Raman spectral evidence for hydration forces between collagen triple helices

Hydration forces are thought to result from the energetic cost of water rearrangement near macromolecular surfaces. Raman spectra, collected on the same collagen samples on which these forces were measured, reveal a continuous change in water hydrogen-bonding structure as a function of separation between collagen triple helices. The varying spectral parameters track the force-distance curve. The energetic cost of water “restructuring,” estimated from the spectra, is consistent with the measured energy of intermolecular interaction. These correlations support the idea that the change in water structure underlies the exponentially varying forces seen in this system at least over the 13–18-Å range of interaxial separations.

Influences of Hydration Force and Elastic Strain Energy on the Stability of Solid Film in a Very Thin Solid-on-Liquid Structure

Since hydration forces become very strong at short range and are particularly important for determining the magnitude of the adhesion between two surfaces or interaction energy, the influences of the hydration force and elastic strain energy due to hydration-induced layering of liquid molecules close to a solid film surface on the stability of a solid film in a solid-on-liquid (SOL) nanostructure are studied in this paper. The liquid of this thin SOL structure is a kind of water solution. Since the surface forces play an important role in the structure, the total free energy change of SOL structures consists of the changes in the bulk elastic energy within the solid film, the surface energy at the solid-liquid interface and the solid-air interface, and highly nonlinear volumetric component associated with interfacial forces. The critical wavelength of one-dimensional undulation, the critical thickness of the solid film, and the critical thickness of the liquid layer are studied, and the stability regions of the solid film have been determined. Emphasis is placed on calculation of critical values, which are the basis of analyzing the stability of the very thin solid film.

Measurement of forces between and within bilayers of neutral phospholipids

Phospholipids in water form lamellar phases made up of alternating layers of water and bimolecular lipid leaflets. Three complementary methods, osmotic, mechanical, and vapour pressures, were used to measure the work of removing water from lamellar phases composed of frozen dipalmitoylphosphatidylcholine ( DPPC ), melted DPPC, egg phosphatidylethanolamine or equimolar mixtures of DPPC and cholesterol ( DPPC/CHOL ), Concurrently the structural changes that resulted from this water removal were measured using X-ray diffraction. The work was divided into that which forces the bilayers together ( F ) and that which compresses the molecules together within the bilayers ( F )# A large repulsive force exists between bilayers composed of each of the lipids studied and this force increases exponentially as bilayer separation is decreased. F is affected by the nature of the head groups, conformation of the acyl chains and heterogeneity of these chains. In general all of the melted phosphatidylcholines ( melted DPPC, egg lecithin and DPPC/CHOL ) have large equilibrium separations in excess water resulting from large repulsive hydration forces between these bilayers. By comparison, egg PE has an increased attractive force, and frozen DPPC has a decreased hydration force; each results in smaller separations in water for these two lipids. The chemical potentials of the water between the bilayers for all these lipids lie on a continuum, indicating that interbilayer water cannot be characterized by two discrete states, usually referred to as "bound" or "non**bound". For all lipids studied a maximum of 25 % of the total work done on the system goes into deforming the bilayers. The method used here viii to separate repulsion from deformation, developed for us by v. A. Parsegian, provides a unique method for the measurement of lateral pressure of a bilayer and its modulus of deformability ( Y ). Lateral pressure is affected by the nature of the head group, conformation and heterogeneity of the acyl chains. For small changes in molecular surface area ( A ) near equilibrium, both melted and frozen DPPC have similar values for the deformability modulus. Thus in this regime it requires about the same force to change the angle of tilt of frozen chains as it does to compress the fluid bilayer. The introduction of cholesterol into bilayers of DPPC reduces dramatically the lateral pressure of the bilayers over a large range of molecular surface areas ( A ). The variation in the magnitude of bilayer repulsion with different phospholipids provides a basis for the mechanism of lipid segregation in mixed lipid systems and suggests that interacting heterogeneous membranes may influence or modulate the composition of the opposing membrane. The measurements of deformabilities of bilayers provides a direct comparison of them with the properties of monolayers.

