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The local environments of Sc and Y in predominantly ⟨002⟩ textured, Al 1- x Do x N (Do = Sc, x = 0.25, 0.30 or Y, x = 0.25) sputtered thin films with wurtzite symmetry were investigated using X-ray absorption (XAS) and photoelectron (XPS) spectroscopies. We present evidence from the X-ray absorption fine structure (XAFS) spectra that, when x = 0.25, both Sc 3+ and Y 3+ ions are able to substitute for Al 3+ , thereby acquiring four tetrahedrally coordinated nitrogen ligands, i.e., coordination number (CN) of 4. On this basis, the crystal radius of the dopant species in the wurtzite lattice, not available heretofore, could be calculated. By modeling the scandium local environment, extended XAFS (EXAFS) analysis suggests that when x increases from 0.25 to 0.30, CN for a fraction of the Sc ions increases from 4 to 6, signaling octahedral coordination. This change occurs at a dopant concentration significantly lower than the reported maximum concentration of Sc (42 mol % Sc) in wurtzite (Al, Sc)N. XPS spectra provide support for our observation that the local environment of Sc in (Al, Sc)N may include more than one type of coordination., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Using viscosity and dynamic light scattering (DLS) measurements, we monitored the changes in the properties of dispersions of chitosan (a cationic polysaccharide) in acidic solution over a period of up to 700 h. Different polymer concentrations, weight average molecular weights, and degrees of deacetylation were examined. We found that the solution rheology and chitosan aggregates continue to change even up to 700 h. It was observed, remarkably, using both capillary and cone and plate viscometry that the viscosity decreased significantly during the storage period of the chitosan dispersions, with a rapid initial decrease and a slow approach to the steady state value. DLS measurements over this period could be interpreted in terms of a gradual decrease in the size of the chitosan aggregates in the dispersion. This behavior is puzzling, insofar as one expects the dissolution of compact polymer aggregates with time into individual polymer chains to increase the viscosity rather than decrease it as observed: We attribute this apparently anomalous behavior to the fact that the chitosan aggregates are rigid crystalline rod-like entities, which dissolved with time from dispersion of overlapping rods (with high viscosity) into solution of individual random coils (with lower viscosity). A detailed model comparing the hydrodynamic behavior of the initial overlapping rod-like aggregates with the subsequent free coils in solution is in semi-quantitative agreement with our observation.

Riboflavin phosphate (RFP) is an essential compound in the treatment of keratoconus - a degenerative, non-inflammatory disease of the cornea. Currently, the quantitative and efficient transport of riboflavin to the cornea is possible after mechanical removal of the epithelium. To avoid surgical intervention, it is therefore important to develop a method for quantitatively transporting riboflavin across the intact epithelium. In the present study, an RFP-loaded microemulsion was prepared, which could potentially function as an ocular drug delivery system crossing the eye epithelium. The specially designed water-dilutable microemulsion was based on a mixture of nonionic surfactants. Propylene glycol and glycerol acted as cosurfactant and cosolvent assisting in the solubilization of the RFP. The glycerol-rich water-free concentrate consisted of direct micelles for which glycerol served as the hydrophilic phase. In formulations with up to 40wt% water, the hydrophilic surfactant headgroups and glycerol strongly bind water molecules (DSC and SD-NMR). Above 60wt% water, globular, O/W nanodroplets, ∼14nm in diameter, are formed (SAXS, cryo-TEM, and SD-NMR). The structure of microemulsions loaded with 0.14-4.25wt% RFP (0.29-8.89mmol per 100g formulation) is not significantly influenced by the presence of the RFP. However, in the microemulsions containing 10-80wt% water, the mobility of RFP in the microemulsion is constrained by strong interactions with the surfactants and cosurfactant, and therefore free transport of the molecule can be achieved only upon higher (>80wt%) water dilutions., (Copyright © 2015 Elsevier Inc. All rights reserved.)

