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1.
Phys Chem Chem Phys ; 25(47): 32709-32714, 2023 Dec 06.
Article in English | MEDLINE | ID: mdl-38014720

ABSTRACT

Ice nucleation and formation play pivotal roles across various domains, from environmental science to food engineering. However, the exact ice formation mechanisms remain incompletely understood. This study introduces a novel ice formation process, which can be either heterogeneous or homogeneous, depending on the initial conditions. The process initiates ice crystal growth from a nucleus composed of a micron-sized partially melted ice particle. We explore the role of van der Waals (Lifshitz)-free energy and its resulting stress in the accumulation of ice at the interface with water vapor. Our analysis suggests that this process could lead to thicknesses ranging from nanometers to micrometers, depending on the size and degree of initial melting of the ice nucleus. We provide evidence for the growth of thin ice layers instead of liquid water films on a partially melted ice-vapor interface, offering some insights into mist and fog formation. We also link it to potential atmospheric and astrogeophysical applications.

2.
Phys Chem Chem Phys ; 22(20): 11362-11373, 2020 May 28.
Article in English | MEDLINE | ID: mdl-32373792

ABSTRACT

Considering ice-premelting on a quartz rock surface (i.e. silica) we calculate the Lifshitz excess pressures in a four layer system with rock-ice-water-air. Our calculations give excess pressures across (1) ice layer, (2) water layer, and (3) ice-water interface for different ice and water layer thicknesses. We analyse equilibrium conditions where the different excess pressures take zero value, stabilized in part by repulsive Lifshitz interactions. In contrast to previous investigations which considered varying thickness of only one layer (ice or water), here we present theory allowing for simultaneous variation of both layer thicknesses. For a given total thickness of ice and water, this allows multiple alternative equilibrium solutions. Consequently the final state of a system will depend on initial conditions and may explain variation in experimental measurements of the thicknesses of water and ice layers.

3.
Langmuir ; 35(12): 4218-4223, 2019 Mar 26.
Article in English | MEDLINE | ID: mdl-30821464

ABSTRACT

Gas bubbles in a water-filled cavity move upward because of buoyancy. Near the roof, additional forces come into play, such as Lifshitz, double layer, and hydrodynamic forces. Below uncharged metallic surfaces, repulsive Lifshitz forces combined with buoyancy forces provide a way to trap micrometer-sized bubbles. We demonstrate how bubbles of this size can be stably trapped at experimentally accessible distances, the distances being tunable with the surface material. By contrast, large bubbles (≥100 µm) are usually pushed toward the roof by buoyancy forces and adhere to the surface. Gas bubbles with radii ranging from 1 to 10 µm can be trapped at equilibrium distances from 190 to 35 nm. As a model for rock, sand grains, and biosurfaces, we consider dielectric materials such as silica and polystyrene, whereas aluminium, gold, and silver are the examples of metal surfaces. Finally, we demonstrate that the presence of surface charges further strengthens the trapping by inducing ion adsorption forces.

4.
Phys Rev E ; 108(3-1): 034801, 2023 Sep.
Article in English | MEDLINE | ID: mdl-37849091

ABSTRACT

We explore the Casimir-Lifshitz free-energy theory for surface freezing of methane gas hydrates near the freezing point of water. The theory enables us to explore different pathways, resulting in anomalous (stabilizing) ice layers on methane hydrate surfaces via energy minimization. Notably, we will contrast the gas hydrate material properties, under which thin ice films can form in water vapor, with those previously predicted to be required in the presence of liquid water. It is predicted that methane hydrates in water vapor near the freezing point of water nucleate ice films, instead of water films.

