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J F Nagle

Publications and source records attributed to J F Nagle.

At least 55 records · Page 3Linked to original sources
PubMed1986

Dilatometric studies of isobranched phosphatidylcholines.

Absolute apparent specific volumes have been obtained for phosphatidylcholine lipids with saturated, isobranched hydrocarbon chains with ni = 15 to 20 carbons, with an emphasis upon phase transition behavior, both equilibrium and kinetic. The temperature of the chain-melting transition extrapolates with increasing chain length to the melting temperature of polyethylene with a small odd/even alternation. There are also odd/even alternations in the volume of transition and in the hysteresis of the chain-melting transition, but with the odd and even reversed when compared with the larger odd/even alternation in the lower solid-solid transition that occurs in the longer chain ni lipids. A phenomenological picture is given for the coalescence of the two transitions for shorter ni lipids and this picture is used to sharpen the discussion of the kinetic mechanism of melting. A temperature-reversal experiment shows that the melting from the lowest temperature crystal or C phase to the fluid F phase does not proceed via the metastable gel G phase for 16i. The dilatometric results are combined with recent X-ray structural results for the C and G phases of 17i and 20i to deduce various structural information, including the hydration numbers and the volume of the headgroup, VH = 341 A3, which agrees very well with VH for straight-chain phosphatidylcholines. For the chain-melted F phase the assumption that the methylene volumes of the different ni lipids should be the same at the same temperature is used to obtain the volumes of the methylene and the methyl groups.

Kinetics↗
PubMed1986

Thermodynamic studies of purple membrane.

Differential dilatometric and differential scanning calorimetric measurements have been made of purple membrane with an emphasis upon the temperature range 5 degrees C less than T less than 45 degrees C. The coefficient of thermal expansion alpha is about 7 X 10(-4)/Cdeg up to 30 degrees C and decreases at higher temperatures. The specific heat increases rapidly with temperature with absolute values in the range 0.30-0.45 cal/Cdeg per g. A nearly constant alpha juxtaposed with a rapidly increasing specific heat is similar to the properties of lipid bilayers in the gel phase and alkanes in the solid phase. This behavior is explained by the concept of hindered vibrations which would now appear to apply to at least one integral membrane protein. There may also be a small broad transition centered near 20-25 degrees C that would correspond to the melting of less than 25 degrees of freedom per bacteriorhodopsin molecule and associated lipids. Using our measured apparent specific volume the average thickness of purple membrane is calculated to be 43.5 A. The specific volume of interaction of lipids and proteins is estimated, using the amino acid sequence of bacteriorhodopsin and average amino acid volumes from structural studies of other proteins, to be about 11% of the specific volume of the purple membrane lipids or 4% of the volume of the bacteriorhodopsin protein. A positive volume of interaction is consistent with lipid-protein interactions being an important determinant of the thermodynamic properties of purple membrane.

Bacteriorhodopsins↗
PubMed1986

Models of localized energy coupling.

It is proven that any model of localized protonmotive energy coupling that relies upon properties of a homogeneous surface phase must, when operated in the steady state, lead to bulk phase electrochemical potentials for protons that are as large as those required by the delocalized chemiosmotic theory. To obtain models consistent with experiments supporting localized energy coupling requires some kind of surface heterogeneity for the proton conducting pathways. Two general classes of heterogeneous surface models are mentioned. One class involves phase-separated lipid domains. The second class involves hydrogen-bonded chains in proteins that traverse the membrane laterally.

Biological Transport, Active↗
PubMed1984

Metastability in the phase behavior of dimyristoylphosphatidylethanolamine bilayers.

A new subgel phase is demonstrated to occur in hydrated dimyristoylphosphatidylethanolamine ( DMPE ) by using dilatometric and calorimetric techniques. The formation of the subgel phase takes place very slowly at temperatures near 0 degree C, but it can still be observed at 25 degrees C. Once formed, the subgel phase melts (delta Hh = 16.0 +/- 0.6 kcal/mol and delta V = 0.085 +/- 0.014 mL/g) directly into the liquid-crystalline phase at a temperature, Th = 56.3 degrees C, that is higher than the gel to liquid-crystalline transition temperature, Tm = 49.6 degrees C. Thus, the gel phase appears to be metastable over its entire temperature range. In this regard, DMPE behaves differently from dipalmitoylphosphatidylcholine and distearoylphosphatidylcholine but similarly to dilaurylphosphatidylethanolamine . This unusual long-lived metastability provides cells an additional option in determining the properties of membranes.

