Solid state NMR chemical shifts as an alternative to diffraction data in the determination of SIC polytypic structures

Silicon carbide, which has many polytypic modifications of a very simple and very symmetric structure, is an excellent model system for exploring, the relationship between chemical shift, long-range dipolar shielding, and crystal structure in network solids. A simple McConnell equation treatment of bond anisotropy effects in a poly type predicts chemical shifts for silicon and carbon sites which agree well with the experiment, provided that contributions from bonds up to 100 A are included in the calculation. The calculated chemical shifts depend on three factors: the layer stacking sequence, electrical centre of gravity, and the spacings between silicon and carbon layers. The assignment of peaks to lattice sites is proved possible for three polytypes (6H, 15R, and 3C). The fact that the calculated chemical shifts are very sensitive to layer spacings provides us a potential way to detennine and refine a crystal structure. In this work, the layer spacings of 6H SiC have been calculated and are within X-ray standard deviations. Under this premise, the layer spacings of 15R have been detennined. 29Si and 13C single crystal nmr studies of 6H SiC polytype indicate that all silicons and carbons are magnetically anisotropic. The relationship between a magnetic shielding tensor component and layer spacings has been derived. The comparisons between experimental and semi-empirical chemical shielding tensor components indicate that the paramagnetic shielding of silicon should be included in the single crystal chemical shift calculation.

Can a consecutive double turn conformation be considered as a peptide based molecular scaffold for supramolecular helix in the solid state?

Helices and sheets are ubiquitous in nature. However, there are also some examples of self-assembling molecules forming supramolecular helices and sheets in unnatural systems. Unlike supramolecular sheets there are a very few examples of peptide sub-units that can be used to construct supramolecular helical architectures using the backbone hydrogen bonding functionalities of peptides. In this report we describe the design and synthesis of two single turn/bend forming peptides (Boc-Phe-Aib-Ile-OMe 1 and Boc-Ala-Leu-Aib-OMe 2) (Aib: alpha-aminoisobutyric acid) and a series of double-turn forming peptides (Boc-Phe-Aib-IIe-Aib-OMe 3, Boc-Leu-Aib-Gly-Aib-OMe 4 and Boc-gamma-Abu-Aib-Leu-Aib-OMe 5) (gamma-Abu: gamma-aminobutyric acid). It has been found that, in crystals, on self-assembly, single turn/bend forming peptides form either a supramolecular sheet (peptide 1) or a supramolecular helix (peptide 2). unlike self-associating double turn forming peptides, which have only the option of forming supramolecular helical assemblages. (c) 2005 Elsevier Ltd. All rights reserved.

Conformational heterogeneity of tripeptides containing Boc-Leu-Aib as corner residues in the solid state

A critical analysis of single crystal X-ray diffraction studies on a series of terminally protected tripeptides containing a centrally positioned Aib (alpha-aminoisobutyric acid) residue has been reported. For the tripeptide series containing Boc-Ala-Aib as corner residues, all the reported peptides formed distorted type II beta-turn structures. Moreover, a series of Phe substituted analogues ( tripeptides with Boc-Phe-Aib) have also shown different beta-turn conformations. However, the Leu-modified analogues (tripeptides with Boc-Leu-Aib) disrupt the concept of beta-turn formation and adopt various conformations in the solid state. X-ray crystallography sheds some light on the conformational heterogeneity at atomic resolution. (c) 2007 Elsevier Ltd. All rights reserved.

Self-assembly of beta-turn forming synthetic tripeptides into supramolecular beta-sheets and amyloid-like fibrils in the solid state

We have described here the self-assembling properties of the synthetic tripeptides Boc-Ala(1)-Aib(2) -Val (3)-OMe 1, BocAla(l)-Aib(2)-Ile(3)-OMe 2 and Boc-Ala(l)-Gly(2)-Val(3)-OMe 3 (Aib=alpha-arnino isobutyric acid, beta-Ala=beta-alanine) which have distorted beta-turn conformations in their respective crystals. These turn-forming tripeptides self-assemble to form supramolecular beta-sheet structures through intermolecular hydrogen bonding and other noncovalent interactions. The scanning electron micrographs of these peptides revealed that these compounds form amyloid-like fibrils, the causative factor for many neurodegenerative diseases including Alzheimer's disease, Huntington's disease and Prion-related encephalopathies. (C) 2004 Elsevier Ltd. All rights reserved.