5.
J Cell Biochem ; 110(5): 1226-33, 2010 Aug 01.
Article in English | MEDLINE | ID: mdl-20544797

ABSTRACT

Connective tissue growth factor (CTGF/CCN2) is a matricellular protein induced by transforming growth factor (TGF)-beta and intimately involved with tissue repair and overexpressed in various fibrotic conditions. We previously showed that keratinocytes in vitro downregulate TGF-beta-induced expression of CTGF in fibroblasts by an interleukin (IL)-1 alpha-dependent mechanism. Here, we investigated further the mechanisms of this downregulation by both IL-1alpha and beta. Human dermal fibroblasts and NIH 3T3 cells were treated with IL-1alpha or beta in presence or absence of TGF-beta1. IL-1 suppressed basal and TGF-beta-induced CTGF mRNA and protein expression. IL-1alpha and beta inhibited TGF-beta-stimulated CTGF promoter activity, and the activity of a synthetic minimal promoter containing Smad 3-binding CAGA elements. Furthermore, IL-1alpha and beta inhibited TGF-beta-stimulated Smad 3 phosphorylation, possibly linked to an observed increase in Smad 7 mRNA expression. In addition, RNA interference suggested that TGF-beta activated kinase1 (TAK1) is necessary for IL-1 inhibition of TGF-beta-stimulated CTGF expression. These results add to the understanding of how the expression of CTGF in human dermal fibroblasts is regulated, which in turn may have implications for the pathogenesis of fibrotic conditions involving the skin.


Subject(s)
Connective Tissue Growth Factor/metabolism , Fibroblasts/drug effects , Interleukin-1alpha/pharmacology , Interleukin-1beta/pharmacology , Animals , Blotting, Western , Connective Tissue Growth Factor/genetics , Dermis/cytology , Fibroblasts/cytology , Fibroblasts/metabolism , Gene Expression Regulation/drug effects , Humans , MAP Kinase Kinase Kinases/genetics , MAP Kinase Kinase Kinases/metabolism , Mice , NIH 3T3 Cells , Phosphorylation/drug effects , Promoter Regions, Genetic/genetics , RNA Interference , Reverse Transcriptase Polymerase Chain Reaction , Smad3 Protein/metabolism , Smad7 Protein/genetics , Smad7 Protein/metabolism , Transforming Growth Factor beta/pharmacology
6.
Langmuir ; 26(5): 3323-8, 2010 Mar 02.
Article in English | MEDLINE | ID: mdl-20175572

ABSTRACT

A modified Poisson-Boltzmann analysis is made of the double layer interaction between two silica surfaces and two alumina surfaces in chloride electrolyte. The analysis incorporates nonelectrostatic ion-surface dispersion interactions based on ab initio ionic excess polarizabilities with finite ion sizes. A hydration model for the tightly held hydration shell of kosmotropic ions is introduced. A direct Hofmeister series (K > Na > Li) is found at the silica surface while the reversed series (Li > Na > K) is found at alumina, bringing theory in line with experiment for the first time. Calculations with unhydrated ions also suggest that surface-induced dehydration may be occurring at the alumina surface.


Subject(s)
Metals, Alkali/chemistry , Water/chemistry , Aluminum Oxide/chemistry , Chlorides/chemistry , Electrolytes/chemistry , Hydrogen-Ion Concentration , Salts/chemistry , Silicon Dioxide/chemistry , Static Electricity , Surface Properties
7.
J Phys Chem B ; 113(23): 8124-7, 2009 Jun 11.
Article in English | MEDLINE | ID: mdl-19441847

ABSTRACT

In two-phase finite volume systems of electroneutral phospholipids, the electrolyte concentration is different in the two phases. The partitioning is highly anion-specific, a phenomenon not accounted for by classical electrolyte theories. It is explained if ionic dispersion forces that lead to specific ion binding are taken into account. The mechanism provides a contribution to active ion pumps not previously considered.


