Home About us Contact
|
Home About us Contact | ||
|
|
||
Field Gradient (field + gradient)
Kinds of Field Gradient Selected AbstractsBacteria concentration using a membrane type insulator-based dielectrophoresis in a plastic chipELECTROPHORESIS, Issue 18 2009Yoon-Kyoung Cho Abstract We report an insulator-based (or, electrodeless) dielectrophoresis utilizing microfabricated plastic membranes. The membranes with honeycomb-type pores have been fabricated by patterning the SU-8 layer on a substrate which was pretreated with self-assembled monolayer of octadecyltrichlorosilane for the easy release. The fabricated membrane was positioned between two electrodes and alternating current field was applied for the particle trap experiments. The particle could be trapped due to the dielectrophoresis force generated by the non-uniformities of the electric fields applied through the membranes with pores. Simulations using CFD-ACE+(CFD Research, Huntsville, Alabama) suggested that the dielectrophoresis force is stronger in the edge of the pores where the field gradient is highest. The bacteria could be captured on the near edge of the pores when the electric field was turned on and the trapped bacteria could be released when the field was turned off with the release efficiency of more than 93±7%. The maximal trapping efficiency of 66±7% was obtained under the electric fields (E=128,V/mm and f=300,kHz) when the dilute bacteria solution (Escherichia coli: 9.3×103,cell/mL, 0.5,mS/m) flowed with a flow rate of 100,,L/min. [source] Red blood cell quantification microfluidic chip using polyelectrolytic gel electrodesELECTROPHORESIS, Issue 9 2009Kwang Bok Kim Abstract This paper reports on a novel microfluidic chip with polyelectrolytic gel electrodes (PGEs) used to rapidly count the number of red blood cells (RBCs) in diluted whole blood. The proposed microdevice is based on the principle that the impedance across a microchannel between two PGEs varies sensitively as RBCs pass through it. The number and amplitude of impedance peaks provide the information about the number and size of RBCs, respectively. This system features a low-voltage dc detection method and non-contact condition between cells and metal electrodes. Major advantages include stable detection under varying cellular flow rate and position in the microchannel, little chance of cell damage due to high electric field gradient and no surface fouling of the metal electrodes. The performance of this PGEs-based system was evaluated in three steps. First, in order to observe the size-only dependence of the impedance signal, three different sizes of fluorescent microbeads (7.2, 10.0, and 15.0,,m; Bangs laboratories, USA) were used in the experiment. Second, the cell counting performance was evaluated by using 7.2,,m fluorescent microbeads, similar in size to RBCs, in various concentrations and comparing the results with an animal hematoanalyzer (MS 9-5; Melet schloesing laboratories, France). Finally, in human blood sample tests, intravenously collected whole blood was just diluted in a PBS without centrifuge or other pretreatments. The PGE-based system produced almost identical number of RBCs in over 800-fold diluted samples to the results from a commercialized human hematoanalyzer (HST-N402XE; Sysmex, Japan). [source] Cover Picture: Electrophoresis 13/2008ELECTROPHORESIS, Issue 13 2008Article first published online: 11 JUL 200 Issue 13 is a regular issue including an Emphasis Section offering a series of 10 papers on "Fundamentals and Methodologies". These papers are related to peptide isoelectric point calculation, DNA separation by MEKC, modeling mobility of apothioneins, protein expression in osteoarthritis, capillary coating, preparative separation of proteins by dynamic field gradient focusing, determination of pKa, speciation analysis by CE-inductively coupled plasma MS, etc. [source] Characterization of voltage degradation in dynamic field gradient focusingELECTROPHORESIS, Issue 5 2008Jeffrey M. Burke Abstract Dynamic field gradient focusing (DFGF) is an equilibrium gradient method that utilizes an electric field gradient to simultaneously separate and concentrate charged analytes based on their individual electrophoretic mobilities. This work describes the use of a 2-D nonlinear, numerical simulation to examine the impact of voltage loss from the electrodes to the separation channel, termed voltage degradation, and distortions in the electric field on the performance of DFGF. One of the design parameters that has a large impact on the degree of voltage degradation is the placement of the electrodes in relation to the separation channel. The simulation shows that a distance of about 3,mm from the electrodes to the separation channel gives the electric field profile with least amount of voltage degradation. The simulation was also used to describe the elution of focused protein peaks. The simulation shows that elution under constant electric field gradient gives better performance than elution through shallowing