Origin of the twist of cellulosic materials.

Molecular Mechanics, Hartree-Fock, and semi-empirical geometry optimizations were carried out on cellulose oligomers and crystallites with and without water solvation. The intramolecular bonding is visualized with the Delocalized Molecular Orbitals (DLMOs). Internal coordinates were relaxed and the structures were gradient optimized for cellulose oligomers composed of 4, 10, 12, 14, 19, and 65 glucose units. The cellulose conformation of minimum energy deviates from the flat ribbon conformation giving rise to half-twist repeating units of about 3-4nm and 60nm along the chain axis. An optimized cellulose chain which is ten glucose units long is 9.57kcal/mol more stable than the flat ribbon model. The DLMOs show the twisted model retains the same hydrogen bonding scheme as the flat model while minimizing steric interactions between H1 and H4'. In cellulose crystallites the twist, which can be left- or right-handed, calls into question the assumption of twofold symmetry in the current flat unit cell. Additionally the hydrogen bonded sheets reorient themselves, suggesting the crystallites are in fact crystalloids. The overall length of the crystal twist is dependent on the cross-section of the crystal. Powder X-ray diffraction patterns of the optimized crystallites were simulated.

Molecular orbital studies of gas-phase interactions between complex molecules.

Describing interactions among large molecules theoretically is a challenging task. As an example, we investigated gas-phase interactions between a linear nonionic oligomer and various model compounds (cofactors), which have been reported to associate experimentally, using PM3 semiempirical molecular orbital theory. As oligomer, we studied the hexamer of poly(ethylene oxide) (PEO), and as cofactors, we studied corilagin and related compounds containing phenolic groups (R-OH). These systems are of interest because they are models for PEO/cofactor flocculation systems, used in industrial applications. The PM3 delocalized molecular orbitals (DLMO) describe the bonding between (PEO)6 and cofactors, and some of them cover the complete complex. The DLMOs which cover the traditionally considered hydrogen bonds R-OH...O or R-CH...O show a distinct "pinch", a decrease of the electron density, between the H...O atoms. Calculations of Gibbs free energy, entropy, and enthalpy show that the PEO/cofactor complexes do not form at room temperature, because the loss of entropy exceeds the increase in enthalpy. The change in enthalpy is linearly related to the change in entropy for the different complexes. Even though bond lengths, bond angles, DLMOs, and electron densities for the PEO/cofactor complexes are consistent with the definition of hydrogen bonds, the number of intermolecular R-OH...O and R-CH...O bonds does not correlate with the enthalpy of association, indicating that the bonding mechanism for these systems is the sum of many small contributions of many delocalized orbitals.

Hydrogen-bond self-assembly of DNA-analogues into hexameric rosettes.

The self-assembly of a DNA-analogue hexameric rosette from triaminopyrimidine and cyanuric acid-based nucleosides, and its subsequent aggregation into rod-like morphologies is reported.

Novel self-assembly of amphiphilic copolymers into nanotubes: characterization by small-angle neutron scattering.

The self-assembly into nanotubes in solution of an amphiphilic copolymer is characterized by small-angle neutron scattering (SANS). This study confirmed the shape and the size of the tubular association and the 3-D association of the tubes predicted by molecular orbital theory. Moreover, the characterization of the stability of the association has revealed that the addition of a very small amount of salt to the solution increases the size of the association. When more salt is added, the size of the association decreases, and the structure is altered. The association was found to be independent of temperature and therefore is very stable.

Linear conformation of poly(styrene-alt-maleic anhydride) capable of self-assembly: a result of chain stiffening by internal hydrogen bonds.

A careful conformational analysis of poly(styrene-alt-maleic anhydride) at different pH values is presented. It is found that a strong internal hydrogen bond is formed at intermediate pH, which induces a change in the conformation of the polymer chain, which becomes linear. This linearity does not depend on the chirality of the polymer. The linearity of the chain occurs only at intermediate pH and can explain the association among the chains observed by dynamic light scattering at pH 7.

Templated crystallization of octadecanol on patterned nanoassemblies.

A serial templating methodology using linked aminosilane/stannane units and simple beaker chemistry yields thin film nanoassemblies on semiconductor surfaces that provide nucleating sites for crystallization of octadecanol, the morphologies of which could be tailored using subtle variations in the backbone structure of bridged aminosilane/stannanes.

Photoresponsive supramolecular systems: self-assembly of azodibenzoic acid linear tapes and cyclic tetramers.

A new strategy to effect photoinduced control over molecular self-assembly is reported. This strategy uses the reversible trans-cis photoisomerization of a novel azobenzene system, where the trans- and cis-forms self-assemble into dramatically different higher-order structures. The trans-azobenzene form of this molecule associates into infinite hydrogen-bonded linear tapes, while the cis-azobenzene form undergoes hydrogen-bonded self-assembly into cyclic tetramers. This results in a second level of association, where the cis-hydrogen-bonded supramolecular cycles ultimately form long, rod-like aggregates through stacking interactions.