Measurement of repulsive forces between charged phospholipid bilayers

Electrostatic forces between membranes containing charged lipids were assumed to play an important role in influencing interactions between membranes long before quantitative measurements of such forces were available. ~ur measurements were designed to measure electrostatic forces between layers of lecithin charged with lipi~s carrying ionizable head groups. These experiments have shown that the interactions between charged lipid bila.yere are dominated by electrostatic forces only at separations greater than 30 A. At smaller separations the repulsion between charged bilayers is dominated by strong hydration forces. The net repulsive force between egg lecithin bilayers containing various amounts of cherged lipids (phosphatidylglycerol (PG) 5,10 ano 50 mole%, phosphatidyli. nosi tol (PI) 10 mole% and sodium oleate (Na-Ol) 3,5 and 10 mole%, where mole% gives the ratio of the number of moles' of .charged lipid to the total number of moles of all lipids present in the sample) was stuoied with the help ('If the osmotic streas technique described by LeNeveu et aI, (1977). Also, the forces between pure PG were j_nvestigated in the same manner. The results have been plotted showing variation of force as a function of bilay- _ er separation dw• All curVes 90 obtained called force curves, were found to be similar in sha.pe, showing two distinct regions, one when dw<.30 A is a region cf very rapid iiivariation of force with separation ( it is the region dominated by hydre,tion force) and second when dw> 40 A is a region of very slow variation of force with separB.tion ( it is the region dominated by the electrostatic force). Between these two regions there exists a transition area in which, in most systems studied, a phase separation of lipids into fractions containing different amounts of charged groups, was observed. A qualitative analysis showed that our results were v/ell described by the simple electrostatic double -le.yer theory. For quantitative agreement between measured and calculated force curves however, the charge density for the calculations had to be taken as half of that given by the number density of charged lipids present in the lecithin bilayers. It is not clear at the moment what causes such low apparent degree of ionization among the charged head groups, and further study is needed in this area.

Effect of cations/polycations on the efficiency of formation of a hybrid bilayer membrane that mimics the inner mitochondrial membrane

We aim in this study to characterize the effect of cations and polycations on the formation of hybrid bilayer membranes (HBMs), especially those that mimic the inner mitochondrial membrane (IMM), with a proper composition of phosphatidylcholine (PC), phosphatidylethanolamine (PE) and cardiolipin (CL) adsorbed on an alkanethiol monolayer. HBMs are versatile membrane mimetics that show promising results in sensor technology. Its formation depends on the fusion of vesicles on hydrophobic surfaces, a process that is not well understood at the molecular level. Our results showed to which extend and in which condition the presence of cations and polycations facilitate the formation of HBMs. The required time for lipid layer formation was reduced several times and the lipid layer reaches the expected thickness of 19.5 +/- 1.8 angstrom, in contrast to only 2 +/- 1.5 angstrom usually observed in the absence of cations. In the presence of specific concentrations of spermine and Ca2+ the amount of adsorbed phospholipids on the thiol layer increased nearly 70% compared to that observed when Na+ was used at concentrations 10 times higher. Divalent cations and polycations adsorb specifically on the lipid headgroups destabilizing the hydration forces, facilitating the process of vesicle fusion and formation of lipid monolayers. The concepts and conditions described in the manuscript will certainly help the development of the field of membrane biosensors. (C) 2011 Elsevier B.V. All rights reserved.

Contribution of different physical forces to the disjoining pressure of a thin water film being pressed by an oil droplet

