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PubMed1998

Proton Diffusion and T1 Relaxation in Polyacrylamide Gels: A Unified Approach Using Volume Averaging.

The structure of polyacrylamide gels was studied using proton spin-lattice relaxation and PFG diffusion methods. Polyacrylamide gels, with total polymer concentrations ranging from 0.25 to 0.35 g/ml and crosslinker concentrations from 0 to 10% by weight, were studied. The data showed no effect of the crosslinker concentration on the diffusion of water molecules. The Ogston-Morris and Mackie-Meares models fit the general trends observed for water diffusion in gels. The diffusion coefficients from the volume averaging method also fit the data, and this theory was able to account for the effects of water-gel interactions that are not accounted for in the other two theories. The averaging theory also did not require the physically unrealistic assumption, required in the other two theories, that the acrylamide fibers are of similar size to water molecules. Contrary to the diffusion data, T1 relaxation measurements showed a significant effect of crosslinker concentration on the relaxation of water in gels. The model developed using the Bloch equations and the volume averaging method described the effects of water adsorption on the gel medium on both the diffusion coefficients and the relaxation measurements. In the proposed model the gel medium was assumed to consist of three phases (i.e., bulk water, uncrosslinked acrylamide fibers, and a bisacrylamide crosslinker phase). The effects of the crosslinker concentration were accounted for by introducing the proton partition coefficient, Keq, between the bulk water and crosslinker phase. The derived relaxation equations were successful in fitting the experimental data. The partition coefficient, Keq, decreased significantly as the crosslinker concentration increased from 5 to 10% by weight. This trend is consistent with the idea that bisacrylamide tends to form hydrophobic regions with increasing crosslinker concentration. Copyright 1998 Academic Press.

Journal Article↗
PubMed2003

Disseminating innovations in health care.

Health care is rich in evidence-based innovations, yet even when such innovations are implemented successfully in one location, they often disseminate slowly-if at all. Diffusion of innovations is a major challenge in all industries including health care. This article examines the theory and research on the dissemination of innovations and suggests applications of that theory to health care. It explores in detail 3 clusters of influence on the rate of diffusion of innovations within an organization: the perceptions of the innovation, the characteristics of the individuals who may adopt the change, and contextual and managerial factors within the organization. This theory makes plausible at least 7 recommendations for health care executives who want to accelerate the rate of diffusion of innovations within their organizations: find sound innovations, find and support "innovators," invest in "early adopters," make early adopter activity observable, trust and enable reinvention, create slack for change, and lead by example.

Diffusion of Innovation↗
PubMed1989

Diffusion of rat atrial natriuretic factor in thermoreversible poloxamer gels.

Concentrated poloxamer 407 solutions display a negative thermorheological behaviour, resulting in a higher viscosity at body temperature than below. This could be exploited for various controlled delivery applications including the nasal delivery of peptides. The rheology of the gel and the diffusion of ANF were studied as a function of temperature. A theory is proposed, according to which a temperature rise creates an intermicellar network resulting in a viscosity increase. The diffusion of the drug appears limited only by the presence of micelles which lengthens the diffusion pathways and is not significantly influenced by the formation of this network.

Atrial Natriuretic Factor↗
PubMed1989

Mutual diffusion of interacting membrane proteins.

The generalized Stokes-Einstein equation is used, together with the two-dimensional pressure equation, to analyze mutual diffusion in concentrated membrane systems. These equations can be used to investigate the role that both direct and hydrodynamic interactions play in determining diffusive behavior. Here only direct interactions are explicitly incorporated into the theory at high densities; however, both direct and hydrodynamic interactions are analyzed for some dilute solutions. We look at diffusion in the presence of weak attractions, soft repulsions, and hard-core repulsions. It is found that, at low densities, attractions retard mutual diffusion while repulsions enhance it. Mechanistically, attractions tend to tether particles together and oppose the dissipation of gradients or fluctuations in concentration, while repulsions provide a driving force that pushes particles apart. At higher concentrations, changes in the structure of the fluid enhance mutual diffusion even in the presence of attractions. It is shown that the theoretical description of postelectrophoresis relaxation and fluorescence correlation spectroscopy experiments must be modified if interacting systems are studied. The effects of interactions on mutual diffusion coefficients have probably already been seen in postelectrophoresis relaxation experiments.