Subject(s)
Anions , Models, Theoretical , Phospholipids/chemistry
8.
Bone Joint J ; 101-B(4): 386-389, 2019 04.
Article in English | MEDLINE | ID: mdl-30929492

ABSTRACT

AIMS: The aim of this study was to evaluate fretting and corrosion in retrieved oxidized zirconium (OxZr; OXINIUM, Smith & Nephew, Memphis, Tennessee) femoral heads and compare the results with those from a matched cohort of cobalt-chromium (CoCr) femoral heads. PATIENTS AND METHODS: A total of 28 OxZr femoral heads were retrieved during revision total hip arthroplasty (THA) and matched to 28 retrieved CoCr heads according to patient demographics. The mean age at index was 56 years (46 to 83) in the OxZr group and 70 years (46 to 92) in the CoCr group. Fretting and corrosion scores of the female taper of the heads were measured according to the modified Goldberg scoring method. RESULTS: The OxZr-retrieved femoral heads showed significantly lower mean corrosion scores than the CoCr heads (1.3 (1 to 2.75) vs 2.1 (1 to 4); p < 0.01). Mean fretting scores were also significantly lower in the OxZr cohort when compared with the CoCr cohort (1.3 (1 to 2) vs 1.5 (1 to 2.25); p = 0.02). OxZr heads had more damage in the proximal region compared with the distal region of the head. Location had no impact on damage of CoCr heads. A trend towards increased corrosion in large heads was seen only in the CoCr heads, although this was not statistically significant. CONCLUSION: Retrieval analysis of OxZr femoral heads showed a decreased amount of fretting and corrosion compared with CoCr femoral heads. OxZr seems to be effective at reducing taper damage. Cite this article: Bone Joint J 2019;101-B:386-389.


Subject(s)
Arthroplasty, Replacement, Hip/methods , Femur Head/surgery , Hip Prosthesis , Zirconium/pharmacology , Aged , Aged, 80 and over , Corrosion , Female , Follow-Up Studies , Humans , Male , Materials Testing , Middle Aged , Prosthesis Design , Retrospective Studies , Surface Properties , Time Factors
9.
Bone Joint J ; 101-B(7_Supple_C): 108-114, 2019 07.
Article in English | MEDLINE | ID: mdl-31256654

ABSTRACT

AIMS: It is increasingly appreciated that coordinated regulation of angiogenesis and osteogenesis is needed for bone formation. How this regulation is achieved during peri-implant bone healing, such as osseointegration, is largely unclear. This study examined the relationship between angiogenesis and osteogenesis in a unique model of osseointegration of a mouse tibial implant by pharmacologically blocking the vascular endothelial growth factor (VEGF) pathway. MATERIALS AND METHODS: An implant was inserted into the right tibia of 16-week-old female C57BL/6 mice (n = 38). Mice received anti-VEGF receptor-1 (VEGFR-1) antibody (25 mg/kg) and VEGF receptor-2 (VEGFR-2) antibody (25 mg/kg; n = 19) or an isotype control antibody (n = 19). Flow cytometric (n = 4/group) and immunofluorescent (n = 3/group) analyses were performed at two weeks post-implantation to detect the distribution and density of CD31hiEMCNhi endothelium. RNA sequencing analysis was performed using sorted CD31hiEMCNhi endothelial cells (n = 2/group). Osteoblast lineage cells expressing osterix (OSX) and osteopontin (OPN) were also detected with immunofluorescence. Mechanical pull-out testing (n = 12/group) was used at four weeks post-implantation to determine the strength of the bone-implant interface. After pull-out testing, the tissue attached to the implant surface was harvested. Whole mount immunofluorescent staining of OSX and OPN was performed to determine the amount of osteoblast lineage cells. RESULTS: Flow cytometry revealed that anti-VEGFR treatment decreased CD31hiEMCNhi vascular endothelium in the peri-implant bone versus controls at two weeks post-implantation. This was confirmed by the decrease of CD31 and endomucin (EMCN) double-positive cells detected with immunofluorescence. In addition, treated mice had more OPN-positive cells in both peri-implant bone and tissue on the implant surface at two weeks and four weeks, respectively. More OSX-positive cells were present in peri-implant bone at two weeks. More importantly, anti-VEGFR treatment decreased the maximum load of pull-out testing compared with the control. CONCLUSION: VEGF pathway controls the coupling of angiogenesis and osteogenesis in orthopaedic implant osseointegration by affecting the formation of CD31hiEMCNhi endothelium. Cite this article: Bone Joint J 2019;101-B(7 Supple C):108-114.