Chemical Phenomena↗
PubMed1982

Dilatometric studies of the subtransition in dipalmitoylphosphatidylcholine.

The phase transition between the newly discovered low-temperature subgel phase and the gel phase of dipalmitoylphosphatidylcholine has been studied by using dilatometry. Equilibrium measurements show that the subtransition upon heating is centered at 13.5 degrees C, has a dilatometric half-width of 0.6 degree C, and comprises a specific volume change of 0.009 mL/g (about one-fourth the size of the main transition). When the gel phase is cooled, the subtransition does not occur until below 5 degrees C. The rate of formation as a function of incubation temperature for 1 degree C less than TI less than 6 degrees C was determined; it is not well fit by quantitative theories based upon homogeneous nucleation. However, some form of nucleation is present since temperature-jump studies show that once the subgel phase has started to form, it continues to grow in the range 6 degrees C less than TJ less than 12.8 degrees C. Thus, the true transition temperature lies between 12.8 and 13.5 degrees C, but nucleation of the subgel phase is severely retarded above 6 degrees C, leading to the large hysteresis observed upon cooling.

Calorimetry↗
PubMed1982

Specific heats of lipid dispersions in single phase regions.

Differential scanning calorimetry has been used for the first time to measure the specific heat, Cp, as a function of temperature in the single phase regions above and below the main phase transition temperature, Tm, for dispersions of saturated phosphatidylcholines and phosphatidylethanolamines. Within error limits Cp, when expressed per gram, does not vary in any systematic way with chain length or headgroup. Its temperature dependence in both single phase regions qualitatively resembles that of n-alkanes. Contributions to Cp from intrachain vibrations and interchain van der Waals' interactions have been calculated and account for nearly all the measured Cp at temperatures above Tm. However, these contributions do not yield the observed temperature dependence below Tm. It is conjectured that such a temperature dependence arises from the unhindering of chain vibrations as the lipids undergo thermal expansion, and the result of a preliminary calculation which supports this conjecture is presented.

Calorimetry↗
PubMed1982

Procedure for testing kinetic models of the photocycle of bacteriorhodopsin.

Given some simple kinetic models of the photocycle of bacteriorhodopsin (bR) and data taken at many wavelengths and under conditions that avoid photoselection and steady-state cycling complications, it is shown how to extract the apparent rate constants and the spectra of the intermediates. Special consideration was given to establishing the range of error of these results. There are many criteria, which we explicitly discuss, that the spectra should satisfy in order that the kinetic model be acceptable. New data for the photocycle of purple membrane fragments in dilute buffer at pH 7.0 has been obtained at 15 measuring wavelengths and four temperatures. The procedure, which can be generalized to more complex models, has been applied to these data to test two kinds of kinetic models: the unidirectional unbranched model and the undirectional model with simple branching straight back to bR from any intermediate. In these models the spectrum of the O intermediate is highly temperature sensitive, even with branching, and/or has two broad maxima. Moreover, the spectrum of the M intermediate has a secondary maximum and two M-like states appear to be required. Thus, neither model satisfies the physical criteria.

Bacteriorhodopsins↗
PubMed1981

Dilatometry and calorimetry of saturated phosphatidylethanolamine dispersions.

The specific volumes of a series of saturated phosphatidylethanolamine dispersions with 12, 14, and 16 carbon atoms per chain have been measured in the region of the chain melting transition, Tm. The change in specific volume at Tm for the 12 and 14 carbon compounds are 0.0160 and 0.0204 mL/g, respectively. Comparisons are drawn between this class of lipids and phosphatidylcholines. In both cases, Tm extrapolates with increasing chain length to the melting point of polyethylene. Both types of lipids appear to be packed in a similar way below Tm. One major difference is that dilaurylphosphatidylethanolamine undergoes a second transition above Tm.