of the electric field. Qualitative agreement between the numerical simulation and experimental results is shown. The simulation also illustrates that the presence of a defocusing region at the cathodic end of the separation channel causes peak dispersion during elution. The numerical model is then used to design a system that does not suffer from a defocusing region. Peaks eluted under this design experienced no band broadening in our simulations. Preliminary experimental results using the redesigned chamber are shown. [source] Auxiliary functions for molecular integrals with Slater-type orbitals.INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 1 2008Abstract The Gauss transform of Slater-type orbitals is used to express several types of molecular integrals involving these functions in terms of simple auxiliary functions. After reviewing this transform and the way it can be combined with the shift operator technique, a master formula for overlap integrals is derived and used to obtain multipolar moments associated to fragments of two-center distributions and overlaps of derivatives of Slater functions. Moreover, it is proved that integrals involving two-center distributions and irregular harmonics placed at arbitrary points (which determine the electrostatic potential, field and field gradient, as well as higher order derivatives of the potential) can be expressed in terms of auxiliary functions of the same type as those appearing in the overlap. The recurrence relations and series expansions of these functions are thoroughly studied, and algorithms for their calculation are presented. The usefulness and efficiency of this procedure are tested by developing two independent codes: one for the derivatives of the overlap integrals with respect to the centers of the functions, and another for derivatives of the potential (electrostatic field, field gradient, and so forth) at arbitrary points. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] A computational NQR study on the hydrogen-bonded lattice of cytosine-5-acetic acidJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 5 2008Mahmoud Mirzaei Abstract A computational study at the level of density functional theory (DFT) employing 6-311++G** standard basis set was carried out to evaluate nuclear quadrupole resonance (NQR) spectroscopy parameters in cytosine-5-acetic acid (C5AA). Since the electric field gradient (EFG) tensors are very sensitive to the electrostatic environment at the sites of quadruple nuclei, the most possible interacting molecules with the target one were considered in a five-molecule model system of C5AA using X-ray coordinates transforming. The hydrogen atoms positions were optimized and two model systems of original and H-optimized C5AA were considered in NQR calculations. The calculated EFG tensors at the sites of 17O, 14N, and 2H nuclei were converted to their experimentally measurable parameters, quadrupole coupling constants and asymmetry parameters. The evaluated NQR parameters reveal that the nuclei in original and H-optimized systems contribute to different hydrogen bonding (HB) interaction. The comparison of calculated parameters between optimized isolated gas-phase and crystalline monomer also shows the relationship between the structural deformation and NQR parameters in C5AA. The basis set superposition error (BSSE) calculations yielded no significant errors for employed basis set in the evaluation of NQR parameters. All the calculations were performed by Gaussian 98 package of program. © 2007 Wiley Periodicals, Inc. J Comput Chem 2008 [source] Prograde metamorphic sequence of REE minerals in pelitic rocks of the Central Alps: implications for allanite,monazite,xenotime phase relations from 250 to 610 °CJOURNAL OF METAMORPHIC GEOLOGY, Issue 5 2008E. JANOTS Abstract The distribution of REE minerals in metasedimentary rocks was investigated to gain insight into the stability of allanite, monazite and xenotime in metapelites. Samples were collected in the central Swiss Alps, along a well-established metamorphic field gradient that record conditions from very low grade metamorphism (250 °C) to the lower amphibolite facies (,600 °C). In the Alpine metapelites investigated, mass balance calculations show that LREE are mainly transferred between monazite and allanite during the course of prograde metamorphism. At very low grade metamorphism, detrital monazite grains (mostly Variscan in age) have two distinct populations in terms of LREE and MREE compositions. Newly formed monazite crystallized during low-grade metamorphism (<440 °C); these are enriched in La, but depleted in Th and Y, compared with inherited grains. Upon the appearance of chloritoid (,440,450 °C, thermometry based on chlorite,choritoid and carbonaceous material), monazite is consumed, and MREE and LREE are taken up preferentially in two distinct zones of allanite distinguishable by EMPA and X-ray mapping. Prior to garnet growth, allanite acquires two growth zones of clinozoisite: a first one rich in