Diffusion↗
PubMed2003

Analysis of molecular diffusion in ftsK cell-division mutants using laser surgery.

Escherichia coli cells that lack the carboxy-terminal part of FtsK fail to segregate their chromosomes properly during cytokinesis and tend to form chains. These chains are possibly formed as a result of DNA being trapped in the division planes or a failure to fuse the membrane during septum formation. If so, small molecules might diffuse between the apparent cell compartments. To investigate this theory, we developed an optical workstation that allows simultaneous imaging of and surgical operations on cellular objects in the sub-micrometre range. By surgical incisions of E. coli cell poles, diffusion of propidium iodide (PI) can be followed in real time. This analysis showed that PI was unable to diffuse from one cell equivalent to another in chain-forming ftsK mutants. Thus, the cytoplasm of the cell compartments in the chains seems to be fully separated.

Cell Division↗
PubMed1999

Dielectric and transport properties of a supercooled symmetrical molten salt.

The liquid-glass transition of the restricted primitive model for a symmetrical molten salt is studied using mode-coupling theory. The transition at high densities is predicted to obey the Lindemann criterion for melting, and the charge-density peak found in neutron-scattering experiments on ionic glass formers is qualitatively reproduced. Frequency-dependent dielectric functions, shear viscosities, and dynamical conductivities of the supercooled liquid are presented. Comparing the latter to the diffusion constant, we find that mode-coupling theory reproduces the Nernst-Einstein relation. The Stokes-Einstein radius is found to be approximately equal to the particle radius only near the high-density glass transition.

Journal Article↗
PubMed2003

Hydration and ion pairing in aqueous sodium oxalate solutions.

Dielectric spectra have been measured for aqueous sodium oxalate solutions up to the saturation concentration (0.04 < or = c[mmol L-1] < or = 0.25) at 25 degrees C over the approximate frequency range 0.2 < or = v [GHz] < or = 20. The spectra exhibit a process at about 1 GHz associated with the presence of ion pairs, in addition to the dominant solvent relaxation process at about 18 GHz. Detailed analysis of the solvent dispersion amplitude indicates that the oxalate ion is highly hydrated but that its solvation sheath is "fragile", decreasing quickly with increasing solute concentration. The NaOx(aq)- ion pair is shown to be of the double-solvent-separated (2SIP) type, with an infinite dilution association constant KA = 1.04 +/- 0.02. Analysis of the ion-pair relaxation time as a function of solute concentration gave rate constants for the formation (k12 = (7.3 +/- 0.4) 10(9) L mol-1 s-1) and dissociation (k21 = (6.7 +/- 0.5) 10(8) s-1) of the ion pair. These values are reasonably close to the diffusion-controlled values predicted by the Eigen theory, consistent with a 2SIP structure for the ion pair.

Journal Article↗
PubMed2005

[The effects of recurrent otitis media with effusion on speech development].

Otitis media with effusion (OME) may have adverse effects on children's cognitive, language, speech and psychosocial development. This has been demonstrated using several lines of research, the results of which, however, are not unequivocal. The question of how OME can interact with language, speech and cognitive development is also a subject of debate. According to the acoustic-phonetic theory, reduced perceptual ability during episodes of OME results in a degraded representation of subphonemic features of speech sounds, leading to speech delay. The mediated theory holds that fluctuant hearing loss endangers diffuse cognitive-linguistic effects, affecting speech perception and production.

Animals↗
PubMed1994

A model for the binding of E. coli single-strand binding protein to supercoiled DNA.