Subject(s)
Angiogenesis Inhibitors/pharmacology , Bone-Implant Interface/pathology , Osseointegration/drug effects , Prostheses and Implants , Tibia/surgery , Titanium , Vascular Endothelial Growth Factor A/antagonists & inhibitors , Animals , Disease Models, Animal , Female , Mice , Mice, Inbred C57BL , Tibia/drug effects , Tibia/metabolism , Tibia/pathology
10.
Bone Joint J ; 101-B(6_Supple_B): 68-76, 2019 Jun.
Article in English | MEDLINE | ID: mdl-31146558

ABSTRACT

AIMS: Custom flange acetabular components (CFACs) are a patient-specific option for addressing large acetabular defects at revision total hip arthroplasty (THA), but patient and implant characteristics that affect survivorship remain unknown. This study aimed to identify patient and design factors related to survivorship. PATIENTS AND METHODS: A retrospective review of 91 patients who underwent revision THA using 96 CFACs was undertaken, comparing features between radiologically failed and successful cases. Patient characteristics (demographic, clinical, and radiological) and implant features (design characteristics and intraoperative features) were collected. There were 74 women and 22 men; their mean age was 62 years (31 to 85). The mean follow-up was 24.9 months (sd 27.6; 0 to 116). Two sets of statistical analyses were performed: 1) univariate analyses (Pearson's chi-squared and independent-samples Student's t-tests) for each feature; and 2) bivariable logistic regressions using features identified from a random forest analysis. RESULTS: Radiological failure and revision rates were 23% and 12.5%, respectively. Revisions were undertaken at a mean of 25.1 months (sd 26.4) postoperatively. Patients with radiological failure were younger at the time of the initial procedure, were less likely to have a diagnosis of primary osteoarthritis (OA), were more likely to have had ischial screws in previous surgery, had fewer ischial screw holes in their CFAC design, and had more proximal ischial fixation. Random forest analysis identified the age of the patient and the number of locking and non-locking screws used for inclusion in subsequent bivariable logistic regression, but only age (odds ratio 0.93 per year) was found to be significant. CONCLUSION: We identified both patient and design features predictive of CFAC survivorship. We found a higher rate of failure in younger patients, those whose primary diagnosis was not OA, and those with more proximal ischial fixation or fewer ischial fixation options. Cite this article: Bone Joint J 2019;101-B(6 Supple B):68-76.


Subject(s)
Acetabulum/surgery , Arthroplasty, Replacement, Hip/methods , Acetabulum/diagnostic imaging , Adult , Aged , Aged, 80 and over , Arthroplasty, Replacement, Hip/instrumentation , Bone Screws , Female , Hip Prosthesis , Humans , Male , Middle Aged , Osteoarthritis, Hip/diagnostic imaging , Osteoarthritis, Hip/surgery , Prosthesis Design , Prosthesis Failure , Reoperation/statistics & numerical data , Retrospective Studies , Tomography, X-Ray Computed
11.
J Phys Chem B ; 112(6): 1580-5, 2008 Feb 14.
Article in English | MEDLINE | ID: mdl-18205350

ABSTRACT

Mean-field theories that include nonelectrostatic interactions acting on ions near interfaces have been found to accommodate many experimentally observed ion specific effects. However, it is clear that this approach does not fully account for the liquid molecular structure and hydration effects. This is now improved by using parametrized ionic potentials deduced from recent nonprimitive model molecular dynamics (MD) simulations in a generalized Poisson-Boltzmann equation. We investigate how ion distributions and double layer forces depend on the choice of background salt. There is a strong ion specific double layer force set up due to unequal ion specific short-range potentials acting between ions and surfaces.