HREE + Y and a second one containing low REE contents. Following garnet growth, close to the chloritoid,out zone boundary (,556,580 °C, based on phase equilibrium calculations), allanite and its rims are partially to totally replaced by monazite and xenotime, both associated with plagioclase (± biotite ± staurolite ± kyanite ± quartz). In these samples, epidote relics are located in the matrix or as inclusions in garnet, and these preserve their characteristic chemical and textural growth zoning, indicating that they did not experience re-equilibration following their prograde formation. Hence, the partial breakdown of allanite to monazite offers the attractive possibility to obtain in situ ages, representing two distinct crystallization stages. In addition, the complex REE + Y and Th zoning pattern of allanite and monazite are essential monitors of crystallization conditions at relatively low metamorphic grade. [source] Metamorphism and microstructures along a high-temperature metamorphic field gradient: the north,eastern boundary of the Královský hvozd unit (Bohemian Massif, Czech Republic)JOURNAL OF METAMORPHIC GEOLOGY, Issue 4 2002D. Scheuvens Abstract A metamorphic field gradient has been investigated in the Moldanubian zone of the central European Variscides encompassing, from base to the top, a staurolite,kyanite zone, a muscovite,sillimanite zone, a K-feldspar,sillimanite zone, and a K-feldspar,cordierite zone, respectively. The observed reaction textures in the anatectic metapsammopelites of the higher grade zones are fully compatible with experimental data and petrogenetic grids that are based on fluid-absent melting reactions. From structural and microstructural observations it can be concluded that the boundary between the kyanite,staurolite zone and the muscovite- and K-feldspar,sillimanite zones coincides with an important switch in deformation mechanism(s). Besides minor syn-anatectic shearing (melt-enhanced deformation), microstructural criteria point (a) to a switch in deformation mechanism from rotation recrystallization (climb-accommodated dislocation creep) to prism Nonlinear modeling of protein separation in a preparative-scale dynamic field gradient focusing instrumentAICHE JOURNAL, Issue 1 2009Noah I. Tracy Abstract Dynamic field gradient focusing (DFGF) uses an electric field gradient opposed by a counter-flow of buffer to separate milligrams of proteins according to their electrophoretic mobilities. A nonlinear model of protein separation in a preparative-scale DFGF device was developed to aid in refining the instrument's design and finding optimal run conditions prior to performing experiments. The model predicted the focal points of bovine serum albumin (BSA), and bovine hemoglobin (Hb) to within the 95% confidence intervals about the means of the experimental values. The resolution between the proteins in the model was 2.08, which was 3% less than the lower limit of the 95% confidence interval about the experimental value. The model predicted 67% more dispersion than was present in the experimental device, which made the simulated BSA peak 22% wider than the experimentally measured width. © 2008 American Institute of Chemical Engineers AIChE J, 2009 [source] Pulsed field gradient (PFG) NMR spectroscopy: An effective tool for the analysis of mixtures of lubricating oil componentsLUBRICATION SCIENCE, Issue 4 2000G. S. Kapur Abstract In the presently reported work, the multinuclear two-dimensional (2D) diffusionordered nuclear magnetic resonance (NMR) spectroscopy (DOSY) technique based on the pulsed field gradient (PFG) has been used in experiments to analyse mixtures of lubricating oil components. One-dimensional (1D) PFG experiments have also been used to simplify and edit the NMR spectra of the mixtures. Such experiments provide a clean spectrum of the highest molecular weight (slower diffusing) component by eliminating the signals of lower molecular weight (faster diffusing) components, without any prior physical separation. These pulsed field gradient experiments not only facilitate the separation of resonance signals of different components, but also lead to their subsequent identification, and provide information about the number and structure of components in a mixture. Some examples of our initial efforts to establish 1D and 2D PFG-based NMR experiments for the analysis of mixtures of lubricating oil components are given and assessed to illustrate the potential applications of such techniques in the field of lubricating oils. [source] Solid-state NMR characterization of 69Ga and 71Ga in crystalline solidsMAGNETIC RESONANCE IN CHEMISTRY, Issue 9 2006Jason T. Ash Abstract Gallium model systems containing four- and six-coordinate gallium sites have been investigated using solid-state NMR. Measurement of the isotropic chemical shift and electric field gradient (EFG) have been performed at 9.4 T on ,-Ga2O3, ,-Ga2O3, LiGaO2, NaGaO2, KGaO2, Ga2(SO4)3, and LaGaO3 using a variety of techniques on both NMR active nuclei (69Ga and 