Propofol (2,6-diisopropylphenol) is a drug for both induction and maintenance of anesthesia. Pure propofol cannot be injected because of its lipophilic character, low water-solubility, and low bioavailability. Presently, propofol is formulated in an unstable emulsion, easily oxidized, and easily contaminated with bacteria. We are proposing new, propofol-loaded modified microemulsions, stable thermodynamically, and microbiologically safe; the microemulsions are fully dilutable with water. Structural characterization of the empty and the propofol-loaded systems as a function of water dilution was accomplished using advanced analytical tools such as SD-NMR, SAXS, cryo-TEM, DSC, electrical conductivity, and viscosity. Upon water dilution the propofol-loaded concentrate forms swollen reverse micelles that upon further dilution (40 wt% water) progressively transform into a bicontinuous mesophase and then invert (>65 wt% water) into O/W nanodroplets without "losing" the solubilized propofol. The drug exhibits strong interactions with the surfactant (DSC and SD-NMR). Propofol increases the size of the microemulsion nanodroplets, but does not modify the microemulsion behavior. Water, ethanol, and PG are essential structural components, but do not interact directly with propofol., (Copyright © 2015. Published by Elsevier B.V.)

The usual treatment of hypercholesterolemia includes a class of drugs known as statins (simvastatin among them), which inhibit the production of cholesterol. Another way of reducing cholesterol levels is with the use of phytosterols, which reduce the transport of exogenic cholesterol from the intestine into the blood stream. The two treatments can be combined, achieving an additive effect. However, both simvastatin and phytosterols are practically insoluble in water, and therefore their absorption and activity are low. Nanosized self-assembled structured liquid systems are modified microemulsions that present an alternative pathway for improving the bioavailability of poorly water-soluble drugs. The goal of this study was to solubilize the maximal quantity of both simvastatin and phytosterols in a single, fully dilutable microemulsion system. We constructed a water-dilutable liquid drug delivery system that includes sucrose monolaurate, propylene glycol, and oleyl lactate. This system exhibits high solubilization capacity for both simvastatin (7.0 wt%) and phytosterols (3.5 wt%) when each is solubilized separately in a water-free concentrate. When simvastatin and phytosterols were solubilized together at a wt ratio of 2.5:1, maximum solubilization was obtained with 4.7 wt% simvastatin and 1.9 wt% phytosterols. Structural and analytical methods were applied including rheology, DSC, SD-NMR, SAXS, and cryo-TEM. The water-free "concentrate" consisted of direct micelles for which propylene glycol served as the hydrophilic phase. Upon water dilution, the direct micelles appear to form "lipophilic compounds dispersed in hydrophilic continuous phase". The solubilizates are located in the droplet core and/or at the interface., (Copyright © 2013. Published by Elsevier B.V.)

The crown form of nona-octanoyloxy tribenzocyclononatriene (C8) with C(3) symmetry was prepared and separated into its enantiomers (C8A and C8B) by HPLC. Like the racemate, the neat enantiomers are also mesogenic, exhibiting two mesophases, M and Col(h). Differential scanning calorimetry, X-ray diffraction, carbon-13 NMR and UV circular dichroism are used to study the structural and dynamic properties of these chiral mesophases. The high-temperature mesophase (Col(h)) was identified by X-ray diffraction as columnar hexagonal; this phase is thermally unstable, undergoing racemization on heating before its clearing point is reached. The low-temperature mesophase (M) is most likely also columnar, but its symmetry could not be determined. In comparison with the racemate, the chiral mesophases are less well ordered, more tightly packed and they have a lower tendency to crystallize. On the other hand they are considerably more mobile, as reflected in their NMR spectra. No helical structure has been identified in the X-ray diffraction of the mesophases.

The paper concerns the structural and optical isomers of nonamethoxy-tribenzocyclononene (compound 1). In the first part of the paper it is shown that 1 exists in two structural isomers: a rigid crown (c-1) with C3 symmetry and a flexible saddle (s-1) with C1 symmetry. The latter, not previously known, can be prepared from the as-synthesized c-1 by quenching a hot solution (or the melt) followed by HPLC separation. The crown/saddle equilibrium, isomerization kinetics, and associated thermodynamic parameters in various organic solvents are reported. Carbon-13 MAS NMR, X-ray diffraction, and differential scanning calorimetry (DSC) of polycrystalline c-1 and s-1 racemates are also reported. The different melting points of the isomers and their rapid isomerization in the melt result in unconventional DSC thermograms involving multiple endothermic and exothermic transitions. The second part of the paper concerns the chiral properties of 1. Both the saddle and crown isomers are structurally chiral, but due to the fast pseudorotation of s-1 in solution, it cannot be separated into its enantiomers. Those of c-1 were separated by HPLC using a chiral column. Their X-ray structure and melting points differ considerably from those of the racemate. This and their fast racemization in the melt lead to complex DSC thermograms with multiple transitions. Solutions of the neat enantiomers exhibit a relatively small specific optical rotation. In the UV they show circular dichroism for the B1u and B2u transitions, with the latter exhibiting a clear couplet structure. Infrared and vibrational circular dichroism spectra of the enantiomers in solution are reported. Comparison of these spectra with quantum mechanical simulations provides unambiguous identification of the enantiomers.

