S. N. Thennadil Abstract The extraction of chemical information from dense particulate suspensions, such as industrial slurries and biological suspensions, using near-infrared (NIR) spectroscopic measurements is complicated by sample-to-sample path length variations due to light scattering. Empirical preprocessing techniques such as multiplicative scatter correction (MSC), extended MSC and derivatives have been applied to remove these effects and in some cases have shown promise. While the performance of these techniques and other related approaches is known to depend on the nature and extent of the variations and on the measurement configuration, detailed investigations into the efficacy of these approaches under various conditions have not been previously undertaken. The main obstacle to carrying out such investigations has been the lack of, and the difficulty in obtaining, an accurate and comprehensive experimental data set. In this work, simulations that generate ,actual' measurements were carried out to obtain ,experimental' spectroscopic data on particulate systems. This was achieved by solving the exact transport equation for light propagation. A model system comprising four chemical components with one consisting of spherical submicron particles was considered. Total diffuse transmittance and reflectance data generated through simulations for moderate particle concentrations were used as the basis for examining the effect of particle size variations and measurement configurations on the efficacy of a number of preprocessing techniques in enhancing the performance of partial least squares (PLS) models for predicting the concentration of one of the non-scattering chemical species. Additionally, a form of extended multiplicative signal correction based on considerations arising from fundamental light scattering theory is proposed and found to perform better than the other techniques for the cases considered in the study. Copyright © 2005 John Wiley & Sons, Ltd. [source] A comparison of methods for analysing regression models with both spectral and designed variablesJOURNAL OF CHEMOMETRICS, Issue 10 2004Kjetil Jørgensen Abstract In many situations one performs designed experiments to find the relationship between a set of explanatory variables and one or more responses. Often there are other factors that influence the results in addition to the factors that are included in the design. To obtain information about these so-called nuisance factors, one can sometimes measure them using spectroscopic methods. The question then is how to analyze this kind of data, i.e. a combination of an orthogonal design matrix and a spectroscopic matrix with hundreds of highly collinear variables. In this paper we introduce a method that is an iterative combination of partial least squares (PLS) and ordinary least squares (OLS) and compare its performance with other methods such as direct PLS, OLS and a combination of principal component analysis and least squares. The methods are compared using two real data sets and using simulated data. The results show that the incorporation of external information from spectroscopic measurements gives more information from the experiment and lower variance in the parameter estimates. We also find that the introduced algorithm separates the information from the spectral and design matrices in a nice way. It also has some advantages over PLS in showing lower bias and being less influenced by the relative weighting of the design and spectroscopic variables. Copyright © 2005 John Wiley & Sons, Ltd. [source] Synthesis and physicochemical properties of new 1N o -(m - and p -) bromobenzyl substituted derivatives of 5-(aminodialkyl)methylcytosineJOURNAL OF HETEROCYCLIC CHEMISTRY, Issue 5 2007Dorota Prukala Simple alkylation of 5-(aminodialkyl)methylcytosine a-d gives twelve new, potentially biologically active 1N o -(m - or p -) bromobenzyl derivatives of 5-substituted cytosine 1-12 with high regioselectivity. The structures of all compounds have been confirmed by elemental analysis, IR, 1H NMR and 13C NMR spectroscopic measurements. [source] Synthesis of some pyrazole-3-carboxylic acid-hydrazide and pyrazolopyridazine compoundsJOURNAL OF HETEROCYCLIC CHEMISTRY, Issue 1 2005Furan-2,3-diones 1a-c react with various hydrazines 2a-c under different conditions to yield the pyrazole-3-carboxylic acid-hydrazide 3a-d. Cyclocondensation reactions of 1a or 7 with phenylhydrazine lead to derivatives of pyrazolo[3,4- d]pyridazinones 6 and 8, respectively. The structures of all products were confirmed by elemental analysis, IR, 1H- and 13C-NMR spectroscopic measurements. [source] Interaction between amyloid ,-protein aggregates and membranesJOURNAL OF PEPTIDE SCIENCE, Issue 10 2004Atsuko Kakio Abstract The conversion of soluble, nontoxic amyloid ,-protein (A,) to aggregated, toxic A, rich in ,-sheet structures is considered to be the key step in the development of Alzheimer's disease. Therefore, extensive studies have been carried out on the mechanisms involved in A, aggregation and the characterization of A, aggregates formed in aqueous solutions mimicking biological fluids. On the other hand, several investigators pointed out that