A model is proposed for the binding of E. coli single strand binding protein (SSB) to supercoiled DNA. The basic tetrameric binding units of SSB are assumed to bind in pairs to the complementary single strands of a locally melted region. The cooperativity of the binding includes contributions from both protein-protein and base-pair stacking interactions. Each bound SSB tetramer is assumed to unwind l = 34 bp, which implies an unwinding angle of 3.27 turns. The resulting loss of superhelical strain is the essential driving force for binding SSB to supercoiled DNAs. All molecular parameters entering into the theory are estimated from available data, except for the composite binding constant (Ka), which is adjusted to best-fit the theory to the fluorescence quenching (FQ) and diffusion coefficient (D0) data of Langowski et al. Very good fits are obtained with optimum values of Ka that are consistent with estimates from other data. This binding model predicts several noteworthy features. (1) SSB binds essentially always in a single contiguous stack on a supercoiled plasmid, and relative fluctuations in stack length are quite small, in agreement with results of electron microscopy studies. (2) The progressive loss of superhelical strain with increasing bound ligand decreases the affinity of the DNA for SSB. This anti-cooperativity offsets the cooperativity of the binding and causes apparent saturation of the binding at rather low binding ratios. Consequently, over the limited span of the measurements, the FQ data can also be satisfactorily fitted by a non-cooperative model comprising a small number of independent sites. (3) When SSB binds to a population of different topoisomers, the distribution of linking differences of the resulting complexes is extremely narrow. Thus, SSB acts to level any differences in superhelical strain in a population of topoisomers. Finally, the effects of restricting binding to a region comprising only part of the plasmid are assessed.

Binding Sites↗
PubMed2006

Metabotropic glutamate receptors as a strategic target for the treatment of epilepsy.

Epilepsy is a chronic neurological disorder that has many known types, including generalized epilepsies that involve cortical and subcortical structures. A proportion of patients have seizures that are resistant to traditional anti-epilepsy drugs, which mainly target ion channels or postsynaptic receptors. This resistance to conventional therapies makes it important to identify novel targets for the treatment of epilepsy. Given the involvement of the neurotransmitter glutamate in the etiology of epilepsy, targets that control glutamatergic neurotransmission are of special interest. The metabotropic glutamate receptors (mGluRs) are of a family of eight G-protein-coupled receptors that serve unique regulatory functions at synapses that use the neurotransmitter glutamate. Their distribution within the central nervous system provides a platform for both presynaptic control of glutamate release, as well as postsynaptic control of neuronal responses to glutamate. In recent years, substantial efforts have been made towards developing selective agonists and antagonists which may be useful for targeting specific receptor subtypes in an attempt to harness the therapeutic potential of these receptors. We examine the possibility of intervening at these receptors by considering the specific example of absence seizures, a form of generalized, non-convulsive seizure that involves the thalamus. Views of the etiology of absence seizures have evolved over time from the "centrencephalic" concept of a diffuse subcortical pacemaker toward the "cortical focus" theory in which cortical hyperexcitability leads the thalamus into the 3-4 Hz rhythms that are characteristic of absence seizures. Since the cortex communicates with the thalamus via a massive glutamatergic projection, ionotropic glutamate receptor (iGluR) blockade has held promise, but the global nature of iGluR intervention has precluded the clinical effectiveness of drugs that block iGluRs. In contrast, mGluRs, because they modulate iGluRs at glutamatergic synapses only under certain conditions, may quell seizure activity by selectively reducing hyperactive glutamatergic synaptic communication within the cortex and thalamus without significantly affecting normal response rates. In this article, we review the circuitry and events leading to absence seizure generation within the corticothalamic network, we present a comprehensive review of the synaptic location and function of mGluRs within the thalamus and cerebral cortex, and review the current knowledge of mGluR modulation and seizure generation. We conclude by reviewing the potential advantages of Group II mGluRs, specifically mGluR2, in the treatment of both convulsive and non-convulsive seizures.

Animals↗
PubMed2001

Spatial range of autocrine signaling: modeling and computational analysis.

