987 resultados para Electron resonance


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We analyze the linewidth narrowing in the fluorescence spectrum of a two-level atom driven by a squeezed vacuum field of a finite bandwidth. It is found that the fluorescence spectrum in a low-intensity squeezed field can exhibit a (omega - omega(0))(-6) frequency dependence in the wings. We show that this fast fall-off behavior is intimately related to the properties of a narrow-bandwidth squeezed field and does not extend into the region of broadband excitation. We apply the Linear response model and find that the narrowing results from a convolution of the atom response with the spectrum of the incident field. On the experimental side, we emphasize that the linewidth narrowing is not sensitive to the solid angle of the squeezed modes coupled to the atom. We also compare the fluorescence spectrum with the quadrature-noise spectrum and find that the fluorescence spectrum for an off-resonance excitation does not reveal the noise spectrum. We show that this difference arises from the competing three-photon scattering processes. [S1050-2947(98)04308-X].

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We study the resonance fluorescence from two interacting atoms driven by a squeezed vacuum field and show that this system produces an interference pattern with a dark center. We discuss the role of the interatomic interactions in this process and find that the interference pattern results from an unequal population of the symmetric and antisymmetric states of the two-atom system. We also identify intrinsically nonclassical effects versus classical squeezed field effects, (C) 1998 Elsevier Science B.V. All rights reserved.

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Electron paramagnetic resonance (EPR) spectra and X-ray absorption (EXAFS and XANES) data have been recorded for the manganese enzyme aminopeptidase P (AMPP, PepP protein) from Escherichia coli. The biological function of the protein, a tetramer of 50-kDa subunits, is the hydrolysis of N-terminal Xaa-Pro peptide bonds. Activity assays confirm that the enzyme is activated by treatment with Mn2+. The EPR spectrum of Mn2+-activated AMPP at liquid-He temperature is characteristic of an exchange-coupled dinuclear Mn(II) site, the Mn-Mn separation calculated from the zero-field splitting D of the quintet state being 3.5 (+/- 0.1) Angstrom. In the X-ray absorption spectrum of Mn2+-activated AMPP at the Mn K edge, the near-edge features are consistent with octahedrally coordinated Mn atoms in oxidation state +2. EXAFS data, limited to k less than or equal to 12 Angstrom(-1) by traces of Fe in the protein, are consistent with a single coordination shell occupied predominantly by O donor atoms at an average Mn-ligand distance of 2.15 Angstrom, but the possibility of a mixture of O and N donor atoms is not excluded. The Mn-Mn interaction at 3.5 Angstrom, is not detected in the EXAFS, probably due to destructive interference from light outer-shell atoms. The biological function, amino acid sequence and metal-ion dependence of E. coli AMPP are closely related to those of human prolidase, an enzyme that specifically cleaves Xaa-Pro dipeptides. Mutations that lead to human prolidase deficiency and clinical symptoms have been identified. Several known inhibitors of prolidase also inhibit AMPP. When these inhibitors are added to Mn2+-activated AMPP, the EPR spectrum and EXAFS remain unchanged. It can be inferred that the inhibitors either do not bind directly to the Mn centres, or substitute for existing Mn ligands without a significant change in donor atoms or coordination geometry. The conclusions from the spectroscopic measurements on AMPP have been verified by, and complement, a recent crystal structure analysis.

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The gamma-radiolysis of poly(tetrafluoroethylene-co-perfluoromethyl vinyl ether) (TFE/PMVE) was investigated using chemical and mechanical analyses. The polymer was found to form an insoluble network with a dose of gelation of 15.8 kGy. Tensile and glass transition temperature measurements indicated the predominance of crosslinking, with optimal elastomeric properties reached in the dose range of 120 to 200 kGy. Photoacoustic FTIR spectroscopy CPAS) showed the formation of new carboxylic acid end groups on irradiation. These new end groups were shown to decrease the thermal oxidative stability of the crosslinked network as determined by thermal gravimetric analysis. Electron spin resonance (ESR) studies of the polymer at 77 K indicated the presence of radical precursors. A G-value of 1.1 was determined for radical production at 77 K. Comparison of radical concentrations for a copolymer with a different mole ratio of PMVE, indicated that the PMVE units contribute to scission reactions. (C) 1998 Elsevier Science Ltd. All rights reserved.

