Fast Exchange Rate Research Articles

Preparation of Sulfonated PVA-TMSP Membranes for Direct Methanol Fuel Cell

Normal 0 false false false IN X-NONE X-NONE MicrosoftInternetExplorer4 /* Style Definitions */ table.MsoNormalTable {mso-style-name:"Table Normal"; mso-tstyle-rowband-size:0; mso-tstyle-colband-size:0; mso-style-noshow:yes; mso-style-priority:99; mso-style-qformat:yes; mso-style-parent:""; mso-padding-alt:0cm 5.4pt 0cm 5.4pt; mso-para-margin:0cm; mso-para-margin-bottom:.0001pt; mso-pagination:widow-orphan; font-size:11.0pt; font-family:"Calibri","sans-serif"; mso-ascii-font-family:Calibri; mso-ascii-theme-font:minor-latin; mso-fareast-font-family:"Times New Roman"; mso-fareast-theme-font:minor-fareast; mso-hansi-font-family:Calibri; mso-hansi-theme-font:minor-latin; mso-bidi-font-family:"Times New Roman"; mso-bidi-theme-font:minor-bidi;} Novel p reparation and characterization of sul f onated p olyvinyl alcohol (P VA )–trimethoxysilyl propanethiol (TMSP) membrane s for direct methanol fuel cell (DMFC) application ha ve been investigated . P reparation of sul f onated PVA-TMSP membrane was conducted by crosslinking step s using sol-gel method and a catalyst of concentrated HCl . T MSP concentrations were varied from 1% to 3%. The gel solution was cast on to the membrane metal plate to obtain membrane sheets. The membrane was then oxidized in H 2 O 2 concentrations of (10 - 30%) to convert the mercapto groups into sulfonate group . Investigations of the cross-linkin g process and the exist e nce of sulfonate group w ere conducted by i nfrared spectroscopy as shown for frequencies at 1140–1200 cm -1 and 1200–1145 cm -1 respectively. The scanning electron microscope – energy dispersive X-rays (SEM–EDX ) of the membrane s indicated that the distribution of silica particles from sol–gel reaction products was uneven due to the fast exchange rate of condensation. The degree of swelling decrease d as methanol concentrations increase for sul f onated PVA–TMSP membrane which opposed to ward the value of commercial Nafion membrane. The maximum value of ion exchange capacity o f the membrane was 1.82 mmol/g whereas the highest proton conductivity was 3.9 x 10 -4 Scm -1 . Therefore it can be concluded that the membrane was a potential candidate for application in DMFC. Normal 0 false false false IN X-NONE X-NONE MicrosoftInternetExplorer4 /* Style Definitions */ table.MsoNormalTable {mso-style-name:"Table Normal"; mso-tstyle-rowband-size:0; mso-tstyle-colband-size:0; mso-style-noshow:yes; mso-style-priority:99; mso-style-qformat:yes; mso-style-parent:""; mso-padding-alt:0cm 5.4pt 0cm 5.4pt; mso-para-margin:0cm; mso-para-margin-bottom:.0001pt; mso-pagination:widow-orphan; font-size:11.0pt; font-family:"Calibri","sans-serif"; mso-ascii-font-family:Calibri; mso-ascii-theme-font:minor-latin; mso-fareast-font-family:"Times New Roman"; mso-fareast-theme-font:minor-fareast; mso-hansi-font-family:Calibri; mso-hansi-theme-font:minor-latin; mso-bidi-font-family:"Times New Roman"; mso-bidi-theme-font:minor-bidi;} Keywords: DMFC, fuel cell, nafion, PVA, TMSP

MR chemical exchange imaging with spin-lock technique (CESL): a theoretical analysis of the Z-spectrum using a two-pool R1ρ relaxation model beyond the fast-exchange limit