Autocrine loops formed by growth factors and their receptors have been identified in a large number of developmental, physiological, and pathological contexts. In general, the spatially distributed and recursive nature of autocrine signaling systems makes their experimental analysis, and often even their detection, very difficult. Here, we combine Brownian motion theory, Monte Carlo simulations, and reaction-diffusion models to analyze the spatial operation of autocrine loops. Within this modeling framework, the ability of autocrine cells to recapture the endogenous ligand and the distances traveled by autocrine ligands are explicitly related to ligand diffusion coefficients, density of surface receptors, ligand secretion rate, and rate constants of ligand binding and endocytic internalization. Applying our models to study autocrine loops in the epidermal growth factor receptor system, we find that autocrine loops can be highly localized--even at the level of a single cell. We demonstrate how the variations in molecular and cellular parameters may "tune" the spatial range of autocrine signals over several orders of magnitude: from microns to millimeters. We argue that this versatile regulation of the spatial range of autocrine signaling enables autocrine cells to perceive a broad spectrum of environmental information.

Autocrine Communication↗
PubMed1997

Strain in the folding nucleus of chymotrypsin inhibitor 2.

BACKGROUND: Chymotrypsin inhibitor 2 (CI2) is a member of the class of fast-folding small proteins, which is very suitable for testing theories of folding. CI2 folds around a diffuse extended nucleus consisting of the single alpha helix and a set of hydrophobic residues. In particular, Ala16 has been predicted and independently found to interact with Leu49 and Ile57, hydrophobic residues that are highly conserved among homologues. We have characterised in detail the interactions between these residues in the folding nucleus of the protein by using double-mutant cycles. RESULTS: Surprisingly, we find that there is some destabilising strain in the transition state for folding of the wild-type protein between Ala16 and Ile57. Further, we find that the strain is larger in the native state of the protein. This is shown directly in the unfolding kinetics, which clearly show a release of strain. The net result of this is that the presence of both residues speeds up folding. Ala16 and Leu49 interact favourably in the transition state, but have no net interaction energy in the native state. CONCLUSIONS: Part of the folding nucleus of the protein fits together more snugly in the transition state than it does in the native state. Interactions between some of the closely packed residues in the folding nucleus of CI2 may perhaps be optimised for the rate of folding and not for stability.

Alanine↗
PubMed2001

Predicting divalent metal sorption to hydrous Al, Fe, and Mn oxides.

Intraparticle diffusion in microporous amorphous oxides of aluminum, iron, and manganese affects contaminant mobility and bioavailability in soils and sediments. This sorption is a lengthy process, as such, predictive methods to assess thermodynamic and transport parameters would be useful. Based on enthalpies observed in recent work, adsorption of Zn, Cd, and Sr to amorphous oxides is a physical type of reaction where the metal ions retain their waters of hydration. Consequently the adsorbate-surface interactions are a function of electrostatic forces of attraction. Accordingly, knowing the hydrated radius and the hydration number of a metal cation, a correlation is used to predict enthalpy and hence affinity. Using the resulting enthalpy and the Polanyi relation, the activation energy was evaluated for Ni and Ca. This Polanyi relationship reveals that for a given metal the activation energies with respect to these oxides are comparable. Additionally, metals of the same periodic group appear to form similar sorption complexes with a particular oxide and therefore have an equivalent Polanyi constant, alpha. Assuming a sinusoidal function describes the surface potential along the oxide surface, the surface diffusivity was predicted from the site activation theory. In this work, the predicted sorption parameters proved to be equivalent to experimental ones given the associated errors.

Adsorption↗
PubMed2006

Hyperconjugation and the increasing bulk of OCOCX3 substituents in trans-1,4-disubstituted cyclohexanes destabilize the diequatorial conformer.

