Measuring the crystallinity index of cellulose by solid state 13C nuclear magnetic resonance

The crystallinity index of cellulose is an important parameter to establish because of the effect this property has on the utilization of cellulose as a material and as a feedstock for biofuels production. However, it has been found that the crystallinity index varies significantly depending on the choice of instrument and data analysis technique applied to the measurement. We introduce in this study a simple and straightforward method to evaluate the crystallinity index of cellulose. This novel method was developed using solid state ¹³C NMR and subtraction of the spectrum of a standard amorphous cellulose. The crystallinity indexes of twelve different celluloses were measured and the values from this method were compared with the values obtained by other existing methods, including methods based on X-ray diffraction. An interesting observation was that the hydration of the celluloses increased their crystallinity indexes by about 5%, suggesting that addition of water increased cellulose order for all the cellulose samples studied.     

Suppression of electron-hole correlations in 3D polymer materials

We present an ab initio study of the optical absorption spectra of isolated as well as crystalline trans-polyacetylene. We include excitonic effects by solving the Bethe-Salpeter equation for the electron-hole two-particle correlation function. We observe that the strength of the electron-hole interactions drastically reduces when going from an isolated polymer chain to a crystalline arrangement. This is not only a result of enhanced screening in the 3D material, but also of the increased spatial extent of the exciton perpendicular to the polymer chains. We point out that these findings apply to crystalline phases of conjugated polymers and molecular crystals in general.     

Inadequacy of perfect-reflector models in cavity QED for systems with low-frequency excitations

It is shown that the model of perfectly reflecting boundaries widely employed in cavity QED is unsuitable for systems that have long-wavelength excitations. A prime example is a free charged particle near a reflecting wall. Modeling the wall as perfectly reflecting from the outset ignores evanescent waves that couple to the particle through virtual excitations at low energies, which can lead to errors in order of magnitude and even sign. The example of a free electron near an imperfectly reflecting wall characterized by a constant frequency-independent refractive index n is investigated in detail by determining its energy shift relative to an electron in vacuum through both nonrelativistic and relativistic calculations.     

QALE analysis of CO dissociative kinetics of Ru(CO)4L (L = P-donor ligands): accelerating effects of hydrogen in PHnR(3 - n) ligands (n = 1-2)

Studies of CO-dissociative substitution reactions of the complexes Ru(CO)4L (L = a wide variety of P-donor ligands) have been extended and analysis of the results by the QALE methodology has been refined (QALE = quantitative analysis of ligand effects). Rates increase substantially with increasing size of L, mainly as a consequence of increasingly favourable activation entropies. These can be associated with increasing Ru-CO bond breaking that is compensated enthalpically by increasing Ru-P bond making allowed by release of steric strain. Explicit allowance for pi-acidity shows that these effects are just significant while sigma-donor and aryl effects are negligible. However, pendent hydrogen atoms, attached directly to the phosphorus atoms, have a pronounced and unique positive effect on the rates, with significant kinetic isotope effects (KIE). This is associated with the novel occurrence of direct Ru-H or incipient Ru-(eta2-P-H) agostic bond making as the CO ligand departs.     

Introduction of 4(S)-oxazolidineacetic acid, 2-oxo (D-Oxac) motif in a polypeptide chain: synthesis and conformational analysis

A four step synthesis of 4(S)-oxazolidineacetic acid, 2-oxo benzyl ester (D-Oxac-OBn) from L-Asp-OH in 45% overall yield is reported. The formation of by-products is completely avoided, by microwave irradiation and by the use of caesium carbonate as base. Moreover the synthesis and IR and 1H NMR conformational analysis of the tetramers Boc-L-Val-D-Oxac-L-Ala-OBn and Boc-L-Val-D-Oxac-Aib-L-Ala-OBn in solution is reported.     

Core of projective dimension one modules

The core of a projective dimension one module is computed explicitly in terms of Fitting ideals. In particular, our formula recovers previous work by R. Mohan on integrally closed torsionfree modules over a two-dimensional regular local ring. The first author was partially supported by a Faculty Research Fellowship from the University of Kentucky. The second and third authors gratefully acknowledge partial support from the NSF.Mathematics Subject Classification (2000):Primary 13A30, 13B21; Secondary 13C99     

Acridinone-based anion receptors and sensors

The interaction of a variety of acridinone derivatives containing hydrogen-bond donor groups in the 4- and 5-positions with anions demonstrate the potential of this new scaffold in anion receptor and sensor design.