Modelling the uptake and growth kinetics of Penicillium glabrum in a tannic acid-containing solid-state fermentation for tannase production

A mathematical growth model for the batch solid-state fermentation process for fungal tannase production was developed and tested experimentally. The unstructured model describes the uptake and growth kinetics of Penicillium glabrum in an impregnated polyurethane foam substrate system. In general, good agreement between the experimental data and model simulations was obtained. Biomass, tannase and spore production are described by logistic kinetics with a time delay between biomass production and tannase and spore formation. Possible induction mechanisms for the latter are proposed. Hydrolysis of tannic acid, the main carbon source in the substrate system, is reasonably well described with Michaelis-Menten kinetics with time-varying enzyme concentration but a more complex reaction mechanism is suspected. The metabolism of gallic acid, a tannase-hydrolysis product of tannic acid, was shown to be growth limiting during the main growth phase. (c) 2004 Elsevier Ltd. All rights reserved.

Miscibility studies in poly(methyl vinyl ether)/hydroxypropylcellulose binary system in aqueous solutions and solid state

The phase separation behaviour in aqueous mixtures of poly(methyl vinyl ether) and hydroxypropylcellulose has been studied by cloud points method and viscometric measurements. The miscibility of these blends in solid state has been assessed by infrared spectroscopy; methanol vapours sorption experiments and scanning electron microscopy. The values of Gibbs energy of mixing of the polymers and their blends with methanol as well as between each other were calculated. It was found that in solid state the polymers can interact with methanol very well but the polymer-polymer interactions are unfavourable. Although in aqueous solutions the polymers exhibit some intermolecular interactions their solid blends are not completely miscible. (C) 2005 Elsevier Ltd. All rights reserved.

Structural Characterization of Rare-Earth Doped Yttrium Aluminoborate Laser Glasses Using Solid State NMR

The structure of laser glasses in the system (B(2)O(3))(0.6){(Al(2)O(3))(0.4-x)(Y(2)O(3))(x)} (0.1 <= x <= 0.25) has been investigated by means of (11)B, (27)Al, and (89)Y solid state NMR as well as Y-3d core-level X-ray photoelectron spectroscopy, (11)B magic-angle spinning (MAS) NMR spectra reveal that the majority of the boron atoms are three-coordinated, and a slight increase of four-coordinated boron content with increasing x can be noticed. (27)Al MAS NMR spectra show that the alumina species are present in the coordination states four, five and six. All of them are in intimate contact with both the three- and the four-coordinate boron species and vice versa, as indicated by (11)B/(27)Al rotational echo double resonance (REDOR) data. These results are consistent with the formation of a homogeneous, nonsegregated glass structure. For the first time, (89)Y solid state NMR has been used to probe the local environment of Y(3+) ions in a glass-forming system. The intrinsic sensitivity problem associated with (89)Y NMR has been overcome by combining the benefits of paramagnetic doping with those of signal accumulation via Carr-Purcell spin echo trains. Both the (89)Y chemical shifts and the Y-3d core level binding energies are found to be rather sensitive to the yttrium bonding state and reveal that the bonding properties of the yttrium atoms in these glasses are similar to those found in the model compounds YBO(3) and YAl(3)(BO(3))(4), Based on charge balance considerations as well as (11)B NMR line shape analyses, the dominant borate species are concluded to be meta- and pyroborate anions.