The trans diesters of 1,4-cyclohexanediol with a number of acetic acid analogues, CX3COOH, of varying steric hindrance and polarity (CX3 = Me, Et, iso-Pr, tert-Bu, CF3, CH2Cl, CHCl2, CCl3, CH2Br, CHBr2, CBr3) were synthesized, and the axial,axial/equatorial,equatorial conformational equilibria were studied by low-temperature 1H NMR spectroscopy in CD2Cl2. The structures and relative energies of the axial,axial and equatorial,equatorial conformers were calculated at both the MP2/6-311G* and the MP2/6-311+G* levels of theory, and it was only by including diffuse functions that a good correlation of deltaG(o)calcd vs deltaG(o)exptl could be obtained. Both the structures and the energy differences of the axial,axial and equatorial,equatorial conformers are discussed with respect to the established models of conformational analysis, viz., steric 1,3-diaxial and hyperconjugative interactions. Interestingly, the hyperconjugative interactions sigma(C-C)/sigma(C-H) --> sigma*(C-O), together with a steric effect which also destabilizes the equatorial,equatorial conformers on increasing bulk of the substituents, proved to dominate the position of the conformational equilibria. In addition, the preference of the axial,axial conformers with respect to their equatorial,equatorial analogues was greater than expected from the conformational energies of the corresponding substituents in the monosubstituted cyclohexyl esters. The reason for this very interesting and unexpected result is also discussed.

Journal Article↗
PubMed1994

Transcellular transport of benzoic acid across Caco-2 cells by a pH-dependent and carrier-mediated transport mechanism.

The pH-dependent transcellular transport of [14C]benzoic acid across a Caco-2 cell monolayer is shown to be mediated by a monocarboxylic acid-specific carrier-mediated transport system, localized on the apical membrane. Evidence for the carrier-mediated transport of benzoic acid includes (a) the significant temperature and concentration dependence, (b) the metabolic energy dependence, (c) the inhibition by unlabeled benzoic acid and other monocarboxylic acids, (d) countertransport effects on the uptake of [14C]benzoic acid, and (e) effects of a proteinase (papain) and amino acid-modifying reagents. Furthermore, since carbonylcyanide p-trifluoromethoxyphenylhydrazone and nigericin significantly inhibited the transport of [14C]benzoic acid, the direct driving force for benzoic acid transport is suggested to be the inwardly directed proton gradient. From these results, together with previous observations using intestinal brush border membrane vesicles, the pH dependence of the transcellular transport of certain organic weak acids across Caco-2 cells is considered to result mainly from a proton gradient-dependent, carrier-mediated transport mechanism, rather than passive diffusion according to the pH-partition theory.

Acetates↗
PubMed1997

The nitric oxide donor nitroprusside intraperitoneally affects peritoneal permeability in CAPD.

Nitroprusside is a nitric oxide (NO) donor. To investigate effects of nitroprusside i.p. on peritoneal permeability and perfusion, standard peritoneal permeability analyses were performed. Ten stable CAPD patients were studied twice within one week with glucose based dialysate (1.36% Dianeal) with and without addition of nitroprusside 4.5 mg/liter. Mass transfer area coefficients (MTAC) of CO2 were calculated to estimate peritoneal blood flow. Nitrate, a stable metabolite of NO, and cGMP, a second messenger of NO synthesis, were measured in plasma and dialysate. The MTACs of low molecular weight solutes were greater with nitroprusside (NP) compared to the control dwell (C): creatinine median 14.1 (NP) versus 9.9 ml/min (C), urea 21.7 (NP) versus 18.5 ml/min (C) and urate 10.5 (NP) versus 8.6 ml/min (C) (P < 0.05 for all). This points to an increased effective peritoneal surface area with nitroprusside. Furthermore, the restriction coefficient for the low molecular weight solutes decreased from 1.28 (C) to 1.23 (NP) (P = 0.02), suggesting some effect also on the size selectivity to these solutes. The effect of nitroprusside on the clearances of serum proteins was more pronounced. The increase with nitroprusside was 34% for beta 2-microglobulin, 70% for albumin, 77% for IgG and 143% for alpha 2-macroglobulin. This reduction in size selectivity was reflected in a decrease in the restriction coefficient for macromolecules from 2.29 (C) to 1.86 (NP), P < 0.01. This implies an increase in the intrinsic permeability of the peritoneal membrane. Kinetic modeling, using computer simulations, was done to analyze these effects in terms of the pore theory, using a convection model and a diffusion model for the transport of macromolecules. Nitroprusside led to an increase of both the large pore radius and the small pore radius and of the unrestricted area over diffusion distance. These effects were more pronounced with the diffusion model. The MTAC CO2 was not different: NP 76.9 and C 84.1 ml/min. MTACs of nitrate were not greater than expected on the basis of the molecular weight during both dwells. The dialysate/plasma (D/P) ratio of cGMP was greater after addition of nitroprusside: 0.36, range 0.21 to 0.77 (C) and 0.74, 0.23 to 2.50 (NP), P = 0.02. With nitroprusside the D/P ratio of cGMP was greater than expected on the basis of its molecular weight (P < 0.001). This points to local generation of cGMP after the addition of nitroprusside, induced by NO. No differences were found in the dialysate concentrations of the prostaglandins (PG) PGE2 and 6-keto-PGF1 alpha and thromboxane B2 after addition of nitroprusside. The transcapillary ultrafiltration rate and the net ultrafiltration rate during four hours were not different with nitroprusside. In conclusion, nitroprusside i.p. increased the effective peritoneal surface area and the intrinsic permeability, but the peritoneal blood flow did not change. The greater than expected D/P ratios of cGMP point to local generation of cGMP with nitroprusside, induced by NO.