The chemical exchange (CE) process has been exploited as a novel and powerful contrast mechanism for MRI, which is primarily performed in the form of chemical exchange saturation transfer (CEST) imaging. A spin-lock (SL) technique can also be used for CE studies, although traditionally performed and interpreted quite differently from CEST. Chemical exchange imaging with spin-lock technique (CESL), theoretically based on the Bloch–McConnell equations common to CEST, has the potential to be used as an alternative to CEST and to better characterize CE processes from slow and intermediate to fast proton exchange rates through the tuning of spin-lock pulse parameters. In this study, the Z-spectrum and asymmetric magnetization transfer ratio (MTRasym) obtained by CESL are theoretically analyzed and numerically simulated using a general two-pool R1ρ relaxation model beyond the fast-exchange limit. The influences of spin-lock parameters, static magnetic field strength B0 and physiological properties on the Z-spectrum and MTRasym are quantitatively revealed. Optimization of spin-lock frequency and spin-lock duration for the maximum CESL contrast enhancement is also investigated. Numerical simulation results in this study are compatible with the findings in the existing literature on CE imaging studies.

Characterization of estrogen-receptor-targeted contrast agents in solution, breast cancer cells, and tumors in vivo.

The estrogen receptor (ER) is a major prognostic biomarker of breast cancer, currently determined in surgical specimens by immunohistochemistry. Two new ER-targeted probes, pyridine-tetra-acetate-Gd chelate (PTA-Gd) conjugated either to 17β-estradiol (EPTA-Gd) or to tamoxifen (TPTA-Gd), were explored as contrast agents for molecular imaging of ER. In solution, both probes exhibited a micromolar ER binding affinity, fast water exchange rate (∼10(7) s(-1)), and water proton-relaxivity of 4.7-6.8 mM(-1) s(-1). In human breast cancer cells, both probes acted as estrogen agonists and enhanced the water protons T1 relaxation rate and relaxivity in ER-positive as compared to ER-negative cells, with EPTA-Gd showing a higher ER-specific relaxivity than TPTA-Gd. In studies of breast cancer tumors in vivo, EPTA-Gd induced the highest enhancement in ER-positive tumors as compared to ER-negative tumors and muscle tissue, enabling in vivo detection of ER. TPTA-Gd demonstrated the highest enhancement in muscle tissue indicating nonspecific interaction of this agent with muscle components. The extracellular contrast agents, PTA-Gd and GdDTPA, showed no difference in the perfusion capacity of ER-positive and -negative tumors confirming the specific interaction of EPTA-Gd with ER. These findings lay a basis for the molecular imaging of the ER using EPTA-Gd as a template for further developments.

Treatment of Natural Mordenite with Alkali and the Ammonium Exchange Capacity of the Modified Zeolite

The natural mordenite was treated hydrothermally with NaOH solutions, either with or without fusion with NaOH powder as pretreatment. Zeolite Na-P and analcime were identified as the reacted products, depending on the reaction conditions. The zeolites were identified by X-raydiffraction, and their cation exchange capacity (CEC) was determined. Zeolite Na-P has higher CEC (338 meq/100g) contrasted with the mordenite (181 meq/100g). Further more, the uptakes of NH4+ onto the zeolites have also been investigated. The Na-P has faster exchange rate, higher exchange amounts and better regeneration ability. The ammonium removal efficiency for the Na-P is above 90% at the ammonium initial concentrations less than 150 mg NH4+/g. It seemed that Na-P was fit for the further treatment of waters polluted with ammonium.

Using frequency‐labeled exchange transfer to separate out conventional magnetization transfer effects from exchange transfer effects when detecting ParaCEST agents

Paramagnetic chemical exchange saturation transfer agents combine the benefits of a large chemical shift difference and a fast exchange rate for sensitive MRI detection. However, the in vivo detection of these agents is hampered by the need for high B(1) fields to allow sufficiently fast saturation before exchange occurs, thus causing interference of large magnetization transfer effects from semisolid macromolecules. A recently developed approach named frequency-labeled exchange transfer utilizes excitation pulses instead of saturation pulses for detecting the exchanging protons. Using solutions and gel phantoms containing the europium (III) complex of DOTA tetraglycinate (EuDOTA-(gly)(-) (4) ), it is shown that frequency-labeled exchange transfer allows the separation of chemical exchange effects and magnetization transfer (MT) effects in the time domain, therefore allowing the study of the individual resonance of rapidly exchanging water molecules (k(ex) >10(4) s(-1) ) without interference from conventional broad-band MT.