71Ga) including static, high speed magic-angle spinning (MAS), satellite transition (ST) spectroscopy, and rotor-assisted population transfer (RAPT). The chemical shift is found to correlate well with the coordination number, with four-coordinate gallium having values of approximately 50 ppm and six-coordinate gallium having values near 225 ppm (referenced to 1 M gallium nitrate solution). The magnitude of the EFG is found to be correlated to the distortion of the gallium polyhedra, with the strained systems having EFGs of 3 × 1021 Vm,2 or more, while the less strained systems have values of 1.5 × 1021 Vm,2 or less. A plot of chemical shift versus EFG suggests that solid-state NMR of gallium oxyanions can be more discriminating than liquid state NMR chemical shifts alone. Copyright © 2006 John Wiley & Sons, Ltd. [source] Solid-state NMR spectroscopy of the quadrupolar halogens: chlorine-35/37, bromine-79/81, and iodine-127MAGNETIC RESONANCE IN CHEMISTRY, Issue 4 2006David L. Bryce Abstract A thorough review of 35/37Cl, 79/81Br, and 127I solid-state nuclear magnetic resonance (SSNMR) data is presented. Isotropic chemical shifts (CS), quadrupolar coupling constants, and other available information on the magnitude and orientation of the CS and electric field gradient (EFG) tensors for chlorine, bromine, and iodine in diverse chemical compounds is tabulated on the basis of over 200 references. Our coverage is through July 2005. Special emphasis is placed on the information available from the study of powdered diamagnetic solids in high magnetic fields. Our survey indicates a recent notable increase in the number of applications of solid-state quadrupolar halogen NMR, particularly 35Cl NMR, as high magnetic fields have become more widely available to solid-state NMR spectroscopists. We conclude with an assessment of possible future directions for research involving 35/37Cl, 79/81Br, and 127I solid-state NMR spectroscopy. Copyright © 2006 John Wiley & Sons, Ltd. [source] Slice-selective images of free radicals in mice with modulated field gradient electron paramagnetic resonance (EPR) imagingMAGNETIC RESONANCE IN MEDICINE, Issue 4 2008Hideo Sato-Akaba Abstract Continuous wave (CW) electron paramagnetic resonance (EPR) imaging can be used to obtain slice-selective images of free radicals without measuring three-dimensional (3D) projection data. A method that incorporated a modulated magnetic field gradient (MFG) was combined with polar field gradients to select a slice in the subject noninvasively. The slice-selective in vivo EPR imaging of triarylmethyl radicals in the heads of live mice is reported. 3D surface-rendered images were successfully obtained from slice-selective images. In the experiment in mice, a slice thickness of 1.8 mm was achieved. Magn Reson Med 59:885,890, 2008. © 2008 Wiley-Liss, Inc. [source] 3T MR of the prostate: Reducing susceptibility gradients by inflating the endorectal coil with a barium sulfate suspensionMAGNETIC RESONANCE IN MEDICINE, Issue 5 2007Yael Rosen Abstract Most prostate MRI/MRS examinations are performed with an endorectal coil inflated with air, leading to an air,tissue interface that induces magnetic susceptibility gradients within the gland. Inflation of the coil with a barium sulfate suspension is described and compared to inflation with air or liquid perfluorocarbon (PFC). The B0 field in the prostate gland was mapped for five healthy volunteers when the endorectal coil was inflated with each of the three agents. A marked decrease in the posterior-anterior (P-A) field gradient and a significant improvement in field homogeneity were evident in the presence of a barium suspension and PFC relative to air. MRS data acquired from the prostate gland in the presence of air, PFC, and a barium suspension in the endorectal coil showed similar trends, demonstrating improvement in line-widths and spectral resolution when the barium suspension or the PFC were inflating the endorectal coil. On this basis we conclude that a barium suspension provides an available, cheap, and safe alternative to PFC, and we suggest that inflating the endorectal coil with a barium suspension should be considered for prostate MR studies, especially at high field strengths (such as 3T). Magn Reson Med 57:898,904, 2007. © 2007 Wiley-Liss, Inc. [source] Correction of concomitant magnetic field-induced image artifacts in nonaxial echo-planar imaging,MAGNETIC RESONANCE IN MEDICINE, Issue 3 2002Yiping P. Du Abstract Echo-planar images acquired in nonaxial planes are often distorted. Such image distortion has limited the applications of the echo-planar imaging (EPI) technique. In this article, it is demonstrated that a considerable amount of the distortion is caused by the higher-order magnetic field concomitant with the linear magnetic field gradient, or the concomitant magnetic field. The image distortion caused by the concomitant magnetic field is more prominent when a higher gradient amplitude is used for readout. It is also shown that the concomitant magnetic