An improved model for calculating the optical rotation of simple saccharides.

A calculational model for the optical rotation (OR) at the sodium D-line of simple saccharides has been developed that eliminates deficiencies of a previous model. Conformational conclusions based on the earlier model are not affected, as established by a recalculation of the OR phi,psi-map of methyl 3-O-(alpha-D-mannopyranosyl)-alpha-D-mannopyranoside. The model relocates the strong long-wavelength sigma-sigma* circular dichroism (CD) component, which is mainly responsible for the NaD OR from 160 to below 130 nm, where it is now known to occur. That correction allows future modeling of CD bands of different origins that appear in the 150-190 nm region. In order to demonstrate the utility of the revised model, it was applied to calculating the OR of methyl 3-O-(alpha-L-rhamnopyranosyl)-alpha-L-rhamnopyranoside. The results provide experimental support for conformational conclusions derived from a molecular mechanics study of that molecule.

Anhydro sugar and linkage contributions to circular dichroism of agarose and carrageenan, with conformational implications.

The geometry-dependent linkage contributions to the circular dichroism (CD) of agarose and carrageenan were determined by subtracting the monomeric CD from the CD of the polymers. For this purpose, the CD of methyl 3,6-anhydro-alpha-D-galactopyranoside, and of other anhydro sugars, was measured. Application of empirical quadrant rules indicates the observed CD to be that expected for the helical conformations of agarose and carrageenan as derived from diffraction data and modeling calculations. The difference in CD sign in the two polymers arises from a translocation of the beta-D-galactose O-2 atom from one quadrant to the neighboring quadrant of the C-5-O-5-C-1 ether chromophore of the preceding anhydro sugar residue, demonstrating the unusually high spatial resolution of conformational analysis that can be achieved with CD under favorable circumstances.

Experimental chiroptical verification of linkage flexibility in methyl 3-O-(alpha-d-mannopyranosyl)-alpha-d-mannopyranoside.

Vacuum UV CD spectra of methyl 3-O-(alpha-D-mannopyranosyl)-alpha-D- mannopyranoside in D2O and as a cast film were obtained in the 145-200 nM region. The disaccharide solution CD per residue is nearly identical to that of the monosaccharide solution CD, and to the monosaccharide film CD. Conversely, the disaccharide film spectrum exhibits a strong positive CD linkage contribution in the 160-170 nm range, which is consistent with the known crystal conformation under the aegis of previously determined sector rules. The close similarity between the monosaccharide and disaccharide solution spectra, therefore, reflects conformational averaging in which the net linkage contribution is approximately zero. The present observation of significant solution linkage flexibility confirms previous conclusions based on optical rotation, as well as conclusions of others based on nmr data. Moreover, when combined with those earlier results, the present work demonstrates the population of at least three distinct potential energy wells on the disaccharide phi,psi potential energy surface.

Vacuum ultraviolet circular dichroism of gellan-family polymer films from water and dimethyl sulfoxide.

The denaturing effect of dimethyl sulfoxide (Me2SO) on the conformation of the gellan-welan-rhamsan family of microbial polysaccharides is directly demonstrated by circular dichroism (CD). The three polysaccharides display strikingly similar CD spectra (140-210 nm) for films cast from Me2SO. The disrupting effect of Me2SO on gellan and welan conformations has previously been reported by others on the basis of light-scattering and viscosity studies. Films cast from aqueous solutions at room temperature show more-intense CD bands, both at 182 nm, as is also observed for aqueous solutions, and in the 150-175 nm region. These features correspond to the ordered helical chains found by X-ray diffraction studies of similarly prepared films.

A conformational study of agarose by vacuum UV CD.