It is well documented that phytosterols inhibit the uptake of exogenic cholesterol and do not interfere with cholesterol synthesis or cause side effects. The mechanism by which phytosterols interfere with cholesterol absorption is not completely clear and there are at least three hypotheses for their beneficial activity. Among these is that of competitive solubilization of phytosterols and cholesterol in dietary mixed micelles. In the present study we investigated the competitive solubilization of phytosterols (approximately 50% beta-sitosterol) and cholesterol in a nonionic microemulsion system constructed as a model for the dietary mixed micelles. We studied the effect of the competitive solubilization of cholesterol and phytosterols on the structural transformations and physical properties of the microemulsion and evaluated the locus of the solubilizates within the nanodroplets of each sterol separately and when they are loaded together at different weight ratios along one dilution line. Our results show that chemical and structural differences between cholesterol and phytosterols significantly influence the solubilization capacity of the nonionic microemulsion. Cholesterol, being more amphiphilic, is solubilized more efficiently at the W/O microemulsion interface, while in the O/W microemulsion phytosterols are dissolved somewhat more efficiently in the droplet core.

An organic-inorganic hybrid material, TPPhA-Ti, was constructed by non-hydrolytic condensation of a dendritic tetrakis-1,3,5,7-(4-phosphonatophenyl)adamantane precursor and titanium(IV) isopropoxide. One preparative pathway yielded insoluble materials with a Ti/P ratio of approximately 1 which was confirmed by a combination of FT-IR, TGA, and EDS measurements. N2 sorption experiments showed that TPPhA-Ti is a porous solid (micropores approximately 13 A; mesopores approximately 38 A) with a high surface area, approximately 550 m2 g(-1). The structure and morphology of the TPPhA-Ti as investigated by transmission and scanning electron microscopy showed a layered-type material. Additional X-ray diffraction data suggest a paracrystalline material; an optimization of possible molecular arrangements of TPPhA-Ti was simulated that was in agreement with the experimental data. A second preparative pathway yielded a Ti oxide-phosphonate with a Ti/P ratio of approximately 3.4. Both TEM and SEM revealed that hollow nanospheres were formed with diameters of approximately 180-300 nm.

Nona-alkanoyloxy tribenzocyclononene (CTV-n, where n is the number of carbons in the side chains) were prepared for n = 2 to 14. The homologues of this series appear in two stable isomeric forms, rigid crown and flexible saddle. We report on their isomerization equilibria and dynamics in solution and on their mesomorphic properties in the neat state. The crown-saddle equilibrium and interconversion kinetics of the CTV-8 isomers were studied in dimethyl formamide solutions using high-resolution (1)H NMR in the temperature range from 50 to 130 degrees C. At lower temperatures, the isomerization is too slow to measure. In this range the equilibrium saddle fraction increases from approximately 0.40 to approximately 0.65, whereas the isomerization rate increases from approximately 10(-)(4) to approximately 1 s(-)(1). The saddle isomer undergoes fast pseudorotation at room temperature, but below about -50 degrees C, it becomes slow enough to affect the NMR line width. The rate parameters for this process were estimated from the carbon-13 spectra in methylene chloride solutions to be, k(p)(-100 degrees C) approximately 1.7 x 10(3) s(-)(1) and E(a) approximately 9.6 kJ/mol. The slow crown-saddle isomerization at room temperature (half-life of about one year) allows quantitative separation (by chromatography) of the two isomers and their separate investigation. When the alkanoyloxy side chains are sufficiently long both isomers are mesogenic (n >or= 4 for the saddle and n >or= 5 for the crown), exhibiting hexagonal columnar mesophases. The structure, dynamics, and mesomorphic properties of these mesophase were investigated by X-ray diffraction, optical polarizing microscopy, differential scanning calorimetry, and NMR. The lattice parameters of the crown and saddle mesophases of corresponding homologues are almost identical and increase monotonically with increasing length of the side chains. The clearing temperatures of the saddle isomers are consistently lower than those of the corresponding crowns. Within each series, the clearing temperatures are almost independent of the length of the side chains (156 to 170 degrees C for the crown and 115 to 148 degrees C for the saddle). The thermal and kinetic properties of the neat compounds lead to peculiar phase sequences, as observed in the polarizing microscope and in the DSC thermogram, involving repeated, back and forth, interconversion between the two isomers. Carbon-13 MAS NMR measurements of the crown and saddle mesophases of several homologues were carried out. The spectra of the crown mesophase exhibit dynamic features consistent with planar 3-fold molecular jumps about the column axes. A quantitative analysis for the CTV-8 crown homologue yielded the following Arrhenius parameters, A = 3.1 x 10(22)s(-)(1) and E(a) = 130.1kJ/mol. These unusually high values suggest that the barrier to the jump process is temperature dependent, decreasing with increasing temperature. The rate of this 3-fold jump process is slower for the lower homologues and faster for the higher ones. In contrast, the saddle isomers in the mesophase do not show dynamic effects in their carbon-13 MAS spectra. They do not undergo pseudorotation, and it appears that the molecules remain locked within the columns in a saddle conformation, up to the clearing temperature. However, on (super-)cooling to room temperature and below, selective line broadening is observed in their carbon-13 MAS spectra. This suggests that the saddle conformation is twisted in the mesophase and undergoes fast high-amplitude jumps between the twisted forms. On cooling, these high-amplitude librations freeze out to give an orientationally disordered state. On a very long time scale (of the order of days at 100 degrees C), the saddle mesophase transforms into that of the crown, apparently by sublimation.