Lanthanide(III) Complexes with Ligands Derived from a Cyclen Framework Containing Pyridinecarboxylate Pendants. The Effect of Steric Hindrance on the Hydration Number

Two new macrocyclic ligands, 6,6′-((1,4,7,10-tetraazacyclododecane-1,7-diyl)bis(methylene))dipicolinic acid (H2DODPA) and 6,6′-((4,10-dimethyl-1,4,7,10-tetraazacyclododecane-1,7-diyl)bis(methylene))dipicolinic acid (H2Me-DODPA), designed for complexation of lanthanide ions in aqueous solution, have been synthesized and studied. The X-ray crystal structure of [Yb(DODPA)](PF6)·H2O shows that the metal ion is directly bound to the eight donor atoms of the ligand, which results in a square-antiprismatic coordination around the metal ion. The hydration numbers (q) obtained from luminescence lifetime measurements in aqueous solution of the Eu(III) and Tb(III) complexes indicate that the DODPA complexes contain one inner-sphere water molecule, while those of the methylated analogue H2Me-DODPA are q = 0. The structure of the complexes in solution has been investigated by 1H and 13C NMR spectroscopy, as well as by theoretical calculations performed at the density functional theory (DFT; mPWB95) level. The minimum energy conformation calculated for the Yb(III) complex [Λ(λλλλ)] is in good agreement with the experimental structure in solution, as demonstrated by the analysis of the Yb(III)-induced paramagnetic 1H shifts. The nuclear magnetic relaxation dispersion (NMRD) profiles recorded for [Gd(Me-DODPA)]+ are typical of a complex with q = 0, where the observed relaxivity can be accounted for by the outer-sphere mechanism. However, [Gd(DODPA)]+ shows NMRD profiles consistent with the presence of both inner- and outer-sphere contributions to relaxivity. A simultaneous fitting of the NMRD profiles and variable temperature 17O NMR chemical shifts and transversal relaxation rates provided the parameters governing the relaxivity in [Gd(DODPA)]+. The results show that this system is endowed with a relatively fast water exchange rate k(ex)(298) = 58 × 10(6) s(–1).

Gadolinium complexes of monophosphinic acid DOTA derivatives conjugated to cyclodextrin scaffolds: efficient MRI contrast agents for higher magnetic fields

Middle-molecular-weight MRI contrast agents based on conjugates of a phosphinic acid DOTA analogue, 1,4,7,10-tetraazacyclododecane-4,7,10-triacetic-1-{methyl[(4-aminophenyl)methyl]phosphinic acid} (DO3AP(ABn)), with amino-substituted cyclodextrins were prepared and studied by a variety of physico-chemical methods. The conjugates were formed by reaction of the corresponding isothiocyanate with per-6-amino-α/β-cyclodextrin and were complexed with the Ln(III) ion to get the final complexes, (LnL)(6)-α-CD and (LnL)(7)-β-CD. Solution structure of the complexes was estimated by investigation of the Eu(III) complexes. The Gd(III) conjugate complexes are endowed with a short water residence time (τ(M) ∼ 10-15 ns at 298 K) and a high abundance of the twisted-square antiprismatic diastereoisomer. They show a high (1)H relaxivity at high fields due to a convenient combination of the fast water exchange rate and the slow rate of the molecular tumbling given by their macromolecular nature. The (1)H relaxation enhancements per molecule of a contrast agent (CA) are very high reaching for a larger (GdL)(7)-β-CD conjugate ∼140 s(-1) mM(-1) and ∼100 s(-1) mM(-1) at 25 °C and magnetic fields 1.5 T and 3 T, respectively, which is the highest reported longitudinal relaxivity for kinetically stable contrast agents of an intermediate molecular mass (<10 kDa) with one water molecule in the first coordination sphere.