Agarose films were prepared using a variety of casting conditions, heat treatments, and solvation treatments. Films represented the high temperature sol, the room temperature gel, and a high temperature state with cross-links intact. The vacuum uv CD of the film samples varies considerably, but the similarities between the film CD and the previously reported solution CD show that dehydration per se does not affect the CD. Combining the CD results for the dried sol with the x-ray results of Foord and Atkins leads to a description of the high temperature sol in terms of locally extended chain conformations. The CD of the gel and its peculiarly high uv absorption are satisfactorily, albeit not uniquely, interpreted in terms of the double-helix model of the gel, in agreement with previous conformational studies based on chiroptical properties.

Making sense of usefulness: an avenue toward satisfaction in later life.

Studies of later life assert that sense of usefulness impacts life satisfaction. This study determines what impacts sense of usefulness. The sample consists of 108 older adults, ages sixty through ninety, who were involved with community organizations. The research instrument was a forty-five-item questionnaire. Findings identify five correlates of sense of usefulness: continuity in respect from younger ages (p < .01), involvement with family (p < .05), involvement with a significant other (p < .01), involvement with community (p < .01), and meeting one's expectations for old age (p < .01). "Continuity in respect," "meeting one's expectations," and "sense of usefulness" combine into a scale that correlates with satisfaction in later life (p < .001). Results contribute to theoretical understanding of later life development and suggest directions for work with the aging client system.

Older women who volunteer: tapping a valuable woman resource.

Older women are increasing in number and are the gender who most often volunteer. Thus, an increasing pool of older women volunteers may be forthcoming. Keeping these women satisfied can serve them and the people they serve. The 119 women in this study range in age from 60 to 93, are racially diverse, and are most often low-to-middle income. For these women, volunteer satisfaction and retention relate to interaction on the job, recognition for their work, and meeting their own expectations. Methods for meeting these needs are suggested.

Vacuum ultraviolet circular dichroism of fibronectin. Dominant tyrosine effects.

The spectroscopic authenticity of a very intense negative band at about 183 nm reported previously from conventional circular dichroism (c.d.) studies of bovine plasma fibronectin has now been confirmed by vacuum ultraviolet c.d. measurements on two prototype spectrometers, one using a conventional light source and the other using synchrotron radiation. Closely similar spectra were obtained from both instruments, and from both solid films and solutions. The spectra show no obvious parentage in the known c.d. of the peptide backbone, but have marked similarities to the c.d. of N-acetyltyrosineamide, both in the strong band at 183 nm and in a characteristic positive band at 230 nm, It is concluded that the c.d. of fibronectin is dominated by contributions from tyrosine side-chains and that, as suggested previously, these may provide a sensitive probe for molecular organization and interactions.

A semiempirical theory of the optical activity of saccharides.

A semiempirical theory of optical activity of saccharides is developed that (a) goes beyond previous empirical treatments, (b) yields calculated NaD rotations which correlate well with experimental data, and (c) accounts for a characteristic c.d. band observed for polysaccharides in the vacuum u.v. spectrum.

Vacuum ultraviolet circular dichroism of keratan sulfate.

The vacuum ultraviolet CD of keratan sulfate reveals an intense negative CD band at 171 nm. Its intensity can be rationalized with a recently proposed quadrant rule in terms of the acetamido group being slightly tilted toward the hexosaminidic linkage oxygen. The same structural feature accounts for the particularly intense negative n-pi CD band near 210 nm.

Conformation of (1----6)-beta-D-glucan by vacuum-ultraviolet circular dichroism.

Gelation of pustulan [(1----6)-beta-D-glucan] likely involves some chain ordering. To characterize the most probable conformation, we previously carried out energy calculations and identified the local energy minimums. Here, we analyze the (previously measured) vacuum-ultraviolet circular dichroism of pustulan by using a quadrant rule recently proposed for the 175-nm c.d. band and our earlier quantum-mechanical model for the 185-nm c.d. band. Most of the local-energy minimum conformations are shown to be inconsistent with the circular dichroism observed. Of the two distinct conformations consistent with the observed circular dichroism, one includes the global-energy minimum calculated earlier, i.e., (phi, psi, omega) = (20 degrees, -90 degrees, gt).