Adult↗
PubMed1990

Electrostatic field around cytochrome c: theory and energy transfer experiment.

Energy transfer in the "rapid diffusion" limit from electronically excited terbium(III) chelates in three different charge states to horse heart ferricytochrome c was measured as a function of ionic strength. Theoretical rate constants calculated by numerical integration of the Forster integral (containing the Poisson-Boltzmann-generated protein electrostatic potential) were compared with the experimental data to evaluate the accuracy of protein electrostatic field calculations at the protein/solvent interface. Two dielectric formalisms were used: a simple coulombic/Debye-Hückel procedure and a finite difference method [Warwicker, J. & Watson, H. C. (1982) J. Mol. Biol. 157, 671-679] that accounts for the low-dielectric protein interior and the irregular protein/solvent boundary. Good agreement with experiment was obtained and the ionic-strength dependence of the reaction was successfully reproduced. The sensitivity of theoretical rate constants to the choices of effective donor sphere size and the energy transfer distance criterion was analyzed. Electrostatic potential and rate-constant calculations were carried out on sets of structures collected along two molecular dynamics trajectories of cytochrome c. Protein conformational fluctuations were shown to produce large variations in the calculated energy transfer rate constant. We conclude that protein fluctuations and the resulting transient structures can play significant roles in biological or catalytic activities that are not apparent from examination of a static structure. For calculating protein electrostatics, large-scale low-frequency conformational fluctuations, such as charged side-chain reorientation, are established to be as important as the computational method for incorporating dielectric boundary effects.

Animals↗
PubMed1996

Characterization of polyion counterion interactions in cartilage by 23Na NMR relaxation.

Nuclear quadrupole relaxation is a sensitive measure of electrolyte environments. We used the relaxation of 23Na to probe mobile ion-matrix interactions and the electrostatic structure of the polyelectrolyte extracellular matrix of cartilage. Specifically, we measured spin-lattice and spin-spin relaxation times of 23Na in bovine nasal cartilage at 132 MHz under several conditions. Matrix fixed charge density was reduced by protonating anionic sites and by matrix digestion with trypsin and the relaxation times compared to controls. Under all conditions studied, measured longitudinal relaxation was monoexponential with values ranging from 16-32 msec. Transverse relaxation exhibited biexponential behavior in all cartilage samples with a fast component in the range of 2 to 5 ms and a slow component between 16 and 53 ms. Reduction in matrix fixed charge density in all cases led to a decrease in the relaxation rates. The results suggest a two-site model for Na+ ions in cartilage and a relaxation mechanism involving both polyion segmental motion and counterion diffusion. In the context of ion condensation theory, the implication of a two-site model is that the mean polyion-polyion spacing may be less than 0.7 nm. The mean polyion-counterion spacings were estimated by calculating correlation times and quadrupole coupling constants. These spacings were found to be 0.5-0.7 nm.

Animals↗