Chemical exchange saturation transfer magnetic resonance imaging of human knee cartilage at 3 T and 7 T

The sensitivity of chemical exchange saturation transfer (CEST) on glycosaminoglycans (GAGs) in human knee cartilage (gagCEST) in vivo was evaluated at 3 and 7 T field strengths. Calculated gagCEST values without accounting for B(0) inhomogeneity (~0.6 ppm) were >20%. After B(0) inhomogeneity correction, calculated gagCEST values were negligible at 3 T and ~6% at 7 T. These results suggest that accurate B(0) correction is a prerequisite for observing reliable gagCEST. Results obtained with varying saturation pulse durations and amplitudes as well as the consistency between numerical simulations and our experimental results indicate that the negligible gagCEST observed at 3 T is due to direct saturation effects and fast exchange rate. As GAG loss from cartilage is expected to result in a further reduction in gagCEST, gagCEST method is not expected to be clinically useful at 3 T. At high fields such as 7 T, this method holds promise as a viable clinical technique.

Unique Structural and Nucleotide Exchange Features of the Rho1 GTPase of Entamoeba histolytica

The single-celled human parasite Entamoeba histolytica possesses a dynamic actin cytoskeleton vital for its intestinal and systemic pathogenicity. The E. histolytica genome encodes several Rho family GTPases known to regulate cytoskeletal dynamics. EhRho1, the first family member identified, was reported to be insensitive to the Rho GTPase-specific Clostridium botulinum C3 exoenzyme, raising the possibility that it may be a misclassified Ras family member. Here, we report the crystal structures of EhRho1 in both active and inactive states. EhRho1 is activated by a conserved switch mechanism, but diverges from mammalian Rho GTPases in lacking a signature Rho insert helix. EhRho1 engages a homolog of mDia, EhFormin1, suggesting a role in mediating serum-stimulated actin reorganization and microtubule formation during mitosis. EhRho1, but not a constitutively active mutant, interacts with a newly identified EhRhoGDI in a prenylation-dependent manner. Furthermore, constitutively active EhRho1 induces actin stress fiber formation in mammalian fibroblasts, thereby identifying it as a functional Rho family GTPase. EhRho1 exhibits a fast rate of nucleotide exchange relative to mammalian Rho GTPases due to a distinctive switch one isoleucine residue reminiscent of the constitutively active F28L mutation in human Cdc42, which for the latter protein, is sufficient for cellular transformation. Nonconserved, nucleotide-interacting residues within EhRho1, revealed by the crystal structure models, were observed to contribute a moderating influence on fast spontaneous nucleotide exchange. Collectively, these observations indicate that EhRho1 is a bona fide member of the Rho GTPase family, albeit with unique structural and functional aspects compared with mammalian Rho GTPases.

High Relaxivity and Stability of a Hydroxyquinolinate-Based Tripodal Monoaquagadolinium Complex for Use as a Bimodal MRI/Optical Imaging Agent

An octadentate ligand based on triazacyclononane and 8-hydroxyquinolinate/phenolate binding units leads to very soluble, highly stable lanthanide complexes. The monoaquagadolinium complex shows a high relaxivity as a result of the unusually long rotational correlation time, fast water exchange rate, and slow electronic relaxation. The ligand also acts as sensitizer of the near-IR luminescence emission of the Yb and Nd ions. It appears as an excellent candidate for use as a bimodal imaging agent.

Control algorithms developed for the enhanced radial field amplifier (ERFA) for JET

The company JEMA has delivered to the Joint European Torus (JET facility at Culham) the enhanced radial field amplifier (ERFA). This device is a high frequency, high power amplifier aimed at correcting instabilities due to fast plasma disturbances. The system is composed of four identical units connected in series through a connection box delivering up to ±12 kV, ±5 kA (60 MVAr) in four quadrant operation. Each unit is composed of an input converter stage, a DC link energy storage stage, an output inverter and an output bypass (for continuing operation in case of a unit failure). ERFA works as an energy exchanger between the internal DC link capacitors bank and the JET radial field coils. The input converter compensates for power losses in the JET coils and the ERFA during operation. The ERFA control system is fundamental for the amplifier performance to meet the speed of response required with the flexibility to achieve this for an unpredictable reference and for a wide range of load coil configurations. This paper covers the control architecture, the real-time evaluation and high speed response to the system requirements, and the fast exchange rate of data among ERFA units.