Energy barriers to rotation in axially chiral analogues of 4-(dimethylamino)pyridine.

The barriers to enantiomerization of a series of axially chiral biaryl analogues of 4-(dimethylamino)pyridine (DMAP) 1-10 were determined experimentally by means of dynamic HPLC measurements and racemization studies. The barriers to rotation in derivatives 1-6 (based on the bicyclic 5-azaindoline core) were lower than those in the corresponding derivatives 7-10 (based on the monocyclic DMAP core). Semiempirical (PM3), ab initio Hartree-Fock (HF/STO-3G), and density functional theory (DFT/B3LYP/6-31G*) calculations reveal that these differences in barriers to rotation are the result of differing degrees of hybridization of the non-pyridyl nitrogen in the enantiomerization transition states (TSs). The importance of heteroatom hybridization as a factor in determining nonsteric contributions to barriers to rotation in azabiaryls of this type is discussed.

General practitioners' and patients' models of obesity: whose problem is it?

Primary care literature emphasises the importance of agreement and shared models in the consultation. This study compared general practitioners' (GPs') and patients' models of obesity. Questionnaires concerning beliefs about the causes, consequences and solutions to obesity were completed by 89 general practitioners (GPs) and 599 patients from practices across UK. In terms of causes, the results showed that the patients were more likely to attribute obesity to a gland/hormone problem, slow metabolism and stress than the GPs, whereas the GPs were more likely to blame eating too much. In terms of consequences, the patients rated difficulty getting to work more highly whereas the GPs regarded diabetes as more important. For the solutions to obesity, the two groups reported similar beliefs for a range of methods, but whereas the patients rated the GP and a counsellor as more helpful, the GPs rated the obese person themselves more highly. It is argued that patients show a self serving model of obesity by blaming internal uncontrollable factors for causing obesity yet expecting external factors to solve it. In contrast, GPs show a victim blaming model by attributing both cause and the solution to internal controllable factors. Such differing models have implications regarding the form of intervention likely to be used in primary care and indicate that whereas patients would prefer a more professional based approach, GPs would prefer a more patient-led one. Further, the results suggest that even if an intervention could be negotiated, success rates would be low as either the patient or the GP would be acting in contradiction to their beliefs about the nature of obesity.

Fractal dimension predicts broadband ultrasound attenuation in stereolithography models of cancellous bone.

There has been considerable debate on the relative dependence of broadband ultrasound attenuation (nBUA, dB MHz(-1) cm(-1)) upon the density and structure of cancellous bone. A nonlinear relationship between nBUA and porosity has recently been demonstrated using stereolithography models, indicating a high structural dependence for nBUA. We report here on the measurement of trabecular perimeter and fractal dimension on the two-dimensional images used to create the stereolithography models. Adjusted coefficients of determination (R2) with nBUA were 94.4% (p < 0.0001) and 98.4% (p < 0.0001) for trabecular perimeter and fractal dimension respectively. The feature of fractal dimension representing both the porosity and connectivity of a given structure is most exciting. Further work is required to determine the relationship between broadband ultrasound attenuation and fractal dimension in complex three-dimensional cancellous bone structures.

Development of a cancellous bone structural model by stereolithography for ultrasound characterisation of the calcaneus.

A novel method for the development of a user-defined structural model simulating cancellous bone of the human calcaneus is described using stereolithography (SL). The digital image of a cancellous bone section was modified by skeletonisation and dilation to produce a structural model of uniform wall thickness, determined by the resolution of the stereolithography system. Six SL models were produced using the same data file. The SL models were assessed using the McCue CUBAclinical ultrasound bone densitometer. The broadband ultrasound attenuation (BUA) and velocity (VOS) values obtained were commensurate with the commercial phantom provided with the CUBAclinical system. The intra- and inter-sample variability for the six SL models were similar at 5% for BUA and 2.5% for VOS. Stereolithography offers the potential to firstly, simulate perforation and thinning of cancellous bone associated with osteoporosis, and secondly, to evaluate the dependence of ultrasonic and mechanical parameters upon cancellous bone structure.

The non-linear relationship between BUA and porosity in cancellous bone.

There is growing interest in assessing the clinical value of ultrasound in the prediction and management of osteoporosis. However, the mechanism of ultrasound propagation in cancellous bone is not well understood. The Biot theory is one approach to modelling the interaction of sound waves with cancellous structure, and porosity is one of its input parameters. In this paper we report the relationship between broadband ultrasonic attenuation (BUA) corrected for specimen thickness (nBUA) and porosity in a porous Perspex cancellous bone mimic, a stereolithography cancellous bone mimic and in natural human and bovine tissue. nBUA and porosity have a non-linear parabolic relationship. The maximum nBUA value (nBUAmax) occurs at approximately 30% porosity in the Perspex mimic, approximately 70% in the stereolithography mimic and approximately 75% in natural cancellous bone. We discuss the effect of structure on the form of the nBUA-porosity relationship.