Subject(s)
Colloids/chemistry , Air , Algorithms , Chemical Phenomena , Chemistry, Physical , Energy Transfer , Linear Models , Poisson Distribution , Surface Properties
12.
Bone Joint Res ; 6(1): 14-21, 2017 Jan.
Article in English | MEDLINE | ID: mdl-28062525

ABSTRACT

Intermittently administered parathyroid hormone (PTH 1-34) has been shown to promote bone formation in both human and animal studies. The hormone and its analogues stimulate both bone formation and resorption, and as such at low doses are now in clinical use for the treatment of severe osteoporosis. By varying the duration of exposure, parathyroid hormone can modulate genes leading to increased bone formation within a so-called 'anabolic window'. The osteogenic mechanisms involved are multiple, affecting the stimulation of osteoprogenitor cells, osteoblasts, osteocytes and the stem cell niche, and ultimately leading to increased osteoblast activation, reduced osteoblast apoptosis, upregulation of Wnt/ß-catenin signalling, increased stem cell mobilisation, and mediation of the RANKL/OPG pathway. Ongoing investigation into their effect on bone formation through 'coupled' and 'uncoupled' mechanisms further underlines the impact of intermittent PTH on both cortical and cancellous bone. Given the principally catabolic actions of continuous PTH, this article reviews the skeletal actions of intermittent PTH 1-34 and the mechanisms underlying its effect. CITE THIS ARTICLE: L. Osagie-Clouard, A. Sanghani, M. Coathup, T. Briggs, M. Bostrom, G. Blunn. Parathyroid hormone 1-34 and skeletal anabolic action: The use of parathyroid hormone in bone formation. Bone Joint Res 2017;6:14-21. DOI: 10.1302/2046-3758.61.BJR-2016-0085.R1.

13.
J Phys Chem B ; 110(19): 9645-9, 2006 May 18.
Article in English | MEDLINE | ID: mdl-16686514

ABSTRACT

Entities such as ion distributions and forces between lipid membranes depend on effects due to the intervening salt solution that have not been recognized previously. These specific ion or Hofmeister effects influence membrane fusion. A typical illustrative example is this: measurements of forces between double-chained cationic bilayers adsorbed onto molecularly smooth mica surfaces across different 0.6-2 mM salt solutions have revealed a large degree of ion specificity [Pashley et al. J. Phys. Chem. 1986, 90, 1637]. This has been interpreted in terms of very specific anion "binding" to the adsorbed bilayers, as it would too for micelles and other self-assembled systems. However, we show here that inclusion of nonelectrostatic (NES) or ionic dispersion potentials acting between ions and the two surfaces explains such "ion binding". The observed Hofmeister sequence for the calculated pressure without any direct ion binding is given correctly. This demonstrates the importance of a source of ion specificity that has been ignored. It is due to ionic physisorption caused by attractive NES ionic dispersion potentials. There appear to be some far reaching consequences for interpretations of membrane intermolecular interactions in salt solutions.


Subject(s)
Membrane Lipids/chemistry , Models, Chemical , Hydrogen-Ion Concentration , Ions , Lipid Bilayers/chemistry , Static Electricity , Surface Properties
14.
J Phys Chem B ; 110(14): 7563-6, 2006 Apr 13.
Article in English | MEDLINE | ID: mdl-16599538

ABSTRACT

Measurements of pH in single-phase cytochrome c suspensions are reported. The pH, as determined by a glass electrode, has a fixed value. With the addition of salt, the supposedly fixed pH changes strongly. The pH depends on salt type and concentration and follows a Hofmeister series. A theoretical interpretation is given that provides insights into such Hofmeister effects. These occur generally in protein solutions. While classical electrostatic models provide partial understanding of such trends in protein solutions, they fail to explain the observed ion specificity. Such models neglect electrodynamic fluctuation (dispersion) forces acting between ions and proteins. We use a Poisson-Boltzmann cell model that takes these ionic dispersion potentials between ions and proteins into account. The observed ion specificity can then be accounted for. Proteins act as buffers that display similar salt-dependent pH trends not previously explained.