Functional Reconstitution of an Atypical G Protein Heterotrimer and Regulator of G Protein Signaling Protein (RGS1) from Arabidopsis thaliana

It has long been known that animal heterotrimeric Gαβγ proteins are activated by cell-surface receptors that promote GTP binding to the Gα subunit and dissociation of the heterotrimer. In contrast, the Gα protein from Arabidopsis thaliana (AtGPA1) can activate itself without a receptor or other exchange factor. It is unknown how AtGPA1 is regulated by Gβγ and the RGS (regulator of G protein signaling) protein AtRGS1, which is comprised of an RGS domain fused to a receptor-like domain. To better understand the cycle of G protein activation and inactivation in plants, we purified and reconstituted AtGPA1, full-length AtRGS1, and two putative Gβγ dimers. We show that the Arabidopsis Gα protein binds to its cognate Gβγ dimer directly and in a nucleotide-dependent manner. Although animal Gβγ dimers inhibit GTP binding to the Gα subunit, AtGPA1 retains fast activation in the presence of its cognate Gβγ dimer. We show further that the full-length AtRGS1 protein accelerates GTP hydrolysis and thereby counteracts the fast nucleotide exchange rate of AtGPA1. Finally, we show that AtGPA1 is less stable in complex with GDP than in complex with GTP or the Gβγ dimer. Molecular dynamics simulations and biophysical studies reveal that altered stability is likely due to increased dynamic motion in the N-terminal α-helix and Switch II of AtGPA1. Thus, despite profound differences in the mechanisms of activation, the Arabidopsis G protein is readily inactivated by its cognate RGS protein and forms a stable, GDP-bound, heterotrimeric complex similar to that found in animals.

Complexation and calcium-induced conformational changes in the cardiac troponin complex monitored by hydrogen/deuterium exchange and FT-ICR mass spectrometry

Cardiac muscle contraction is regulated by the heterotrimeric complex: troponin. We apply solution-phase hydrogen/deuterium exchange monitored by FT-ICR mass spectrometry to study the structural dynamics and the Ca-induced conformational changes of the cardiac isoform of troponin, by comparing H/D exchange rate constants for TnC alone, the binary TnC:TnI complex, and the ternary TnC:TnI:TnT complex for Ca-free and Ca-saturated states. The wide range of exchange rate constants indicates that the complexes possess both highly flexible and very rigid domains. Fast exchange rates were observed for the N-terminal extension of TnI (specific to the cardiac isoform), the DE linker in TnC alone, and the mobile domain of TnI. The slowest rates were for the IT coiled-coil that grants stability and stiffness to the complex. Ca2+ binding to site II of the N-lobe of TnC induces short-range allosteric effects, mainly protection for the C-lobe of TnC that transmits long-range conformational changes that reach the IT coiled-coil and even TnT1. The present results corroborate prior X-ray crystallography and NMR interpretations and also illuminate domains that were truncated or not resolved in those experiments.

Monetary policy and trade imbalance adjustment

The paper sets up a small open economy general equilibrium model to study the dynamics of the adjustment of trade imbalances under different policies based on the Chinese economy. The policies that adjust domestic prices require a long period to achieve trade balance and induce fluctuations of output and inflation, regardless of whether capital markets are open or closed, while policies that adjust the exchange rate quickly result in diminished trade surpluses, and do not cause fluctuations of output and inflation. However, policies that adjust the exchange rate slowly also lead to fluctuations under a capital flow setting. Nominal frictions are important factors to these differences, because they slow down the price adjustment, but do not bother the exchange rate changes. From the perspective of welfare, fast exchange rate adjustment policies are better than price policies, and adjustment under capital flow is better than adjustment under capital control. The implications for China's trade surplus are analyzed.