field can cause ghosting and blurring. A theoretical analysis is performed for the concomitant field effect in nonaxial EPI images. A point-by-point (or line-by-line) phase correction algorithm is developed to correct the image distortion, ghosting, and blurring. A postreconstruction processing algorithm is also developed to correct image distortion with much higher computational efficiency. Experimental results show that both correction methods effectively reduce the image distortion in coronal or sagittal images. Magn Reson Med 48:509,515, 2002. © 2002 Wiley-Liss, Inc. [source] A new hybrid electrospray Fourier transform mass spectrometer: design and performance characteristicsRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 2 2006Peter B. O'Connor A new hybrid electrospray quadrupole Fourier transform mass spectrometry (FTMS) instrument design is shown and characterized. This instrument involves coupling an electrospray source and mass-resolving quadrupole, ion accumulation, and collision cell linear ion trap system developed by MDS Sciex with a home-built ion guide and ion cyclotron resonance (ICR) cell. The iterative progression of this design is shown. The final design involves a set of hexapole ion guides to transfer the ions from the accumulation/collision trap through the magnetic field gradient and into the cell. These hexapole ion guides are separated by a thin gate valve and two conduction limits to maintain the required <10,9,mbar vacuum for FTICR. Low-attomole detection limits for a pure peptide are shown, 220,000 resolving power in broadband mode and 820,000 resolving power in narrow-band mode are demonstrated, and mass accuracy in the <2,ppm range is routinely available provided the signal is abundant, cleanly resolved, and internally calibrated. This instrument design provides high experimental flexibility, allowing Q2 CAD, SORI-CAD, IRMPD, and ECD experiments with selected ion accumulation as well as experiments such as nozzle skimmer dissociation. Initial top-down mass spectrometry experiments on a protein is shown using ECD. Copyright © 2005 John Wiley & Sons, Ltd. [source] Response to Spackman's comment on On the calculation of the electrostatic potential, electric field and electric field gradient from the aspherical pseudoatom modelACTA CRYSTALLOGRAPHICA SECTION A, Issue 2 2007Philip Coppens First page of article [source] Effects of strong static magnetic fields used in magnetic resonance imaging on insulin-secreting cellsBIOELECTROMAGNETICS, Issue 1 2009Tomonori Sakurai Abstract The magnetic flux density of MRI for clinical diagnosis has been steadily increasing. However, there remains very little biological data regarding the effect of strong static magnetic fields (SMFs) on human health. To evaluate the effects of strong SMFs on biological systems, we cultured insulin-secreting cells under exposure to sham and SMF conditions (3,10 T of magnetic flux density, and 0,41.7 T/m of magnetic field gradient) for 0.5 or 1 h, and analyzed insulin secretion, mRNA expression, glucose-stimulated insulin secretion, insulin content, cell proliferation and cell number. Exposure to SMF with a high magnetic field gradient for 1 h significantly increased insulin secretion and insulin 1 mRNA expression. Exposure to SMF with a high magnetic flux density for 0.5 h significantly enhanced responsiveness to glucose stimulation. Exposure to SMF did not affect the insulin content, cell proliferation or cell number. Our results suggested that MRI systems with a higher magnetic flux density might not cause cell proliferative or functional damages on insulin-secreting cells, and that SMF with a high magnetic field gradient might be used clinically after thorough in vivo investigations are conducted. Bioelectromagnetics 30:1,8, 2009. © 2008 Wiley-Liss, Inc. [source] Hydrogen Adsorption and Diffusion in p - tert -Butylcalix[4]arene: An Experimental and Molecular Simulation StudyCHEMISTRY - A EUROPEAN JOURNAL, Issue 38 2010Dr. Saman Alavi Abstract Experimental adsorption isotherms were measured and computer simulations were performed to determine the nature of the H2 gas uptake in the low-density p - tert -butylcalix[4]arene (tBC) phase. 1H,NMR peak intensity measurements for pressures up to 175,bar were used to determine the H2 adsorption isotherm. Weak surface adsorption (up to ,2,mass,% H2) and stronger adsorption (not exceeding 0.25,mass,% or one H2 per calixarene bowl) inside the calixarene phase were detected. The latter type of adsorbed H2 molecule has restricted motion and shows a reversible gas adsorption/desorption cycle. Pulsed field gradient (PFG) NMR pressurization/depressurization measurements were performed to study the diffusion of H2 in the calixarene phases. Direct adsorption isotherms by exposure of the calixarene phase to pressures of H2 gas to ,60,bar are also presented, and show a maximum H2 adsorption of 0.4,H2 per calixarene bowl. Adsorption isotherms of H2 in bulk tBC have been simulated using grand canonical Monte Carlo calculations