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A new cyclic octapeptide, cyclo(Ile-Ser-(Gly)Thz-Ile-Thr-(Gly)Thz) (PatN), related to patellamide A, has been synthesized and reacted with copper(II) and base to form mono- and dinuclear complexes. The coordination environments around copper(TI) have been characterized by EPR spectroscopy. The solution structure of the thermodynamically most stable product, a purple dicopper(TI) compound, has been examined by simulating weakly dipole-dipole coupled EPR spectra based upon structural parameters obtained from force field (MM and MD) calculations. The MM-EPR method produces a saddle-shaped structure for [Cu-2(PatN)(OH2)(6)] that is similar to the known solution structure of patellamide A and the known solid-state structure of [Cu-2(AscidH(2))CO3(OH2)(2)]. Compared with the latter, [Cu-2(PatN)] has no carbonate bridge and a significantly flatter topology. The MM-EPR approach to solution-structure determination for paramagnetic metallopeptides may find wide applications to other metallopeptides and metalloproteins.

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Magnetic resonance imaging (MRI) was used to evaluate and compare with anthropometry a fundamental bioelectrical impedance analysis (BIA) method for predicting muscle and adipose tissue composition in the lower limb. Healthy volunteers (eight men and eight women), aged 41 to 62 years, with mean (S.D.) body mass indices of 28.6 (5.4) kg/m(2) and 25.1 (5.4) kg/m(2) respectively, were subjected to MRI leg scans, from which 20-cm sections of thigh and IO-cm sections of lower leg (calf) were analysed for muscle and adipose tissue content, using specifically developed software. Muscle and adipose tissue were also predicted from anthropometric measurements of circumferences and skinfold thicknesses, and by use of fundamental BIA equations involving section impedance at 50 kHz and tissue-specific resistivities. Anthropometric assessments of circumferences, cross-sectional areas and volumes for total constituent tissues matched closely MRI estimates. Muscle volume was substantially overestimated (bias: thigh, -40%; calf, -18%) and adipose tissue underestimated (bias: thigh, 43%; calf, 8%) by anthropometry, in contrast to generally better predictions by the fundamental BIA approach for muscle (bias:thigh, -12%; calf, 5%) and adipose tissue (bias:thigh, 17%; calf, -28%). However, both methods demonstrated considerable individual variability (95% limits of agreement 20-77%). In general, there was similar reproducibility for anthropometric and fundamental BIA methods in the thigh (inter-observer residual coefficient of variation for muscle 3.5% versus 3.8%), but the latter was better in the calf (inter-observer residual coefficient of variation for muscle 8.2% versus 4.5%). This study suggests that the fundamental BIA method has advantages over anthropometry for measuring lower limb tissue composition in healthy individuals.

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alpha-Conotoxin ImI derives from the venom of Conus imperialis and is the first and only small-peptide ligand that selectively binds to the neuronal alpha(7) homopentameric subtype of the nicotinic acetylcholine receptor (nAChR). This receptor subtype is a possible drug target for several neurological disorders. The cysteines are connected in the pairs Cys2-Cys8 and Cys3-Cys12, To date it is the only alpha-conotoxin with a 4/3 residue spacing between the cysteines, The structure of ImI has been determined by H-1 NMR spectroscopy in aqueous solution, The NMR structure is of high quality, with a backbone pairwise rmsd of 0.34 Angstrom for a family of 19 structures, and comprises primarily a series of nested beta turns. Addition of organic solvent does not perturb the solution structure. The first eight residues of ImI are identical to the larger, but related, conotoxin EpI and adopt a similar structure, despite a truncated second loop. Residues important for binding of ImI to the alpha 7 nAChR are all clustered on one face of the molecule. Once further binding data for EPI and ImI are available, the ImI structure will allow for design of novel alpha(7) nAChR-specific agonists and antagonists with a wide range of potential pharmaceutical applications.

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A causally well-behaved solution of the localization problem for the free electron is given, with natural space-time transformation properties, in terms of Dirac's position operator x. It is shown that, although x is not an observable in the usual sense, and has no positive-energy (generalized) eigenstates, the four-vector density (rho(x, t), j(x, t)/c) is observable, and can be localized arbitrarily precisely about any point in space, at any instant of time, using only positive energy states. A suitable spin operator can be diagonalized at the same time.