Synthesis of graft copolymers from a linear polyolefin through a combination of coordination polymerization and atom transfer radical polymerization

AbstractThis article reports on a facile route for the preparation of methyl acrylate and methyl methacrylate graft copolymers via a combination of catalytic olefin copolymerization and atom transfer radical polymerization (ATRP). The chemistry first involved a transforming process from ethylene/allylbenzene copolymers to a polyolefin multifunctional macroinitiator with pendant sulfonyl chloride groups. The key to the success of the graft copolymerization was ascribed to a fast exchange rate between the dormant species and active radical species by optimization of the various experimental parameters. Polyolefin‐g‐poly(methyl methacrylate) and polyolefin‐g‐poly(methyl acrylate) graft copolymers with controlled architecture and various graft lengths were, thus, successfully prepared under dilute ATRP conditions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

Epitaxial Nature and Transport Properties in (LaBa)Co2O5+δ Thin Films

Epitaxial (LaBa)Co2O5+δ thin films were grown on (001) LaAlO3 single-crystal substrates using pulsed laser deposition. Microstructure characterizations from X-ray diffraction and electron microscopy indicate that the films are highly c-axis oriented with cube-on-cube epitaxy. Transport property measurements indicate that the films have typical semiconductor behavior with a novel phase transition and hysteresis phenomena at 540 K. The chemical dynamic studies reveals that the resistance of the film changes drastically with the change of redox environment, i.e., the magnitude of resistance changes, ΔR = 1 × 102 ⇔ 1 × 106 Ω, is found within a short response time (∼700 ms). These phenomena suggest that the as-grown (LaBa)Co2O5+δ film have extraordinary sensitivity to reducing-oxidizing environment and the exceedingly fast surface exchange rate.

Evidence that D1-His332 in Photosystem II fromThermosynechococcus elongatusInteracts with the S3-State and not with the S2-State

Oxygen evolution by Photosystem II (PSII) is catalyzed by a Mn(4)Ca cluster. Thus far, from the crystallographic three-dimensional (3D) structures, seven amino acid residues have been identified as possible ligands of the Mn(4)Ca cluster. Among them, there is only one histidine, His332, which belongs to the D1 polypeptide. The relationships of the D1-His332 amino acid with kinetics and thermodynamic properties of the Mn(4)Ca cluster in the S(2)- and S(3)-states of the catalytic cycle were investigated in purified PSII from Thermosynechococcus elongatus. This was done by examining site-directed D1-His332Gln and D1-His332Ser mutants by a variety of spectroscopic techniques such as time-resolved UV-visible absorption change spectroscopy, cw- and pulse-EPR, thermoluminescence, and measurement of substrate water exchange. Both mutants grew photo-autotrophically and active PSII could be purified. On the basis of the parameters assessed in this work, the D1-His332(Gln, Ser) mutations had no effect in the S(2)-state. Electron spin-echo envelope modulation (ESEEM) spectroscopy also showed that possible interactions between the nuclear spin of the nitrogen(s) of D1-His332 with the electronic spin S = 1/2 of the Mn(4)Ca cluster in the S(2)-state were not detectable and that the D1-His332Ser mutation did not affect the detected hyperfine couplings. In contrast, the following changes were observed in the S(3)-state of the D1-His332 mutants: (1) The redox potential of the S(3)/S(2) couple was slightly increased by < or = 20 meV, (2) The S(3)-EPR spectrum was slightly modified, (3) The D1-His332Gln mutation resulted in a approximately 3 fold decrease of the slow (tightly bound) exchange rate and a approximately 2 fold increase of the fast exchange rate of the water substrate molecules. All these results suggest that the D1-His332 would be more involved in S(3) than in S(2). This could be one element of the conformational changes put forward in the S(2) to S(3) transition.