in a rigid tBC framework, and yield adsorptions of ,1,H2 per calixarene bowl at saturation. Classical molecular dynamics simulations with a fully flexible calixarene molecular force field are used to determine the guest distribution and inclusion energy of the H2 in the solid with different loadings. [source] Using Diffusion NMR To Characterize Guanosine Self-Association: Insights into Structure and MechanismCHEMISTRY - A EUROPEAN JOURNAL, Issue 1 2005Mark S. Kaucher Abstract This paper presents results from a series of pulsed field gradient (PFG) NMR studies on lipophilic guanosine nucleosides that undergo cation-templated assembly in organic solvents. The use of PFG-NMR to measure diffusion coefficients for the different aggregates allowed us to observe the influences of cation, solvent and anion on the self-assembly process. Three case studies are presented. In the first study, diffusion NMR confirmed formation of a hexadecameric G-quadruplex [G,1]16,4,K+,4,pic, in CD3CN. Furthermore, hexadecamer formation from 5,-TBDMS-2,,3,-isopropylidene G,1 and K+ picrate was shown to be a cooperative process in CD3CN. In the second study, diffusion NMR studies on 5,-(3,5-bis(methoxy)benzoyl)-2,,3,-isopropylidene G,4 showed that hierarchical self-association of G8 -octamers is controlled by the K+ cation. Evidence for formation of both discrete G8 -octamers and G16 -hexadecamers in CD2Cl2 was obtained. The position of this octamer,hexadecamer equilibrium was shown to depend on the K+ concentration. In the third case, diffusion NMR was used to determine the size of a guanosine self-assembly where NMR signal integration was ambiguous. Thus, both diffusion NMR and ESI-MS show that 5,- O -acetyl-2,,3,- O -isopropylidene G,7 and Na+ picrate form a doubly charged octamer [G,7]8,2,Na+,2,pic,9 in CD2Cl2. The anion's role in stabilizing this particular complex is discussed. In all three cases the information gained from the diffusion NMR technique enabled us to better understand the self-assembly processes, especially regarding the roles of cation, anion and solvent. [source] Sensitivity-enhanced Experiments for the Measurement of J and Dipolar Coupling ConstantsCHINESE JOURNAL OF CHEMISTRY, Issue 7 2002Dong-Hai Lin Abstract A sensitivity-enhanced IPAP NMR experiment was described in this paper, which separates the 1H- 15N doublets into two different spectra to alleviate the problem of resonance overlaps and achieve the accurate measurement of J and residual dipolar coupling constants in proteins. This experiment offered 20%,60% sensitivity enhancement over the original IPAP experiment, and therefore produced more measurable resonances. Pulsed field gradient was used for coherence selection. Water-flip-back approach was used for water suppression. The sensitivity-enhanced IPAP experiment was employed in the measurement of 1JNH and 1DNH constants of the protein UBC9. [source] NMR diffusion measurements under chemical exchange between sites involving a large chemical shift differenceCONCEPTS IN MAGNETIC RESONANCE, Issue 2 2010S. Leclerc Abstract This study concerns the thallium-205 cation in aqueous solution in the presence of a calixarene molecule. Although the measurement of the self-diffusion coefficient of pure thallium (without calixarene in the aqueous solution) does not pose any particular problem, major difficulties are encountered with the standard method using gradient strength increment as soon as thallium is partly complexed by calixarene. With static magnetic field gradients, the NMR signal is so weak that it prevents any reliable measurement, whereas radio frequency (rf) field gradients lead to an unrealistic value of the diffusion coefficient. This failure is explained by the fact that thallium is in fast exchange between two sites (complexed and free thallium) thus exhibiting a single NMR signal although, in the course of the experiment, two signals, with an important difference in resonance frequencies (due to the large thallium chemical shift range), are effectively involved. With the objective to understand these quite unexpected observations, the theory underlying NMR diffusion experiments is first reviewed, and criteria of fast exchange are discussed for three parameters: chemical shifts, relaxation rates, and diffusion coefficients. It turns out that off-resonance effects are responsible for unwanted defocusing due to rf pulses in the static magnetic field gradient method and for time-dependent gradients in the rf field gradient method. Concerning the latter, a remedy is proposed which consists in applying the stronger gradient and incrementing the gradient pulse durations. After correction for relaxation, the expected value of the diffusion coefficient is retrieved. © 2010 Wiley Periodicals, Inc. Concepts Magn Reson Part A 36A: 127,137, 2010. [source] Singlet states open the way to longer time-scales in the measurement of diffusion by NMR spectroscopyCONCEPTS IN MAGNETIC RESONANCE, Issue 1 2008Simone Cavadini Abstract Nuclear magnetic resonance is a