With an objective to understand the nature of forces which contribute to the disjoining pressure of a thin water film on a steel substrate being pressed by an oil droplet, two independent sets of experiments were done. (i) A spherical silica probe approaches the three substrates; mica, PTFE and steel, in a 10 mM electrolyte solution at two different pHs (3 and 10). (ii) The silica probe with and without a smeared oil film approaches the same three substrates in water (pH = 6). The surface potential of the oil film/water was measured using a dynamic light scattering experiment. Assuming the capacity of a substrate for ion exchange the total interaction force for each experiment was estimated to include the Derjaguin-Landau-Verwey-Overbeek (DLVO) force, hydration repulsion, hydrophobic attraction and oil-capillary attraction. The best fit of these estimates to the force-displacement characteristics obtained from the two sets of experiment gives the appropriate surface potentials of the substrates. The procedure allows an assessment of the relevance of a specific physical interaction to an experimental configuration. Two of the principal observations of this work are: (i) The presence of a surface at constant charge, as in the presence of an oil film on the probe, significantly enhances the counterion density over what is achieved when both the surfaces allow ion exchange. This raises the corresponding repulsion barrier greatly. (ii) When the substrate surface is wettable by oil, oil-capillary attraction contributes substantially to the total interaction. If it is not wettable the oil film is deformed and squeezed out. (C) 2010 Elsevier Inc. All rights reserved.

Marketplace forces and the history of retailing : The cycle of control

This paper traces the history of store (retailer-controlled) and national (manufacture controlled)brands; identifies the key historical characteristics of the past 200 years of marketing history;describes the four main time periods of U.S. retail marketing (1800 - 2000); and comments on the most likely developments within the current phases of brand marketing. Will the future focus on technology and new forms of communications? The Internet exemplifies an unconventional retailing environment, with etailer numbers growing rapidly. The central proposition of this paper is that a "cycle of control" - a pattern of marketing developments within the history of retailing and national marketing communications - Can indicate the success of marketing strategies in the future.

Project diagnostics : assessing the condition of projects and identifying poor health combing forces

In many cases, construction projects do not achieve the objectives that the project participants set for them. If participants could better understand how their project is performing overall, at various stages of its delivery, then the opportunities to achieve project success would almost certainly be greater. This paper documents a method of assessing the status of a project, at a point in its design or construction phase, or after completion. The status is assessed in terms of up to seven (7) key success factors. Any evidence of less than adequate performance in these performance areas is scrutinised to seek out the root causes of why this situation is happening. Using these identified root causes of under performance, general suggestions can then be made as to how to return the project to good health. A software package that assists in assessing the status of the project has been developed. The package is currently being calibrated before commercial release.

The measurement of applied forces during anterior single rod correction of adolescent idiopathic scoliosis

Adolescent idiopathic scoliosis (AIS) is the most common form of spinal deformity in paediatrics, prevalent in approximately 2-4% of the general population. While it is a complex three-dimensional deformity, it is clinically characterised by an abnormal lateral curvature of the spine. The treatment for severe deformity is surgical correction with the use of structural implants. Anterior single rod correction employs a solid rod connected to the anterior spine via vertebral body screws. Correction is achieved by applying compression between adjacent vertebral body screws, before locking each screw onto the rod. Biomechanical complication rates have been reported as high as 20.8%, and include rod breakage, screw pull-out and loss of correction. Currently, the corrective forces applied to the spine are unknown. These forces are important variables to consider in understanding the biomechanics of scoliosis correction. The purpose of this study was to measure these forces intra-operatively during anterior single rod AIS correction.

Developing a quick and practical screen to improve the identification of poor hydration in geriatric and rehabilitative care

Dehydration has been associated with increased morbidity and mortality. Dehydration risk increases with advancing age, and will progressively become an issue as the aging population increases. Worldwide, those aged 60 years and over are the fastest growing segment of the population. The study aimed to develop a clinically practical means to identify dehydration amongst older people in the clinical care setting. Older people aged 60 years or over admitted to the Geriatric and Rehabilitation Unit (GARU) of two tertiary teaching hospitals were eligible for participation in the study. Ninety potential screening questions and 38 clinical parameters were initially tested on a single sample (n=33) with the most promising 11 parameters selected to undergo further testing in an independent group (n=86). Of the almost 130 variables explored, tongue dryness was most strongly associated with poor hydration status, demonstrating 64% sensitivity and 62% specificity within the study participants. The result was not confounded by age, gender or body mass index. With minimal training, inter-rater repeatability was over 90%. This study identified tongue dryness as a potentially practical tool to identify dehydration risk amongst older people in the clinical care setting. Further studies to validate the potential screen in larger and varied populations of older people are required