Subject(s)
Proteins/chemistry , Algorithms , Animals , Cytochromes c/chemistry , Horses , Hydrogen-Ion Concentration , Models, Chemical , Solutions
15.
Adv Colloid Interface Sci ; 123-126: 5-15, 2006 Nov 16.
Article in English | MEDLINE | ID: mdl-16806030

ABSTRACT

According to classical DLVO theory all ions of background salt solution with the same ionic charge should result in the same effective force between colloidal particles. However, the relative effectiveness of different ions in influencing forces between ceramic oxide surfaces follows either a reversed Hofmeister sequence or a direct Hofmeister sequence depending on the type of oxide and if the pH is above or below the isoelectric point (iep). This ion specificity is inexplicable in classical double layer theory that deals only with pure electrostatic forces acting between the ions and the colloidal particles. A theoretical explanation is given here. At, and above, biological salt concentrations other, non-electrostatic (NES) ion specific forces act that are ignored in such modeling. In this overview we present the basic theory for the double layer near a single oxide surface and for the extended DLVO forces between oxide colloidal particles that accounts for these NES forces. We will demonstrate that ion specificity can be understood to a large degree once NES forces are included consistently in the non-linear theory.


Subject(s)
Algorithms , Colloids/chemistry , Electrochemistry/methods , Models, Chemical , Models, Molecular , Oxides/chemistry , Static Electricity , Computer Simulation , Surface Properties
16.
Bone Joint J ; 103-B(9): 1552, 2021 Sep.
Article in English | MEDLINE | ID: mdl-34465161
17.
Diabetes ; 38(7): 906-10, 1989 Jul.
Article in English | MEDLINE | ID: mdl-2567684

ABSTRACT

The role of an increased sympathetic activation in the development of insulin resistance in diabetic skeletal muscle was investigated. Epitrochlearis muscles from rats with streptozocin-induced diabetes and from controls were incubated in vitro for 0.5-12.0 h. Diabetes decreased maximal insulin-stimulated (20 mU/ml) glucose transport capacity by 60% (P less than .001), but this decreased insulin responsiveness returned to normal on in vitro incubation (3.79 +/- 0.59 before vs. 8.92 +/- 0.64 mumol.ml-1.h-1 after 12 h of incubation). The reversal of decreased insulin responsiveness in diabetic muscles did not require the presence of insulin and was not affected by the presence of 5.0 x 10(-8) M of epinephrine. However, it was possible to partially prevent the development of insulin resistance with regard to glucose transport by treating the rats with the beta-adrenergic antagonist propranolol (0.5 mg/kg) every 12 h during the entire 72-h period in which the animals were kept diabetic (insulin responsiveness was 3.16 +/- 0.40 mumol.ml-1.h-1 for saline-injected group vs. 5.55 +/- 0.46 mumol.ml-1.h-1 for propranolol-treated group). This effect was not present after a single injection of the drug 2 h before the experiment or when propranolol treatment was withdrawn 12 h before the experiment. The beta-adrenergic blockade markedly reduced the plasma concentration of free fatty acids (0.5 +/- 0.01 mumol/ml for propranolol-treated rats vs. 1.1 +/- 0.1 mumol/ml for saline-treated rats; P less than .001).(ABSTRACT TRUNCATED AT 250 WORDS)


Subject(s)
Catecholamines/pharmacology , Diabetes Mellitus, Experimental/physiopathology , Insulin Resistance , Insulin/pharmacology , Muscles/drug effects , Adrenergic beta-Antagonists/pharmacology , Animals , Biological Transport/drug effects , Blood Glucose/analysis , Epinephrine/pharmacology , Fatty Acids, Nonesterified/blood , Glucagon/blood , Glucose/pharmacokinetics , Glycogen/analysis , Male , Muscles/analysis , Propranolol/pharmacology , Rats , Rats, Inbred Strains , Streptozocin
18.
J Phys Chem B ; 109(51): 24489-94, 2005 Dec 29.
Article in English | MEDLINE | ID: mdl-16375452