powerful nonintrusive technique for measuring diffusion coefficients through the use of pulsed field gradients. The main limitation to the application range of this method is imposed by the relaxation time constants of the magnetization. The recently introduced singlet-state spectroscopy affords obtaining relaxation time constants for pairs of coupled spins which can be longer by more than an order of magnitude than the spin-lattice relaxation time constants. We review in this paper the advantages that are offered by these long relaxation time constants for diffusion measurements. Using experiments that combine singlet-state and diffusion spectroscopy, slower diffusion constants can be determined. The coupling of the two methods constitutes an alternative to the use of special probes equipped with strong gradients for the study of large molecules that diffuse slowly in solution. © 2008 Wiley Periodicals, Inc. Concepts Magn Reson Part A 32A: 68,78, 2008. [source] Coarse Grained Molecular Dynamics Simulation of Electromechanically-Gated DNA Modified Conical NanoporesELECTROANALYSIS, Issue 3 2008Lajos Höfler Abstract Nanopore-based devices are emerging as tools for single molecule manipulation, characterization and chemical analysis. Single or random arrays of chemically modified nanopores have been established as platforms for selective chemical and biosensing. However, it is little known about the orientation and behavior of surface tethered species in the nanopore environment as function of applied transpore voltages. In this study we report on coarse grained modeling of short (5-, 15-mer) DNA modified conical gold nanopores subjected to electrical field gradients of 5 and 50,mV/nm. An electromechanical gating effect in the single stranded DNA modified conical nanopores is predicted, which is due to the obstruction of the tip entrance by DNA strands oriented by the external electrical field. The magnitude of the rectification effect increases with increasing DNA length and decreasing tip diameter of the conical nanopore. The direction of on/off switching was found to be dependent on the location of the immobilized DNAs on the membrane supporting the nanopore. [source] A micropillar-integrated smart microfluidic device for specific capture and sorting of cellsELECTROPHORESIS, Issue 24 2007Yan-Jun Liu Abstract An integrated smart microfluidic device consisting of nickel micropillars, microvalves, and microchannels was developed for specific capture and sorting of cells. A regular hexagonal array of nickel micropillars was integrated on the bottom of a microchannel by standard photolithography, which can generate strong induced magnetic field gradients under an external magnetic field to efficiently trap superparamagnetic beads (SPMBs) in a flowing stream, forming a bed with sufficient magnetic beads as a capture zone. Fluids could be manipulated by programmed controlling the integrated air-pressure-actuated microvalves, based on which in situ bio-functionalization of SPMBs trapped in the capture zone was realized by covalent attachment of specific proteins directly to their surface on the integrated microfluidic device. In this case, only small volumes of protein solutions (62.5,nL in the capture zone; 375,nL in total volume needed to fill the device from inlet A to the intersection of outlet channels F and G) can meet the need for protein! The newly designed microfluidic device reduced greatly chemical and biological reagent consumption and simplified drastically tedious manual handling. Based on the specific interaction between wheat germ agglutinin (WGA) and N -acetylglucosamine on the cell membrane, A549 cancer cells were effectively captured and sorted on the microfluidic device. Capture efficiency ranged from 62 to 74%. The integrated microfluidic device provides a reliable technique for cell sorting. [source] The effects of 1.5T magnetic resonance imaging on early murine in-vitro embryo developmentJOURNAL OF MAGNETIC RESONANCE IMAGING, Issue 3 2001MMed (O&G), MRACOG, Stephen Chew MBBS Abstract Although no ionizing radiation is involved, patients undergoing magnetic resonance imaging (MRI) are exposed to powerful static magnetic fields, magnetic field gradients, and radio-frequency fields that may be potentially damaging. Our study aims to document the effect of MRI imaging sequences on early murine embryo development (two-cell to blastocyst stage) in vitro. Two-cell murine embryos were exposed to various lengths of MRI using pulse sequences employed in present day clinical imaging. Early murine embryo development was documented in vitro, and blastocyst development rates were computed for both the control and exposed groups. There were no significant differences detected in the rate of blastocyst formation between the control groups and the embryos exposed to MRI. J. Magn. Reson. Imaging 2001;13:417,420. © 2001 Wiley-Liss, Inc. [source] Anisotropic Particle Synthesis Inside Droplet Templates on Superhydrophobic SurfacesMACROMOLECULAR RAPID COMMUNICATIONS, Issue 