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Paramagnetic Resonance Spectroscopy (paramagnetic + resonance_spectroscopy)
Kinds of Paramagnetic Resonance Spectroscopy Selected AbstractsHigh-Temperature Propagation and Termination Kinetics of Styrene to High Conversion Investigated by Electron Paramagnetic Resonance SpectroscopyMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 6 2004Per B. Zetterlund Abstract Summary: The free radical bulk polymerization of styrene at 120,°C has been investigated over almost the entire conversion range using electron paramagnetic resonance spectroscopy, Fourier-transform near-infrared spectroscopy and gel permeation chromatography. The free radical concentration went through a sharp maximum that coincided with the peak in the rate of polymerization during the gel effect, and shifted to higher conversion with increasing initiator concentration. The termination rate coefficient (kt), decoupled from the initiator efficiency (f) by use of the instantaneous degree of polymerization, remained close to constant up to as high as approximately 80% conversion, at which a dramatic decrease occurred. Both the propagation rate coefficient (kp) and f fell orders of magnitude near 80% conversion in spite of the temperature being above the glass transition temperature of the system. The value of kp increased with the initiator concentration at a given conversion in the highest (diffusion-controlled) conversion range. Termination rate coefficient (kt) versus conversion for bulk free radical polymerization of St initiated by TBP at 120,°C. [TBP],=,0.15 (,), 0.10 (,) and 0.05 M (). [source] Electrochemical Nitric Oxide Sensors for Biological Samples , Principle, Selected Examples and ApplicationsELECTROANALYSIS, Issue 1 2003Fethi Bedioui Abstract The discoveries made in the 1980s that NO could be synthesized by mammalian cells and could act as physiological messenger and cytotoxic agent had elevated the importance of its detection. The numerous properties of NO, that enable it to carry out its diverse functions, also present considerable problems when attempting its detection and quantification in biological systems. Indeed, its total free concentration in physiological conditions has been established to be in nanomolar range. Thus, detection of nitric oxide remains a challenge, pointing out the difficult dual requirements for specificity and sensitivity. Exception made for the electrochemical techniques, most of the approaches (namely UV-visible spectroscopy, fluorescence, electron paramagnetic resonance spectroscopy) use indirect methods for estimating endogenous NO, relying on measurements of secondary species such as nitrite and nitrate or NO-adducts. They also suffer from allowing only ex situ measurements. So, the only strategies that allow a direct and in vivo detection of NO are those based on the use of ultramicroelectrodes. The reality is that surface electrode modification is needed to make the ultramicroelectrode material selective for NO. Therefore, the design of modified electrode surfaces using organized layers is very attractive and provides the ideal strategy. This review addresses a global description of the various approaches that have involved chemically modified microelectrodes specially designed for the electrochemical detection of NO in biological media. Selected significant examples of applications in biological tissues are also reported in order to highlight the importance of this approach in having new insights into the modulatory role of NO in physiology and pathophysiology. [source] High-Temperature Propagation and Termination Kinetics of Styrene to High Conversion Investigated by Electron Paramagnetic Resonance SpectroscopyMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 6 2004Per B. Zetterlund Abstract Summary: The free radical bulk polymerization of styrene at 120,°C has been investigated over almost the entire conversion range using electron paramagnetic resonance spectroscopy, Fourier-transform near-infrared spectroscopy and gel permeation chromatography. The free radical concentration went through a sharp maximum that coincided with the peak in the rate of polymerization during the gel effect, and shifted to higher conversion with increasing initiator concentration. The termination rate coefficient (kt), decoupled from the initiator efficiency (f) by use of the instantaneous degree of polymerization, remained close to constant up to as high as approximately 80% conversion, at which a dramatic decrease occurred. Both the propagation rate coefficient (kp) and f fell orders of magnitude near 80% conversion in spite of the temperature being above the glass transition temperature of the system. The value of kp increased with the initiator concentration at a given conversion in the highest (diffusion-controlled) conversion range. Termination rate coefficient (kt) versus conversion for bulk free radical polymerization of St initiated by TBP at 120,°C. [TBP],=,0.15 (,), 0.10 (,) and 0.05 M (). [source] Influence of iodine molecule adsorption on electronic properties of porous silicon studied by FTIR and EPR spectroscopyPHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 6 2007L. A. Osminkina Abstract The infrared absorption and electron paramagnetic resonance spectroscopy are used for studying the effect of adsorption of iodine (I2) molecules, strong acceptors of electrons, on the electronic properties of silicon nanocrystals in micro- and mesoporous silicon layers with different types of doping impurities. It is found that the concentration of free charge carries (holes) in silicon nanocrystals, obtained by electrochemical etching of p-type and n-type silicon wafers, sharply increases in the presence of I2 molecules. At the same time the decrease of the dangling silicon bonds (Pb -centers) concentration is observed. A microscopic model proposed for explaining this effects presumes the formation of donor-acceptor pairs (Pb1+ -I2,), and shallow acceptor states on the porous silicon surface which, together with the initial dopant and surface defect states, specify the charge carrier type and concentration in the silicon nanocrystals. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Understanding the kinetics and network formation of dimethacrylate dental resinsPOLYMERS FOR ADVANCED TECHNOLOGIES, Issue 6 2001Lale G. Lovell Abstract Dimethacrylate monomers are commonly used as the organic phase of dental restorative materials but many questions remain about the underlying kinetics and network formation in these highly crosslinked photopolymer systems. Several novel experimental and modeling techniques that have been developed for other multifunctional (meth)acrylates were utilized to gain further insight into these resin systems. Specifically, this work investigates the copolymerization behavior ofbis-GMA (2,2-bis[p-(2-hydroxy-3-methacryloxyprop-1-oxy)-phenyl]propane) and TEGDMA (triethylene glycol dimethacrylate), two monomers typically used for dental resin formulations. Near-infrared spectroscopy, electron paramagnetic resonance spectroscopy, as well as dynamic mechanical and dielectric analysis were used to characterize the kinetics, radical populations, and structural properties of this copolymer system. In addition, a kinetic model is described that provides valuable information about the network evolution during the formation of this crosslinked polymer. The results of these numerous studies illustrate that all of the aforementioned techniques can be readily applied to dental resin systems and consequently can be used to obtain a wealth of information about these systems. The application of these techniques provides insight into the complex polymerization kinetics and corresponding network formation, and as a result, a more complete understanding of the anomolous behaviors exhibited by these systems, such as diffusion controlled kinetics and conversion dependent network formation, is attained. Copyright © 2001 John Wiley & Sons, Ltd. [source] The hemoglobins of the trematodes Fasciola hepatica and Paramphistomum epiclitum: A molecular biological, physico-chemical, kinetic, and vaccination studyPROTEIN SCIENCE, Issue 10 2008Sylvia Dewilde Abstract The trematode Fasciola hepatica (Fa.he.) is a common parasite of human and livestock. The hemoglobin (Hb) of Fa.he., a potential immunogen, was chosen for characterization in the search for an effective vaccine. Characterization of trematode Hbs show that they are intracellular single-domain globins with the following remarkable features: (1) Fa.he. expresses two Hb isoforms that differ at two amino acid sites (F1: 119Y/123Q; F2: 119F/123L). Both isoforms are monoacetylated at their N-termini; (2) the genes coding for Fa.he. and Paramphistomum epiclitum (Pa.ep.) Hbs are interrupted by two introns at the conserved positions B12.2 and G7.0.; (3) UV/VIS and resonance Raman spectroscopy identify the recombinant Fa.he. HbF2 as a pentacoordinated high-spin ferrous Hb; (4) electron paramagnetic resonance spectroscopy of cyano-met Fa.he. HbF2 proves that the endogenously bound imidazole has no imidazolate character; (5) the major structural determinants of the globin fold are present, they contain a TyrB10/TyrE7 residue pair on the distal side. Although such distal-site pair is a signature for high oxygen affinity, as shown for Pa.ep. Hb, the oxygen-binding rate parameters for Fa.he. Hb are intermediate between those of myoglobin and those of other trematode Hbs; (6) the three-dimensional structure of recombinant Fa.he. HbF2 from this study closely resembles the three-dimensional structure of Pa.ep. determined earlier. The set of distal-site polar interactions observed in Pa.ep. Hb is matched with small but significant structural adjustments; (7) despite the potential immunogenic character of the fluke Hb, vaccination of calves with recombinant Fa.he. HbF2 failed to promote protection against parasitic infection. [source] Structural Investigation of a High-Affinity MnII Binding Site in the Hammerhead Ribozyme by EPR Spectroscopy and DFT Calculations.CHEMBIOCHEM, Issue 10 2003Effects of Neomycin B on Metal-Ion Binding Abstract Electron paramagnetic resonance spectroscopy and density functional theory methods were used to study the structure of a single, high-affinity MnIIbinding site in the hammerhead ribozyme. This binding site exhibits a dissociation constant Kdof 4.4 ,M in buffer solutions containing 1,M NaCl, as shown by titrations monitored by continuous wave (cw) EPR. A combination of electron spin echo envelope modulation (ESEEM) and hyperfine sublevel correlation (HYSCORE) experiments revealed that the paramagnetic manganese(II) ion in this binding site is coupled to a single nitrogen atom with a quadrupole coupling constant,of 0.7 MHz, an asymmetry parameter,of 0.4, and an isotropic hyperfine coupling constant of Aiso(14N)=2.3 MHz. All three EPR parameters are sensitive to the arrangement of the MnIIligand sphere and can therefore be used to determine the structure of the binding site. A possible location for this binding site may be at the G10.1, A9 site found to be occupied by MnIIin crystals (MacKay et al., Nature 1994, 372, 68 and Scott et al., Science 1996, 274, 2065). To determine whether the structure of the binding site is the same in frozen solution, we performed DFT calculations for the EPR parameters, based on the structure of the MnIIsite in the crystal. Computations with the BHPW91 density function in combination with a 9s7p4d basis set for the manganese(II) center and the Iglo-II basis set for all other atoms yielded values of,(14N)=+0.80 MHz, ,=0.324, and Aiso(14N)=+2.7 MHz, in excellent agreement with the experimentally obtained EPR parameters, which suggests that the binding site found in the crystal and in frozen solution are the same. In addition, we demonstrated by EPR that MnIIis released from this site upon binding of the aminoglycoside antibiotic neomycin B (Kd=1.2 ,M) to the hammerhead ribozyme. Neomycin B has previously been shown to inhibit the catalytic activity of this ribozyme (Uhlenbeck et al., Biochemistry 1995, 34, 11,186). [source] Carbon Dioxide Activation by Surface Excess Electrons: An EPR Study of the CO2, Radical Ion Adsorbed on the Surface of MgOCHEMISTRY - A EUROPEAN JOURNAL, Issue 4 2007Mario Chiesa Dr. Abstract The CO2, radical anion has been generated at the surface of MgO by direct electron transfer from surface trapped excess electrons and characterized by electron paramagnetic resonance spectroscopy. Both 13C and 17O hyperfine structures have been resolved for the first time, leading to a detailed mapping of the unpaired electron spin density distribution over the entire radical anion. The magnetic equivalence of the two O nuclei has been ascertained allowing a side-on adsorption structure at low-coordinate Mg2+ ions to be proposed for the surface stabilized radical. [source] | |||||||||||||