The stability and the ionic conductivity of biological membranes and of lipid bilayers depend on their hydration. A small number of water molecules adhere strongly to the different residues of the lipid headgroups and are oriented by them. An additional number of water molecules adhere more weakly, preserving their freedom of rotation, but are essential for bestowing the thermodynamic properties of hydrated bilayers and of biological membranes. Around six water molecules are attached so strongly to the headgroups of different phospholipids (PL) that they are rendered unfreezable, or their freezing is extended over such a wide range of temperatures that it cannot be detected by differential scanning calorimetry (DSC). If cholesterol is added to the PL above the concentration at which phase separation of the cholesterol phase occurs, the number of unfreezable water molecules per PL increases, indicating that the PL molecules on the border line between the two phases attach nearly twice as many water molecules as those in the middle of the phase. The orientation of about seven or eight water molecules attached to PL headgroups (seven to phosphatidyl serine (PS)) can be detected by polarized FTIR. The dichroic ratio of the successively adhering water molecules to the headgroup of PS fluctuates between 2.6 and 2.9, with the cumulative value of about 2.8 for the seven water molecules adhering to the headgroup of PS. In addition, in this case, the number of water molecules oriented by PL molecule residues on the border line of the two phases is much larger ( approximately 13 for PS). Interaction between two opposite negatively charged layers containing PS approaching each other may lead, after correlated electrostatic attraction, to change in the conformation of the headgroups with concomitant dehydration. This process is enhanced by Ca(+) and by Li(+), but it may also occur with Na(+) and K(+) as counter-ions if the layers are mutually aligned. This process may be important in the fusion mechanism of biological membranes, and its molecular modeling has been carried out.

The enhanced stress resistance exhibited by starved bacteria represents a central facet of virulence, since nutrient depletion is regularly encountered by pathogens in their natural in vivo and ex vivo environments. Here we explore the notion that the regular stress responses, which are mediated by enzymatically catalyzed chemical transactions and promote endurance during the logarithmic growth phase, can no longer be effectively induced during starvation. We show that survival of bacteria in nutrient-depleted habitats is promoted by a novel strategy: finely tuned and fully reversible intracellular phase transitions. These non-enzymatic transactions, detected and studied in bacteria as well as in defined in vitro systems, result in DNA sequestration and generic protection within tightly packed and highly ordered assemblies. Since this physical mode of defense is uniquely independent of enzymatic activity or de novo protein synthesis, and consequently does not require energy consumption, it promotes virulence by enabling long-term bacterial endurance and enhancing antibiotic resistance in adverse habitats.