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Imaging of the head and neck is the most commonly performed clinical magnetic resonance imaging (MRI) examination [R. G. Evans and J. R. G. Evans, AJR 157, 603 (1991)]. This is usually undertaken in a generalist MRI instrument containing superconducting magnet system capable of imaging all organs. These generalist instruments are large, typically having a bore of 0.9-1.0 m and a length of 1.7-2.5 m and therefore are expensive to site, somewhat claustrophobic to the patient, and offer little access by attending physicians. In this article, we present the design of a compact, superconducting MRI magnet for head and neck imaging that is less than 0.8 m in length and discuss in detail the design of an asymmetric gradient coil set, tailored to the magnet profile. In particular, the introduction of a radio-frequency FM modulation scheme in concert with a gradient sequence allows the epoch of the linear region of the gradient set to be much closer to the end of the gradient structure than was previously possible. Images from a prototype gradient set demonstrate the effectiveness of the designs. (C) 1999 American Institute of Physics. [S0034-6748(99)04910-2].

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Methods of promoting the radiation-induced cross linking of poly(tetrafluoro-ethylene-co-perfluoromethyl vinyl ether) (TFE/PMVE) have been investigated. Greater control of the crosslinking and chain-scission reactions was achieved by varying the radiolysis temperature. This was attributed to temperature affecting the mobilities of reactive species such as polymeric free radicals. These reactive species are precursors to radiation-induced cross links and chain-ends. Analysis of the sol/gel behaviour, tensile properties and FTIR indicated that the optimum temperature for the radiation crosslinking of TFE/PMVE, at a dose of 150 kGy, was 263 K. This temperature was 10 K below the glass transition temperature. Incorporation of 1 wt% triallyl isocyanurate (TAIC) greatly amplified the radiation crosslinking of TFE/PMVE, The dose for gelation was decreased by 70%, and the additive imparted superior mechanical properties compared to the neat irradiated TFE/PMVE. Electron spin resonance (ESR) measurements showed higher radical yields at 77 K with the 1 wt% TAIC, indicating that the crosslinking promoter was acting as a radical trap. (C) 1999 Society of Chemical Industry.

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The bis(mu-hydroxo) complex [Cu-2(Me-2[9]aneN(2)S)(2)(OH)(2)](PF6)(2) (Me-2[9]aneN(2)S = N,N'-dimethyl-1-thia-4,7-diazacyclononane) results after reaction of [Cu(Me-2[9]aneN(2)S)(MeCN)] (PF6) with dioxygen at -78 degrees C in acetonitrile. The complex has been characterized by X-ray crystallography: orthorhombic, space group Pnma, with a 18.710(3), b 16.758(2), c 9.593(2) Angstrom, and Z = 4. The structure refined to a final R value of 0.051. The complex contains two copper(II) ions bridged by two hydroxo groups with Cu ... Cu 2.866(1) Angstrom. The solid-state magnetic susceptibility study reveals ferromagnetic coupling, the fitting parameters being J = +46+/-5 cm(-1), g = 2.01+/-0.01 and theta = -0.58+/-0.03 K. The frozen-solution e.p.r. spectrum in dimethyl sulfoxide is characteristic of a monomeric copper(II) ion (g(parallel to) 2.300, g(perpendicular to) 2.063; A(parallel to) 156.2 x 10(-4) cm(-1), A(perpendicular to) 9.0 x 10(-4) cm(-1)) with an N2O2 donor set. Thioether coordination to the copper(II) in solution is supported by the presence of an intense absorption assigned to a sigma(S)-->Cu-II LMCT transition at c. 34000 cm(-1). The single-crystal spectrum of [Cu-2(Me-2[9]aneN(2)S)(2)(OH)(2)] (PF6)(2) (273 K) reveals d-->d transitions at 14500 and 18300 cm(-1) and a weak pi(S)-->Cu-II charge-transfer band at approximately 25000 cm(-1).

