Thermodynamics of Micellization of Ionized Surfactants: The Equivalence of Enthalpies of Micellization from Calorimetry and the Variation of Critical Micelle Points with Temperature as Exemplified for Aqueous Solutions of an Aliphatic Cationic Surfactant.

There is considerable confusion on experimental and thermodynamic aspects of the formation of ionized surfactant micelles. Recent claims that the van't Hoff and calorimetric enthalpies of micellization of ionized surfactants represent different aspects of micellization are shown to be incorrect. New conductance and surface tension measurements on -dodecyltrimethylammonium bromide (DTAB) in water and in cosolution with 0.

A follow-up study of the in-practice results of pulsed electromagnetic field therapy in the management of nonunion fractures.

During normal fracture repair, healing occurs within a few months. However, for a minority of patients, the processes of bone repair are compromised or interrupted leading to the development of delayed union and nonunion fractures. Noninvasive bone growth stimulators using pulsed electromagnetic field (PEMF) technology are currently in widespread use by patients with impaired fracture healing.

Misuse of thermodynamics in the interpretation of isothermal titration calorimetry data for ligand binding to proteins.

Isothermal titration calorimetry (ITC) has given a mass of data on the binding of small molecules to proteins and other biopolymers, with particular interest in drug binding to proteins chosen as therapeutic indicators. Interpretation of the enthalpy data usually follows an unsound protocol that uses thermodynamic relations in circumstances where they do not apply. Errors of interpretation include incomplete definitions of ligand binding and equilibrium constants and neglect of the non-ideality of the solutions under study, leading to unreliable estimates of standard free energies and entropies of binding.

The thermodynamics of protein folding: a critique of widely used quasi-thermodynamic interpretations and a restatement based on the Gibbs-Duhem relation and consistent with the Phase Rule.

Interpretations of data in the extensive literature on the unfolding of proteins in aqueous solution follow a variety of methods involving assumptions leading to estimates of thermodynamic quantities associated with the unfolding transition. Inconsistencies and thermodynamic errors in these methods are identified. Estimates of standard molar free energies and enthalpies of unfolding using incompletely defined equilibrium constants and the van't Hoff relation are unsound, and typically contradict model-free interpretation of the data.

Structure-energy relations in hen egg white lysozyme observed during refolding from a quenched unfolded state.

We use infrared spectroscopy to study the evolution of protein folding intermediate structures on arbitrarily slow time scales by rapidly quenching thermally unfolded hen egg white lysozyme in a glassy matrix, followed by reheating of the protein to refold; upon comparison with differential scanning calorimetric experiments, low-temperature structural changes that precede the formation of energetic native contacts are revealed.

Intermolecular forces in lipid monolayers. Two-dimensional virial coefficients for pentadecanoic acid from micromanometry on spread monolayers at the air/water interface.

The lateral intermolecular forces between surfactant or lipid molecules in monolayers at interfaces are fundamental to understanding the phenomena of surface activity and the interactions of lipids in two-dimensional structures such as smectic phases and biomembranes. The classical approach to these forces is via the two-dimensional virial coefficients, which requires precise micromanometry on monolayer isotherms in the dilute gaseous region. Low pressure isotherms out to high surface areas in the two-dimensional gas range have been measured at 15, 25 and 30 degrees C for insoluble monolayers of n-pentadecanoic acid spread at the interface between water-vapour saturated air and a dilute aqueous solution of HCl.

Surveillance of a recently switched non-prescription medicine (Diclofenac) using a pharmacy-based approach.

Purpose: Postmarketing surveillance of prescription medicines is a routine practice, yet similar evaluation of non-prescription medicines, including those recently switched from prescription status, is uncommon. This study presents the methodologic issues and limitations of the use of pharmacies in the 'post-reclassification' surveillance of oral diclofenac potassium 25 mg which had been recently switched from physician prescription to non-prescription sale.

Methods: Consenting user-purchasers were recruited from 175 New Zealand pharmacies over 4 months.

Are electrostatic potentials between regions of different chemical composition measurable? The Gibbs-Guggenheim Principle reconsidered, extended and its consequences revisited.

As indicated by Gibbs and made explicit by Guggenheim, the electrical potential difference between two regions of different chemical composition cannot be measured. The Gibbs-Guggenheim Principle restricts the use of classical electrostatics in electrochemical theories as thermodynamically unsound with some few approximate exceptions, notably for dilute electrolyte solutions and concomitant low potentials where the linear limit for the exponential of the relevant Boltzmann distribution applies. The Principle invalidates the widespread use of forms of the Poisson-Boltzmann equation which do not include the non-electrostatic components of the chemical potentials of the ions.