T cells initiate many immune responses through the interaction of their T-cell antigen receptors (TCR) with antigenic peptides bound to major histocompatibility complex (MHC) molecules. This interaction sends a biochemical signal into the T cell by a mechanism that is not clearly understood. We have used quasielastic light scattering (QELS) to show that, in the presence of MHC molecules bound to a full agonist peptide, TCR/peptide-MHC complexes oligomerize in solution to form supramolecular structures at concentrations near the dissociation constant of the binding reaction. The size of the oligomers is concentration dependent and is calculated to contain two to six ternary complexes for the concentrations tested here. This effect is specific as neither molecule forms oligomers by itself, nor were oligomers observed unless the correct peptide was bound to the MHC. These results provide direct evidence for models of T-cell signalling based on the specific assembly of multiple TCR/peptide-MHC complexes in which the degree of assembly determines the extent and qualitative nature of the transduced signal. They may also explain how T cells maintain sensitivity to antigens present in only low abundance on the antigen-presenting cell.

Closed-circular supercoiled DNA molecules have been shown to form a cholesteric assembly within bacteria as well as in vitro under physiological DNA and salt concentrations. Circular dichroism and X-ray scattering studies indicate that the macroscopic structural properties of the chiral mesophase are directly and uniquely dictated by the supercoiling parameters of the constituent molecules. Specifically, we find that the pitch of the DNA cholesteric phase derived from supercoiled DNA is determined by the superhelical density, which, in turn, is modulated by secondary conformational changes. A direct interrelationship among four DNA structural levels, namely, DNA sequence, secondary structural transitions, the tertiary superhelical conformation, and the quaternary, supramolecular organization is accordingly pointed out. Since secondary conformational changes are both sequence and environment dependent, alterations of cellular conditions may effectively modulate the properties of the packed DNA organization, through their effects on secondary structural transitions and hence on the superhelical parameters. On the basis of these results we suggest that liquid crystallinity represents an effectively regulated packaging mode of plectonemic, nucleosome-free DNA molecules in living systems.

The interaction of cholesterol with a series of saturated phosphatidylglycerols was investigated using differential scanning calorimetry and X-ray diffraction. We find that the miscibility of cholesterol in phosphatidylglycerol bilayers is lower than in the corresponding phosphatidylcholine bilayers and decreases with increasing acyl chain length of the phospholipid. The influence of the negative charge of the phosphatidylglycerol on cholesterol miscibility is discussed.

Miscibility of cholesterol and cholesteryl hemisuccinate was investigated by differential scanning calorimetry and small-angle X-ray scattering. In an excess of cholesterol, above 2:1 mol ratio, phase separation takes place into a mixed phase and an almost pure cholesterol phase.

Extensive effort has been directed toward a quantitative evaluation of forces which operate between biomacromolecules since the characterization of such forces is essential to a thorough understanding of fundamental biological processes. However, all studies hitherto reported were conducted in vitro, using isolated species. Here we report the first quantitative characterization of forces operating between DNA molecules within living bacteria. Evaluation of x-ray scattering studies conducted on intact bacteria indicates that, at DNA-DNA surface separations characteristic of DNA assemblies, interactions are dominated by repulsive hydration forces which originate from the structuring of water molecules. The results support the notion that the mechanisms by means of which macromolecules function, fold, and interact with each other crucially depend upon their hydration properties.

Bacterial plasmids may often reach a copy number larger than 1000 per cell, corresponding to a total amount of DNA that may exceed the amount of DNA within the bacterial chromosome. This observation highlights the problem of cellular accommodation of large amounts of closed-circular nucleic acids, whose interwound conformation offers negligible DNA compaction. As determined by x-ray scattering experiments conducted on intact bacteria, supercoiled plasmids segregate within the cells into dense clusters characterized by a long-range order. In vitro studies performed at physiological DNA concentrations indicated that interwound DNA spontaneously forms liquid crystalline phases whose macroscopic structural properties are determined by the features of the molecular supercoiling. Because these features respond to cellular factors, DNA supercoiling may provide a sensitive regulatory link between cellular parameters and the packaging modes of interwound DNA in vivo.