Dynamics and Structure of Ln(III)−Aqua Ions: A Comparative Molecular Dynamics Study Using ab Initio Based Flexible and Polarizable Model Potentials

Aqueous solutions of a light (Nd3+), a middle (Gd3+), and a heavy (Yb3+) lanthanide ion were studied using ab initio based flexible and polarizable analytical potentials in classical molecular dynamics simulations to describe their thermodynamic, structural, and dynamic features. To avoid the spurious demise of O-H bonds, it was necessary to reparametrize an existing water model, which resulted in an improved description of pure water. The good agreement of the results from the simulations with the experimental hydration enthalpies, the Ln(III)-water radial distribution functions, and the water-exchange rates validated the potentials, though the r(Ln-Ow) distances were 6% longer than the experimentally determined values. A nona-coordinated state was found for Nd3+ in 95% of the simulation, with a tricapped trigonal prism (TCTP) geometry; the corresponding water-exchange mechanism was found to be of dissociative interchange (Id) character through a short-lived octa-coordinated transition state in a square antiprism (SQA) geometry. An octa-coordinated state in SQA geometry was found for Yb3+ in 99% of the simulation, and the observed exchange events exhibited characteristics of an interchange (I) mechanism. For Gd3+ an equilibrium was observed between 8-fold SQA and 9-fold TCTP coordinated states that was maintained by the frequent exchange of a water molecule from the first hydration shell with the bulk, thus producing significant deviations from the ideal geometries, and a fast exchange rate. Though strong water-water interactions prevented a full alignment of the dipoles to the ion's electric field, the screening was found large enough as to limit its range to 5 A; water molecules further apart from the ion were found to have the same dipole as the molecules in the bulk, and a random orientation. The interplay among the water-ion and the water-water interactions determined the different coordination numbers and the different dynamics of the water exchange in the first hydration shell for each ion.

Chemical exchange of hydroxyl protons in quercetin measured by pulsed field gradient NMR

The diffusion behavior of hydroxyl protons (OH) in quercetin in 100% DMSO-d6 (deuterium dimethylsulfoxide) and a 90% DMSO-d6 solution containing 10% H2O was investigated with 600 MHz 1H pulsed field gradient (PFG) nuclear magnetic resonance (NMR). Only resonances of the 5-hydroxyl protons (OH5) were well resolved in NMR spectra of quercetin for all solutions under study. This phenomenon is explained by the intramolecular hydrogen bonding between OH5 protons and the 4-carbonyl oxygen (CO4). During diffusion experiments, the OH5 protons showed a biexponential diffusion decay, indicating an exchange process with water. As water content in the solvents increased, the lifetime (τ q) of the OH5 protons decreased from 96.7±10.0 ms in 100% DMSO-d6 to 14.3±1.4 ms in the 90% DMSO-d6 solution containing 10% H2O, indicating an increase in the exchange rate (k q = l/τ q) of the OH5 protons. This study demonstrates that the diffusion approach with PFG-NMR is much faster and easier for estimating the short lifetime or fast exchange rate of hydroxyl protons in quercetin.

Improving real-time measurement of H/D exchange using a FTIR biospectroscopic probe

We describe the improvement of a novel approach to investigating hydrogen/deuterium (H/D) exchange kinetics in biomolecules using transmission infrared spectroscopy. The method makes use of a Fourier transform infrared spectrometer coupled with a microdialysis flow cell to determine exchange rates of labile hydrogens. With this cell system, the monitoring of exchange reactions has been studied here as a function of some cell characteristics such as: (a) dialysis membrane surface contacting both the H(2)O and D(2)O compartments; (b) molecular cutoff of dialysis membrane; and (c) distance between the cell-filling holes. The best improvement has been obtained by increasing the dialysis membrane surface followed by increase of molecular cutoff. However, not significant differences were found using various distances between filling holes. The fastest exchange rate which can be measured with the cell system used here is found to be k = 0.41 +/- 0.02 min(-1), that is, about threefold greater than the one got in a previous work. This microdialysis flow cell has been used here for the study of H/D exchange in nucleic acids with subsequent structural analysis by 2D correlation spectroscopy.