ABSTRACT

Monte Carlo simulations have been performed for ion distributions outside a single globular macroion and for a pair of macroions, in different salt solutions. The model that we use includes both electrostatic and van der Waals interactions between ions and between ions and macroions. Simulation results are compared with the predictions of the Ornstein-Zernike equation with the hypernetted chain closure approximation and the nonlinear Poisson-Boltzmann equation, both augmented by pertinent van der Waals terms. Ion distributions from analytical approximations are generally very close to the simulation results. This demonstrates that properties that are related to ion distributions in the double layer outside a single interface can to a good approximation be obtained from the Poisson-Boltzmann equation. We also present simulation and integral equation results for the mean force between two globular macroions (with properties corresponding to those of hen-egg-white lysozyme protein at pH 4.3) in different salt solutions. The mean force and potential of mean force between the macroions become more attractive upon increasing the polarizability of the counterions (anions), in qualitative agreement with experiments. We finally show that the deduced second virial coefficients agree quite well with experimental results.


Subject(s)
Computer Simulation , Ions/chemistry , Muramidase/chemistry , Thermodynamics , Animals , Chick Embryo , Hydrogen-Ion Concentration , Monte Carlo Method , Poisson Distribution , Static Electricity
19.
Biophys Chem ; 114(2-3): 95-101, 2005 Apr 22.
Article in English | MEDLINE | ID: mdl-15829342

ABSTRACT

The Born charging equation predicts that the permeability of a cell membrane to ions by the solubility-diffusion mechanism depends on the ionic radius and on the dielectric constant of the membrane. However, experiments, for example, on red blood cells and on lysosome membranes, show that the permeability depends strongly on the choice of salt anion in a way that cannot be accommodated by differences in ionic size. We demonstrate that one step towards understanding this ion specificity is to take account of the previously ignored dispersion self-free energy of the ion. This is the quantum electrodynamic analogue of the (electrostatic) Born self-energy of an ion. We show that the dispersion self-free energy contribution can be and often is of the same order of magnitude as the Born contribution. To understand the observed specificity, it is essential to take into account of both ionic size and ionic polarizability. In parallel and to reinforce these observations, we also give simple estimates for how self-free energy changes that occur when an ion moves into the air-water interface region (which has a density profile for water molecules) can influence the surface tension of salt solutions. Consistency can be found between the Hofmeister sequences observed in ion permeation and in surface tension of electrolytes when these previously ignored self-free energies are included properly.


Subject(s)
Ions , Membranes, Artificial , Electricity , Models, Theoretical , Thermodynamics
20.
Biophys Chem ; 117(3): 217-24, 2005 Oct 03.
Article in English | MEDLINE | ID: mdl-15963625

ABSTRACT

The relative effectiveness of different anions in crystallizing proteins follows a reversed Hofmeister sequence for pHpI. The phenomenon has been known almost since Hofmeister's original work but it has not been understood. It is here given a theoretical explanation. Classical electrolyte and double layer theory deals only with electrostatic forces acting between ions and proteins. Hydration and hydration interactions are dealt with usually only in terms of assumed hard core models. But there are, at and above biological salt concentrations, other non-electrostatic (NES) ion-specific forces acting that are ignored in such modeling. Such electrodynamic fluctuation forces are also responsible for ion-specific hydration. These missing forces are variously comprehended under familiar but generally unquantified terms, typically, hydration, hydrogen bonding, pi-electron-cation interactions, dipole-dipole, dipole-induced dipole and induced dipole-induced dipole forces and so on. The many important body electrodynamic fluctuation force contributions are accessible from extensions of Lifshitz theory from which, with relevant dielectric susceptibility data on solutions as a function of frequency, the forces can be extracted quantitatively, at least in principle. The classical theories of colloid science that miss such contributions do not account for a whole variety of ion-specific phenomena. Numerical results that include these non-electrostatic forces are given here for model calculations of the force between two model charge-regulated hen-egg-white protein surfaces. The surfaces are chosen to carry the same charge groups and charge density as the protein. What emerges is that for pHpI (where anions are co-ions) the forces increase in the order NaCl

Subject(s)
Proteins/chemistry , Biomechanical Phenomena , Hydrogen-Ion Concentration , Ions/chemistry , Models, Biological , Solutions
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