Evidence for a conceptually novel DNA packaging process is presented. X-ray scattering, electron microscopy, and circular dichroism measurements indicate that in the presence of positively charged micellar aggregates and flexible anionic polymers, such as negatively charged polypeptides or single-stranded RNA species, a complex is formed in which DNA molecules are partially embedded within a micellar scaffold and partially condensed into highly packed chiral structures. Based on studies of micelle-DNA and micelle-flexible anionic polymer systems, as well as on the known effects of a high charge density upon the micellar organization, a DNA packaging model is proposed. According to this model, the DNA induces the elongation of the micelles into rodlike aggregates, forming a closely packed matrix in which the DNA molecules are immobilized. In contrast, the flexible anionic polymers stabilize clusters of spherical micelles which are proposed to effect a capping of the rodlike micelles, thus arresting their elongation and creating surfactant-free segments of the DNA that are able to converge and collapse. Thus, unlike other in vitro DNA packaging systems, in which condensation follows encounters between charge-neutralized DNA molecules, a prepackaging phase where the DNA is immobilized within a matrix is proposed in this case. Cellular and nuclear membranes have been implicated in DNA packaging processes in vivo, and negatively charged polyelectrolytes were shown to be involved in the processes. These observations, combined with the basic tenets of the DNA condensation system described here, allow for the progression to the study of more elaborate model systems and thus might lead to insights into the nature and roles of the intricate in vivo DNA-membrane complexes.

The influence of protons or calcium ions on the miscibility of cholesterol in phosphatidylserine has been examined using differential scanning calorimetry and X-ray diffraction. At pH 2.6, where the carboxyl group of the serine moiety is protonated, two endothermic transitions are observed in cholesterol-phosphatidylserine mixtures. The midpoint of the first is at 35 degrees C in the absence of cholesterol and decreases to approx. 15 degrees C for molar fraction of cholesterol 0.5. The second transition is centered at approx. 44 degrees C, almost independent of cholesterol content. The two lower temperature phases are lamellar and the high temperature phase has hexagonal symmetry. Cholesterol is more miscible in protonated phosphatidylserine than in the sodium form: cholesterol crystals are detected at a molar ratio of phosphatidylserine to cholesterol of about 1.7:1 as compared to about 2.3:1 at neutral pH. In the presence of calcium ions (1.3 Ca2+ per phosphatidylserine), a lamellar phase is observed with layer spacing 53 A which is independent of temperature (25 degrees C-65 degrees C) and of cholesterol content. Calcium ions cause reduced cholesterol solubility: crystallites are detected already at a molar ratio of 4:1.

The result of mixing varying concentrations of the nonionic detergent octyl glucoside (OG) with small unilamellar vesicles (SUV) of egg phosphatidylcholine (PC) made by sonication depends on the ratio between OG and PC in the mixed aggregates. When this molar ratio (Re) is lower than 1.4, the detergent partitions between the PC vesicles and the aqueous medium with a partition coefficient of K = 0.033 mM-1. As a consequence of introduction of OG into the bilayers, the vesicles grow in size. The resultant vesicles have a mean diameter that is an increasing function of Re and is independent of the total PC concentration. Experiments in which the vesicles were loaded with high molecular weight dextran prior to being exposed to OG suggest that the mechanism responsible for the size growth involves lipid transfer rather than fusion. Mixtures with Re values within the range of 1.4-3.2 separate into two macroscopic phases: The lower phase is clear but very viscous. It contains constant OG and PC concentrations and is characterized by an Re value of 3.2, independent of the composition of the whole dispersion. The upper phase contains vesicles of varying concentrations of OG and PC, but a constant Re of 1.4. When the saturating level of 1.4 OG molecules per PC molecule is approached, the concentration of OG monomers in the aqueous medium reaches the value of 16.6 +/- 0.3 mM, which is the apparent cmc of OG in the lipid-containing medium. OG-PC mixed micelles contain at least 3.2 OG molecules per PC molecule. The mixed micelles present at Re = 3.2 apparently have the shape of oblate ellipsoids with a minor axis of about 2 nm and two major axes of about 25 nm. The surface area of the mixed micelles at this point is just sufficient for them to undergo conversion into the smallest possible spherical vesicles of a radius of 12 nm. At Re values above 3.2, the major axis of the mixed micelles becomes smaller as Re increases, while at values of Re below 3.2 the micelles would have been expected to grow very rapidly with decreasing Re. This may explain the partial vesicle closure occurring below Re = 3.2.