membranes play an important role in A, aggregation. However, it remains unclear whether A, aggregates formed in solution and membranes are identical and whether the former can bind to membranes. In this study, using a dye-labeled A,-(1,40) as well as native A,-(1,40), the properties of A, aggregates formed in buffer and raft-like membranes composed of monosialoganglioside GM1/cholesterol/sphingomyelin were compared. Fourier transform infrared spectroscopic measurements suggested that A, aggregates formed in buffer and in membranes have different ,-sheet structures. Fluorescence experiments revealed that A, aggregated in buffer did not show any affinity for membranes. Copyright © 2004 European Peptide Society and John Wiley & Sons, Ltd. [source] Investigation of penetratin peptides Part 1.JOURNAL OF PEPTIDE SCIENCE, Issue 4 2002The environment dependent conformational properties of penetratin, two of its derivatives Abstract The homeodomain, the DNA-binding domain of Antennapedia homeoprotein, is composed of three ,-helices and one ,-turn between helices II and III. Its third helix from the N -terminal (helix III) can translocate through the cell membrane into the nucleus and can be used as an intracellular vehicle for the delivery of oligopeptides and oligonucleotides. To the best of our knowledge, this helix III, called penetratin, which consists of 16 amino acids, is internalized by cells in a specific, non-receptor-mediated manner. For a better understanding of the mechanism of the transfer, the structure of penetratin was examined in both extracellular matrix-mimetic and membrane-mimetic environments; 1H-NMR and CD spectroscopic measurements were performed in mixtures of TFE/water with different ratios. The molecular conformations of two analogue peptides [(6,14-Phe)-penetratin and a 12 amino acid penetratin derivative (peptide 3)] were also studied. An atomic level comprehensive analysis of penetratin and its two analogues was performed. In a membrane-mimetic solvent system (TFEd2/water = 9 : 1), on the basis of 553 distance restraints, the 4,12 region of penetratin exhibits a bent, irregular helical structure on NMR examination. Interactions between hydrophobic amino acid residues in conjunction with H-bonds stabilize the secondary structure of the molecule. Thus, both derivatives adopt a helix-like conformation. However, while (6,14-Phe)-penetratin displays both ,-helical and 310 -helical features, the structure of peptide 3 is predominantly a 310 -helix. Of the three peptides, surprisingly (6,14-Phe)-penetratin has the largest helical content. An increase in the polarity of the molecular environment gradually disintegrates these helix-like secondary structures. In a highly aqueous molecular system (TFEd2/water = 1 : 9), the fast exchange of multiple conformers leads to too few distance restraints being extracted, therefore the NMR structures can no longer be determined. The NMR data show that only short-range order can be traced in these peptides. Under these conditions, the molecules adopt nascent helix-like structures. On the other hand, CD spectra could be recorded at any TFE/water ratio and the conformational interconversion could therefore be monitored as a function of the polarity of the molecular environment. The CD data were analysed comprehensively by the quantitative deconvolution method (CCA+). All three penetratin peptides display helical conformational features in a low dielectric medium, with significant differences as a function of their amino acid composition. However, these conformational features are gradually lost during the shift from an apolar to a polar molecular environment. Copyright © 2002 European Peptide Society and John Wiley & Sons, Ltd. [source] Anomalous concentration dependence of the coordination behavior of Cl, ion to Ln3+ ion (Ln3+ = rare-earth ion) in anhydrous LnCl3 alcohol solutionsJOURNAL OF RAMAN SPECTROSCOPY, Issue 7 2007Y. Yoshimura Abstract Raman spectroscopic measurements were carried out for the anhydrous LnCl3·20ROH·XLiCl solutions (Ln3+ = La3+, Lu3+, X = 0,3; ROH = MeOH, EtOH, n -PrOH) in the liquid state. The salt concentration (X) dependence of the wavenumber for the Ln,Cl stretching Raman band (,Ln,Cl) is examined in conjunction with the formation of chloro-rare-earth complexes. We have obtained very intriguing results including the fact that the chloro complexations of the middle rare-earth ions (e.g. gadolinium, holmium ions, etc.) in the MeOH and EtOH solutions show peculiar behavior with regard to the salt concentration dependence: the ,Ln,Cl wavenumber increases with the increasing chloride concentration. However, the ,Ln,Cl wavenumbers of the light and heavy rare-earth (e.g. lanthanum, lutetium, etc.) salt solutions show normal behavior; i.e. ,Ln,Cl decreases with the increasing chloride concentration. On the other hand, in the n -PrOH solutions, the ,Ln,Cl frequency in the solutions of all the rare-earth elements exhibits a normal behavior. We now present a possible mechanism for this anomalous concentration dependence of coordination of Cl, ions to Ln3+ ions in anhydrous LnCl3 alcohol solutions. Copyright © 2007 John Wiley & Sons, Ltd. [source] | ||||||||||||||||||||||||||||