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OBJECTIVE: To use magnetic resonance imaging (MRI) to validate estimates of muscle and adipose tissue (AT) in lower limb sections obtained by dual-energy X-ray absorptiometry (DXA) modelling. DESIGN: MRI measurements were used as reference for validating limb muscle and AT estimates obtained by DXA models that assume fat-free soft tissue (FFST) comprised mainly muscle: model A accounted for bone hydration only; model B also applied constants for FFST in bone and skin and fat in muscle and AT; model C was as model B but allowing for variable fat in muscle and AT. SUBJECTS: Healthy men (n = 8) and women (n = 8), ages 41 - 62 y; mean (s.d.) body mass indices (BMIs) of 28.6 (5.4) kg/m(2) and 25.1 (5.4) kg/m2, respectively. MEASUREMENTS: MRI scans of the legs and whole body DXA scans were analysed for muscle and AT content of thigh (20 cm) and lower leg (10 cm) sections; 24 h creatinine excretion was measured. RESULTS: Model A overestimated thigh muscle volume (MRI mean, 2.3 l) substantially (bias 0.36 l), whereas model B underestimated it by only 2% (bias 0.045 l). Lower leg muscle (MRI mean, 0.6 l) was better predicted using model A (bias 0.04 l, 7% overestimate) than model B (bias 0.1 l, 17% underestimate). The 95% limits of agreement were high for these models (thigh,+/- 20%; lower leg,+/- 47%). Model C predictions were more discrepant than those of model B. There was generally less agreement between MRI and all DXA models for AT. Measurement variability was generally less for DXA measurements of FFST (coefficient of variation 0.7 - 1.8%) and fat (0.8 - 3.3%) than model B estimates of muscle (0.5-2.6%) and AT (3.3 - 6.8%), respectively. Despite strong relationships between them, muscle mass was overestimated by creatinine excretion with highly variable predictability. CONCLUSION: This study has shown the value of DXA models for assessment of muscle and AT in leg sections, but suggests the need to re-evaluate some of the assumptions upon which they are based.

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We wish to report the detection of dimethyl sulfone (methylsulfonylmethane, C2H6O2S) in the brain of a normal 62-year-old male using in vivo proton magnetic resonance spectroscopy. The presence of this exogenous metabolite resulted from ingestion of a dietary supplement containing dimethyl sulfone. The concentration of this compound in the brain was measured to be 2.4 mmol, with a washout half life of approximately 7.5 days. The in vivo T-1 and T-2 relaxation times of dimethyl sulfone were measured to be 2180 ms and 385 ms, respectively. The concentration of major brain metabolites, namely N-acetylaspartate, total Creatine and Choline, and myo-Inositol were within normal limits. (C) 2000 Elsevier Science Inc. All rights reserved.

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This paper describes a hybrid numerical method of an inverse approach to the design of compact magnetic resonance imaging magnets. The problem is formulated as a field synthesis and the desired current density on the surface of a cylinder is first calculated by solving a Fredholm equation of the first, kind. Nonlinear optimization methods are then invoked to fit practical magnet coils to the desired current density. The field calculations are performed using a semi-analytical method. The emphasis of this work is on the optimal design of short MRI magnets. Details of the hybrid numerical model are presented, and the model is used to investigate compact, symmetric MRI magnets as well as asymmetric magnets. The results highlight that the method can be used to obtain a compact MRI magnet structure and a very homogeneous magnetic field over the central imaging volume in clinical systems of approximately 1 m in length, significantly shorter than current designs. Viable asymmetric magnet designs, in which the edge of the homogeneous region is very close to one end of the magnet system are also presented. Unshielded designs are the focus of this work. This method is flexible and may be applied to magnets of other geometries. (C) 2000 American Association of Physicists in Medicine. [S0094-2405(00)00303-5].

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A method is presented for including path propagation effects into models of radiofrequency resonators for use in magnetic resonance imaging. The method is based on the use of Helmholtz retarded potentials and extends our previous work on current density models of resonators based on novel inverse finite Hilbert transform solutions to the requisite integral equations. Radiofrequency phase retardation effects are most pronounced at high field strengths (frequencies) as are static field perturbations due to the magnetic materials in the resonators themselves. Both of these effects are investigated and a novel resonator structure presented for use in magnetic resonance microscopy.