The circularly polarized phosphorescence emitted by the 4-thiouridine base was measured for bulk Escherichia coli tRNA, E. coli tRNA1Val, E. coli tRNAfMet, and E. coli tRNAPhe as a function of ionic strength in the presence of 1 mM Mg2+. The emission anisotropy factor, gem, was found to be dependent on the degree of local stacking in the vicinity of the chromophore. For bulk tRNA and tRNAfMet a marked similarity was observed between the behavior of gem and the translational diffusion coefficient D020,w [Pots, R. O., Wang, C. C., Fritzinger, D. C., Ford, N. C. & Fournier, M. J. (1979) in Cold Spring Harbor Monograph Series (Schimmel, P. R; Söll, D., & Abelson, J. N., Eds.) Part A, p 207, Cold Spring Harbor Laboratory, Cold Spring Harbor, NY]. This was interpreted to mean that a relationship exists between the local stacking around the 4-thiouridine chromophore and the overall general similarity of behavior was observed, each species of tRNA examined exhibited a distinctive dependence of conformation on salt concentration. tRNAPhe was found to be a particular exception in the low-salt region (less than 50 mM). The value of the phosphorescence anisotropy factor was found to be remarkably larger (about 50-fold). Thus minor conformational changes in the tRNA molecule are more readily detected by circular polarization of phosphorescence than by circular dichroism

The solution structure of troponin C from turkey skeletal muscle was studied at low pH by small-angle X-ray-scattering. We find that troponin C at pH 5.3 in the presence of Mg2+ has a triaxial radius of gyration and maximum dimension comparable with those of the crystallized protein. However, the relative disposition of domains is more similar to that found for the highly homologous rabbit protein in solution at pH 7.4.

Infrared spectroscopy, deuterium exchange kinetics and X-ray diffraction experiments on H3-H4 complexes in the condensed state are described. Both salt- and acid-extracted material are shown to contain alpha-helix in an amount comparable to that found under dilute solution conditions. Support for an anisotropic model of these complexes is provided.

The molecular packing density of collagen and hence the intrafibrillar water content appears to be regulated in cartilage by the osmotic pressure gradient existing between the extrafibrillar and the intrafibrillar compartments.

The filamentous bacterial virus Pf1 is a simple model for biological filaments. We have studied the structure of the virion and report here that the helix parameters of Pf1 change sharply with temperature at about 8 degrees C. Local interactions between protein subunits change by only a few tenths of an angstrom, but the changes are amplified between one end and the other of the virion to a rotation of 15 turns and a translation of 1,000 A. The limited nature of the phase transition is probably due to the constraints of 'knobs-into-holes' interaction between side chains of adjacent alpha-helical protein subunits. Treatment of the virion with ether causes a rearrangement of protein subunits into sheets, with the alpha-helices normal to the plane of the sheet. This phase transition suggests a model for virion assembly in the bacterial membrane.

X-ray diffraction data from self-assembled histone fibers are presented for three systems: H4, H3-H4, and the four core histones H2A, H2B, H3 and H4. These data have been obtained under conditions of high ionic strength and high protein concentration which are thought to promote histone conformation similar to that found in intact chromatin. The low angle equatorial scattering (R less than .05 A-1) is analysed, and, with additional constraints imposed by electron microscopy data, four low resolution fibrillar models are derived. Two features common to all the possible models are a maximum outer diameter of approximately 60 A and a subfibril diameter of approximately 25 A. It is the interference of the protein subfibrils across a central region of low electron density - a 10 A "hole" - which gives rise to the characteristic diffraction peak at 36 A. Possible relationships of the models of the histone fibers to the structure of the histone component of chromatin are suggested.

Filamentous bacterial viruses are flexible nucleoprotein rods, about 6 nm in diameter by 1000-2000 nm in length (depending on the virus strain). A protein shell encloses a central core of single-stranded circular DNA. The coat protein subunits forming the shell are largely alpha-helix, elongated in an axial direction, and also sloping radially, so as to overlap each other and give an arrangement of subunits reminiscent of scales on a fish. This arrangement of alpha-helices is rather like some models of myosin filaments. An early step in assembly of the virion is the formation of a complex between the viral DNA and an intracellular packaging protein that is not found in completed virions. Newly synthesized coat protein becomes associated with the plasma membrane of the cell. During the final steps of assembly, the packaging protein is displaced from the DNA and replaced by coat protein as the virion passes out through the plasma membrane of the host cell.

Phosphatidylserine-cholesterol mixtures at a molar ratio of 2:1 were investigated by X-ray diffraction. Phase separation of cholesterol independent of temperature was detected, indicating limited solubility of cholesterol in phosphatidylserine bilayers. The second phase present, the mixed phospholipid-cholesterol phase, continued to undergo melting as determined by changes with temperature in both the small angle scattering profile and in the acyl chain packing.