Temperature dependence of molecular dynamics and supramolecular aggregation in MEH-PPV films: A solid-state NMR, X-ray and fluorescence spectroscopy study

This article presents an investigation of the temperature induced modification in the microstructure and dynamics of poly[2-methoxy-5-(2`-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) cast films using Wide-Angle X-ray Scattering (WAXS), solid-state Nuclear Magnetic Resonance (NMR), and Fluorescence Spectroscopy (PL). MEH-PPV chain motions were characterized as a function of temperature by NMR. The results indicated that the solvent used to cast the films influences the activation energy of the side-chain motions. This was concluded from the comparison of the activation energy of the toluene cast film, E(a) = (54 +/- 8) kJ/mol, and chloroform cast film, E(a) = (69 +/- 5) kJ/mol, and could be attributed to the higher side-chain packing provided by chloroform, that preferentially solvates the side chain in contrast to toluene that solvates mainly the backbone. Concerning the backbone mobility, it was observed that the torsional motions in the MEH-PPV have average amplitude of similar to 10 degrees at 300 K, which was found to be independent of the solvent used to cast the films. In order to correlate the molecular dynamics processes with the changes in the microstructure of the polymer, in situ WAXS experiments as a function of temperature were performed and revealed that the interchain spacing in the MEH-PPV molecular aggregates increases as a function of temperature, particularly at temperatures where molecular relaxations occur. It was also observed that the WAXS peak associated with the bilayer spacing becomes narrower and its intensity increases whereas the peak associated with the inter-backbone planes reduces its intensity for higher temperatures. This last result Could be interpreted as a decrease in the number of aggregates and the reduction of the interchain species during the MEH-PPV relaxation processes. These WAXS results were correlated with PL spectra modifications observed upon temperature treatments. (C) 2008 Elsevier Ltd. All rights reserved.

Solid state NMR as a new approach for the structural characterization of rare-earth doped lead lanthanum zirconate titanate laser ceramics

To facilitate the design of laser host materials with optimized emission properties, detailed structural information at the atomic level is essential, regarding the local bonding environment of the active ions (distribution over distinct lattice sites) and their extent of local clustering as well as their population distribution over separate micro- or nanophases. The present study explores the potential of solid state NMR spectroscopy to provide such understanding for rare-earth doped lead lanthanum zirconate titanate (PLZT) ceramics. As the NMR signals of the paramagnetic dopant species cannot be observed directly, two complementary approaches are utilized: (1) direct observation of diamagnetic mimics using Sc-45 NMR and (2) study of the paramagnetic interaction of the constituent host lattice nuclei with the rare-earth dopant, using Pb-207 NMR lineshape analysis. Sc-45 MAS NMR spectra of scandium-doped PLZT samples unambiguously reveal scandium to be six-coordinated, suggesting that this rare-earth ion substitutes in the B site. Static Pb-207 spin echo NMR spectra of a series of Tm-doped PLZT samples reveal a clear influence of paramagnetic rare-earth dopant concentration on the NMR lineshape. In the latter case high-fidelity spectra can be obtained by spin echo mapping under systematic incrementation of the excitation frequency, benefiting from the signal-to-noise enhancement afforded by spin echo train Fourier transforms. Consistent with XRD data, the Pb-207 NMR lineshape analysis suggests that statistical incorporation into the PLZT lattice occurs at dopant levels of up to 1 wt.% Tm3+, while at higher levels the solubility limit is reached. (C) 2008 Elsevier Masson SAS. All rights reserved.

Solid-state NMR characterization of a series of copolymers containing fluorene, phenylene and thiophene units

Fluorene and thiophene units are commonly used in polymeric materials for electro-optical applications. Due to differences in reactivity, the final composition of polymers containing these components often differs from that used in their preparation. This contribution describes the synthesis of PPV type terpolymers built by fluorene, phenylene and thiophene units and their quantification by CPMAS NMR. The similarity of the three aromatic co-monomers makes it difficult to separate the analytical responses that would allow quantification of each copolymer unit in the chain. In this sense, we show that the combination of dipolar dephased CPMAS with radiofrequency ramp and proper spectral treatment allows a good estimation and quantification of the copolymer constitution. (C) 2011 Elsevier Ltd. All rights reserved.