Calorimetry↗
PubMed1980

Exchange kinetics of the Schiff base proton in bacteriorhodopsin.

Using rapid mixing techniques and resonance Raman spectroscopy, we have found that the 1H/2H exchange time for the Schiff base proton of bacteriorhodopsin in purple membrane is 4.7 msec, when experiments are carried out at pH 2 or pH 7 at room temperature in the dark. We argue that diffusion of neutral water into the membrane is fast on this time scale. Also, model Schiff bases in solution have a pKa between 6 and 7, and we show that such model Schiff bases have much faster exchange rates. Therefore, we conclude that the Schiff base proton in bacteriorhodopsin is protected from interaction with the medium, probably by interaction with a protein group, and this would account for a pKa considerably higher than 6-7.

Bacteriorhodopsins↗
PubMed1979

Dilatometric study of binary mixtures of phosphatidylcholines.

Volumes of lipid dispersions as a function of temperature have been measured for two different kinds of binary mixtures of lecithins, (1) DMPC and DSPC and (2) DMPC and DC20PC. Emphasis was placed on DMPC-rich compositions so as to resolve ambiguities regarding solid-phase immiscibility in DMPC-DSPC mixtures. Special attention has been paid to problems of equilibration in the low-temperature phase and to methods of mixing the lipids. We find that there is no solid-solid immiscibility in DMPC-DSPC mixtures, although this system is close to exhibiting such immiscibility, and that DMPC-DC20PC mixtures exhibit pronounced solid immiscibility.

Kinetics↗
PubMed1978

Lateral compressibility of lipid mono- and bilayers. Theory of membrane permeability.

The passive sodium permeability of pure lipid vesicles and dispersions has a large peak at the bilayer phase transition temperature. We discuss this anomaly in terms of density fluctuations, which can open up cavities in the headgroup region into which small ions can enter, and which may be large if bilayer conditions at the melting point are similar to those near the critical point which seems to exist in monolayers. We present two arguments, one thermodynamic and one microscopic, which suggest that the permeability is proportional to the lateral compressibility. We then calculate the lateral compressibility for two previously published theoretical models and compare the results with experiment.

Chemical Phenomena↗
PubMed1978

Lecithin bilayers. Density measurement and molecular interactions.

Density measurement are reported for bilayer dispersions of a series of saturated lecithins. For chain lengths with, respectively, 14, 15, 16, 17, and 18 carbons per chain, the values for the volume changes at the main transition are 0.027, 0.031, 0.037, 0.040 and 0.045 ml/g. The main transition temperature extrapolates with increasing chain length to the melting temperature of polyethylene. Volume changes at the lower transition are an order of magnitude smaller than the main transition. Single phase thermal expansion coefficients are also reported. The combination of X-ray data and density data indicated that the volume changes are predominantly due to the hydrocarbon chains, thus enabling the volume vCH2 of the methylene groups to be computed as a function of temperature. From this and knowledge of intermolecular interactions in hydrocarbon chains, the change in the interchain van der Waals energy, delta UvdW, at the main transition is computed for the lecithins and also for the alkanes and polyethylene at the melting transition. Using the experimental enthalpies of transition and delta UvdW, the energy equation is consistently balanced for all three systems. This yields estimates of the change in the number of gauche rotamers in the lecithins at the main transition. The consistency of these calculations supports the conclusion that the most important molecular energies for the main transition in lecithin bilayers are the hydrocarbon chain interactions and the rotational isomeric energies, and the conclusion that the main phase transition is analogous to the melting transition in the alkanes from the hexagonal phase to the liquid phase, but with some modifications.

Chemical Phenomena↗
PubMed1978

Molecular mechanisms for proton transport in membranes.

Likely mechanisms for proton transport through biomembranes are explored. The fundamental structural element is assumed to be continuous chains of hydrogen bonds formed from the protein side groups, and a molecular example is presented. From studies in ice, such chains are predicted to have low impedance and can function as proton wires. In addition, conformational changes in the protein may be linked to the proton conduction. If this possibility is allowed, a simple proton pump can be described that can be reversed into a molecular motor driven by an electrochemical potential across the membrane.

Biological Transport, Active↗