Solid-state 13C NMR and X-ray diffraction of dermatan sulfate.

Dermatan sulfate in the solid state has been studied by 13C CP/MAS nmr and X-ray diffraction in order to establish the ring conformation of the L-iduronate moiety. The solid state nmr spectrum is similar to the solution spectrum obtained previously, indicating that a ring conformation at least approximating to 1C4 predominates in the solid state. X-ray powder diffraction data from the same sample indicate the presence of the 8-fold helix form previously observed by fiber diffraction, and interpreted in terms of a 4C1 ring form. A likely explanation of the results is that a distorted 1C4 L-iduronate ring conformation, not considered in the initial X-ray analysis, may emerge to provide a satisfactory interpretation of all available physical-chemical data.

Conformational studies of dextran [alpha-(1----6)-D-glucan].

A theoretical conformational study of dextran, a (1----6)-linked alpha-D-glucan polysaccharide, has been made to allow n explicit comparison with earlier results on pustulan, the corresponding (1----6)-linked beta-D-glucan. The nonbonded, torsional and hydrogen bond contributions to potential energy were calculated as a function of rotational angles phi, psi, and omega. The (phi, psi, omega)-space of the disaccharide and of helices contain many local energy minima with very small energy differences. A comparison of (1----6)-alpha-D-glucans with (1----6)-beta-D-glucans indicates significantly differences in conformational behavior. Specifically, our results shed light on the fact that dextran does not gel, whereas pustulan does. The difference in tendency to gel may be related to the fact that dextran has no particularly favored conformations with structural regularity whereas pustulan does.

Theoretical study of the conformations of pustulan [(1----6)-beta-D-glucan].

The total potential energy including nonbonded, torsional and hydrogen bond contributions has been computed for pustulan, a (1----6) linked beta-D-glucan polysaccharide, as a function of rotational angles phi, psi, and omega. The (phi,psi,omega)-space contains many local minima and at least three distinct deep minima. Two minima at (phi,psi,omega) = (25 degrees, 190 degrees,gg) and (phi,psi,omega) = 65 degrees, 150 degrees,gg) of almost equal energies have helical parameters (n = 5.2, h = 1.0A) and (n = 3.2, h = 1.5A), respectively. A third minimum at (phi,psi,omega) = (40 degrees, 70 degrees gt) leads to an extended zig-zag structure (n = 2.2, h = 2.2A). Energy maps obtained for gentiobiose, the disaccharide of pustulan, also reveal many local minima and the small energy differences among them indicate that gentiobiose is extremely flexible. Gentiodextrins, a family of cyclic molecules of (1----6)-beta-D-glucose residues, were also studied. Conformations free from steric hindrance were found for cyclic molecules with three to six glucose residues.

Galactofuranosyl-containing glycopeptide of Penicillium charlesii. Vacuum ultraviolet circular dichroism.

The far and vacuum u.v. circular dichroism (CD) of peptidophosphogalactomannan from P. charlesii is reported to 182.5 nm in aqueous and aqueous/organic solvents, and to 150nm in films. CD of films of the peptide-free derivative is reported to 150 nm. On the basis of these data we conclude that the peptide chain is unordered, and may best be described as a hydrated coil showing some stiffness. The small observed saccharide CD may result from cancellation of contributions from the various saccharide structures present or from a lack of repeating secondary structure.

Circular dichroism conformational study of the chemotactic peptide formyl-L-methionyl-L-leucyl-L-phenylalanine.

The solution circular dichroism of the chemotactic agent formyl-L-methionyl-L-leucyl-L-phenylalanine was found to be highly solvent dependent. In relatively nonpolar solvents (fluoroalcohols) the circular dichroism is that characteristic of a folded conformation. In H2SO4 the tripeptide remains intact and displays a circular dichroism typical of highly solvated and totally disordered peptides. The order-to-disorder transition can be followed by addition of water to trifluoroethanol.