Pseudo-nonlinear and athermal lensing effects on transverse properties of Cr(3+) based solid-state lasers

Several experiments (time-resolved Z-scan experiments based on pulsed and CW pump lasers, time-resolved divergence diagnostics) have been performed to examine and clarify the question of the converging or diverging population lensing effect occurring in a Cr(3+):Al(2)O(3) ruby laser. The dynamics of the laser far-field divergence of such a laser indeed indicated initially a diverging effect while Z-scan measurements conclude to a converging one. The origin of this discrepancy is thus analysed and elucidated here by introducing the general concept of correlation collapse between the centre and the wings of a laser beam having some clipping. (C) 2010 Elsevier B.V. All rights reserved.

Investigation of microwave dielectric relaxation solid state process in the antiferroelectric phase of NaNbO3 ceramics

This letter reports microwave dielectric measurements performed in the antiferroelectric phase of NaNbO3 ceramics from 100 to 450 K. Remarkable dielectric relaxation was found within the antiferroelectric phase and in the vicinity of the ferroelectric-antiferroelectric phase transition. Such dielectric relaxation process was associated with relaxations of polar nanoregions with strong relaxor-like characteristic. In addition, the microwave dielectric measurements also revealed an unexpected and unusual anomaly in the relaxation strength, which was related to a disruption of the antiferroelectric order induced by a possible AFE-AFE phase transition. (C) 2004 Elsevier Ltd. All rights reserved.

Evaluation of strip rolling directly from the semi-solid state

defect metal alloy strip when thixorolling directly from the semi-solid state. To facilitate the study lead/tin alloys were chosen for their relatively low operating temperature. The objective is to extrapolate these findings to the higher temperature aluminium, alloys. Three alloys (70%Pb30%Sn, 60%Pb-40%Sn, 50%Pb-50%wtSn) were used particularly to study the influence of the solidification interval. The equipment consists of a two roll mill arranged as an upper and lower roller, where both rollers are driven at a controlled speed. The lower roller is fed with semi solid alloy through a ceramic nozzle attached to the lower end of a cooling slope. Several types of nozzle and their position at the roller were tested. This produced different solidifications and consequently different finished strip. The alloys were first cast and then poured onto the cooling slope through a tundish in order to create a continuous laminar flow of slurry and uniformity of metal strip quality. The pouring was tested at different positions along the slope. The cooling slope was coated with colloidal graphite to promote a smooth slurry flow and avoid the problem of adherence and premature solidification. The metallic slurry not only cools along the slope but is also initially super-cooled to a mush by the lower roller whilst at room temperatures, thus enabling thixorolling. It was also found that the nozzle position could be adjusted to enable the upper roller to also contribute to the solidification of the metallic slurry. However the rollers and the cooling slope naturally heat up. Temperature distribution in these zones was analysed by means of three thermocouples positioned along the cooling slope and a fourth in the base of the semi solid pool within the nozzle. The objective being to design an optimum pouring and cooling system. The formed strip was cooled down to room temperature with a shower of water. Microstructures of the thixorolling process were analysed. The differences in solidification conditions resulted in differing qualities of finished strip and corresponding defect types, all of which are a serious quality issue for the rolled product.

Pectinase production by a Brazilian thermophilic fungus Thermomucor indicae-seudaticae N31 in solid-state and submerged fermentation

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Purification and characterization of an exo-polygalacturonase produced by Penicillium viridicatum RFC3 in solid-state fermentation

The pectinolytic enzyme obtained from Penicillium viridicatum RFC by solid-state fermentation was purified to homogeneity by pretreatment with kaolin (40 mg mL(-1) ) and ultrafiltration. followed by chromatography on a Sephadex G50 column. The apparent molecular weight of the enzyme was 24 kDa. Maximal activity occurred at pH 6.0 and at 60 degrees C. The enzyme proved to be an exo-polygalacturonase, releasing galacturonic acid by hydrolysis of highly esterified pectin. The presence of 10 mM Ba2+ increased the enzyme activity by 96% and its thermal stability by 30%. besides increasing its stability at acid pH. The apparent K-m with apple pectin as substrate was 1.82 mg mL(-1) and the V-max was 81 mu mol min(-1). (c) 2007 Elsevier Ltd. All rights reserved.