2 2010Vinayak Rastogi Abstract We demonstrate how droplet templates dispensed on superhydrophobic substrates can be used to fabricate both shape-anisotropic ("doughnut") and composition-anisotropic ("patchy magnetic") supraparticles. The macroscopic shape of the closely-packed particle assemblies is guided by the droplet meniscus. Aqueous droplets of monodisperse microsphere suspensions dispensed on the substrates initially acquire near-spherical shape due to a high contact angle. During the solvent evaporation, however, silica suspension droplets undergo shape transitions (concaving) guiding the structure of the final assemblies into doughnut supraparticles. Composition anisotropy is achieved by drying a droplet containing a mixed suspension of latex and magnetic nanoparticles, while exposing it to magnetic field gradients. Depending on the pattern of the magnetic fields, the magnetic nanoparticles segregate into single, bilateral, or trilateral, patched spherical supraparticles. The physical effects leading to the development of anisotropy are discussed. Unlike the conventional wet self-assembly (WSA) methods where the final structures need to be extracted from the liquid environment, this efficient one-step procedure produces ready to use "dry" supraparticles. [source] SESAME-HSQC for simultaneous measurement of NH and CH scalar and residual dipolar couplings,MAGNETIC RESONANCE IN CHEMISTRY, Issue 4 2007Peter Würtz Abstract We present a novel pulse sequence, SESAME-HSQC, for the simultaneous measurement of several NH and CH scalar and residual dipolar couplings in double labeled proteins. The proposed Spin-statE Selective All Multiplicity Edited (SESAME)-HSQC combines gradient selected and sensitivity enhanced 15N- and constant-time 13C-HSQC experiments with the recently introduced spin-state selective method (Nolis et al., J. Magn. Reson. 180 (2006) 39,50) for measuring couplings simultaneously at amide and aliphatic regions. Excellent resolution and high sensitivity is warranted by removing all coupling interactions during the indirectly detected t1 period, and by employing pulsed field gradients for coherence selection and utilizing coherence order selective spin-state selection. The scalar and residual dipolar couplings can be readily measured from a two-dimensional 15N/13C-HSQC spectrum without additional spectral crowding. SESAME-HSQC can be used for epitope mapping by observing chemical shift changes in both amide and aliphatic regions. Simultaneously, potential conversion in protein conformation can be probed by analyzing changes in residual dipolar couplings induced by ligand binding. The pulse sequence is experimentally verified with a sample of 15N/13C enriched human ubiquitin. The internuclear vector directions determined from the residual dipolar couplings are found to be in excellent correlation with those predicted from ubiquitin's refined solution structure. Copyright © 2007 John Wiley & Sons, Ltd. [source] Density-functional computation of 53Cr NMR chemical shiftsMAGNETIC RESONANCE IN CHEMISTRY, Issue 7 2006Michael Bühl Abstract 53Cr chemical shifts of CrO42,, Cr2O72,, CrO3X,, CrO2X2(X = F, Cl), and Cr(CO)5L (L = CO, PF3, CHNH2, CMeNMe2) are computed, using geometries optimized with the gradient-corrected BP86 density functional, at the gauge-including atomic orbitals (GIAO)-, BPW91-, and B3LYP levels. For this set of compounds, substituent effects on ,(53Cr) are better described with the pure BPW91 functional than with B3LYP, in contrast to most other transition-metal chemical shifts studied so far. For selected cases, 53Cr NMR line widths can be rationalized in terms of electric field gradients (EFGs) computed with the BPW91 functional, but in general other factors such as molecular correlation times appear to be dominating. 53Cr chemical shifts and EFGs are predicted for CrO3, Cr(C6H6)2, Cr(C6H6)CO3, and, with reduced reliability, for Cr2(µ2 -O2CH)4. Copyright © 2006 John Wiley & Sons, Ltd. [source] NMR methods applied to anisotropic diffusionMAGNETIC RESONANCE IN CHEMISTRY, Issue 13 2002István Furó Abstract The methodology of NMR experiments intended to measure anisotropic diffusion is reviewed. Experiments of this kind preferably require oriented samples and/or orientation-dependent spin coupling and/or magnetic field gradients in different directions. One strategy of diffusion experiments in anisotropic systems with broad NMR lines employs line narrowing techniques, thereby allowing for efficient gradient encoding/decoding. Depending on the nuclei, spin couplings and samples, the preferred methods vary from decoupling through echo techniques to magic angle sample orientation and spinning. Another avenue to efficient gradient encoding/decoding is through very strong magnetic field gradients. Either way, anisotropic diffusion reveals new structural features as illustrated by a few selected examples in liquid crystals and in biological tissues. Copyright © 2002 John Wiley & Sons, Ltd. [source]
| | ||||||||||||||||||||||||||||||