Lateral intermolecular forces between biomembrane lipids in two dimensions: 1,2-dipalmitin at the heptane/water interface compared with phospholipids.

The lateral interaction forces between phospholipids in two-dimensional arrays are fundamental to understanding membrane biophysics. In previous studies the related thermodynamic functions have been measured for spread phospholipid monolayers at the oil/water interface over a range of temperatures and densities, and the two-dimensional virial coefficients obtained. These coefficients have been computed from a model that emphasizes the head group zwitterion interactions.

Quarter-salt formation defining the anomalous temperature dependence of the aqueous solubility of sodium monododecyl phosphate.

The salts of monoalkyl phosphates (MAPs) have been identified as a class of inherently mild surfactants for use in household and personal products. They represent an anionic species intermediate in terms of pKa between the sulfates and the carboxylates and are analogous to the carboxylates in that they form acid-salts (which are here termed quarter-salts)-hydrogen-bonded dimers consisting of an undissociated MAP acid and an MAP monosalt. These complexes precipitate from solutions of the monosalt over a range of lower MAP concentrations giving rise to an unusual solubility/temperature relationship.

Reversible flocculation of silica across the phase boundary of poly(vinyl caprolactam) in aqueous solution.

The colloid stability of silica dispersions in water in the presence of poly(vinyl caprolactam) (PVCAP) has been studied below and above the lower consolute temperature (LCT) of its solutions. The dispersion sediments slowly without PVCAP in the temperature range studied (26-40 degrees C) or with PVCAP below the LCT ( approximately 30 degrees C). In contrast, with PVCAP above the LCT, rapid flocculation occurs at acid pH, with re-dispersal on cooling.

Lateral intermolecular forces in the physisorbed state: surface field polarization of benzene and n-hexane at the water/ and mercury/vapor interfaces.

The available experimental data on the dependence of the surface tensions of water and mercury on the adsorption of benzene and hexane from the vapor phase are critically analyzed and interpreted to obtain the two-dimensional second virial coefficients [B(2)(T)] for these adsorbed nonpolar molecules. Calculations based on the unperturbed Lennard-Jones (L-J) 12-6 formalism for benzene and the related 12-5 Salem formalism for long chains in two dimensions for hexane require that B(2)(T) should be negative for both adsorbates. On water, the experimental data indicate that B(2)(T) for both molecules is less negative than expected from the unperturbed L-J and Salem estimates, and on mercury the B(2)(T) values from experiment are positive.

Intermolecular forces in spread phospholipid monolayers at oil/water interfaces.

The lateral intermolecular forces between phospholipids are of particular relevance to the behavior of biomembranes, and have been approached via studies of monolayer isotherms at aqueous interfaces, mostly restricted to air/water (A/W) systems. For thermodynamic properties, the oil/water (O/W) interface has major advantages but is experimentally more difficult and less studied. A comprehensive reanalysis of the available thermodynamic data on spread monolayers of phosphatidyl cholines (PC) and phosphatidyl ethanolamines (PE) at O/W interfaces is conducted to identify the secure key features that will underpin further development of molecular models.

Comparison of potency of inhaled beclomethasone and budesonide in New Zealand: retrospective study of computerised general practice records.

Objective: To determine whether inhaled budesonide and beclomethasone are equipotent in the treatment of asthma in primary care.

Design: Retrospective study of computerised clinical records from 28 general practices in New Zealand.

Subjects: 5930 patients who received 16 725 prescriptions for inhaled budesonide or beclomethasone from 1 July 1994 to 30 June 1995.

The temperature dependence of the facilitated transport ofD(+)-glucose across the human red cell membrane.

The rate of exit ofD(+)-glucose from human red cells was measured as a function of the extracellular glucose concentration over the temperature range 12 to 47°C. The results were analyzed at each temperature, according to the kinetic model of Widdas and of Rosenberg and Wilbrandt, in terms of the apparent maximum exit rate (V max) and the apparent dissociation constant (K m ) of the carrier-glucose complex. When the values ofV max andK m were obtained by the same graphical method as that used by Sen and Widdas, the results were very similar to theirs insofar as the effect of temperature is concerned.