Comparative Reactivity of the Three Glucosyl -OH Positions -2, -3 and -6 during esterification and saponification of starch by nmr spectroscopy of partially Deutero-acetylated material

International audienceThe individual reactivity of the three hydroxyle groups, (OH-2, OH-3, OH-6) of the glucosyl monomer residue in starch, under esterification and saponification conditions, were analyzed by 1H nmr spectroscopy. A first sample, obtained by direct acetylation, led to an intermediate DS of 1.5, leaving half of hydroxyle positions untouched. These free -OH groups were then esterified with deuterated acetic anhydride. In order to analyse the reactivity under saponification conditions, a second sample was fully acetylated, then, half of the acetate groups were removed by saponification with ethanolic KOH. These regenerated OH groups were then re-esterified with deuterated acetic anhydride as per the previous sample. The proton nmr spectra of each sample was recorded in deuterated chloroform. Integration of the (CH3) peaks in the 1 to 2 ppm region allowed the measurement of the relative (1H) acetate level on each of the three hydroxyle positions

Analytical Description of X-Ray Peaks: Application to L X-Ray Spectra Processing of Lanthanide Elements by Means of the Electron Probe Micro-Analyzer

The shape of Lα X-ray peaks analyzed by means of a LiF (200 plane) monochromator was described by a pseudo-Voigt function: P(λ) = 0.35 P1(λ)+ 0.65 P2(λ) where P1(λ) and P2(λ) are a Gaussian and a Lorentzian distribution centered at the same wavelength, with the same amplitude and half-width and in relative proportion 0.35 and 0.65 respectively. For peaks occurring at wavelength greater than ≃ 0.17 nm, a Gaussian offset was added in order to correct the asymmetry of peaks resulting from the monochromator mounting within the spectrometer. The effective wavelength resolution was obtained by quadrature addition of the instrumental resolution and the natural width of the X-ray peaks. It has been shown that the difference in peak width of the L emission peaks of the lanthanide elements resulted from their difference in their natural widths. For these elements, the Lβ2, Lγ1 and Lγ2 were found to be accompanied by non-diagram lines, Lβ14, Lγ9 and Lγ10 respectively. The wavelength separation distances Lβ14-Lβ2, Lγ9-Lγ1 and Lγ10-Lγ2 were found consistent with the distances derived from the plasmon theory

Isolation of bis-indole alkaloids with antileishmanial and antibacterial activities from Peschiera van heurkii (syn. Tabernaemontana van heurkii)

Des extraits de feuilles et d'écorces de tiges de #Peschiera van heurkii (Muell. Arg.) L. Allorge, (Syn. #Tabernaemontana van heurkii Muell. Arg.) ont montré une activité antileishmanienne et antibactérienne significative. Les activités étaient concentrées dans les fractions alcaloïdiques, desquelles ont été isolés et identifiés 20 alcaloïdes indoliques et bis-indoliques. La plus forte activité leishmanicide et antibactérienne fut observée avec les alcaloïdes dimères conodurine (1), N-démethyle - conodurine (=gabunine) et conoduramine. Les deux premiers composés se sont avérés faiblement toxiques vis-à-vis des cellules hôtes les macrophages, tout en présentant une forte toxicité pour les formes intracellulaires du parasite. #In vitro$, l'alcaloïde (1) s'est avéré moins actif que le médicament de référence, le glucantime (=N-methylglucamine antimonate). (Résumé d'auteur

Effect of TiO2 addition on structure, solubility and crystallisation of phosphate invert glasses for biomedical applications

NOTICE: this is the author’s version of a work that was accepted for publication in JOURNAL OF NON-CRYSTALLINE SOLIDS. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in JOURNAL OF NON-CRYSTALLINE SOLIDS, [VOL 356, ISSUE 44-49, (2001)] DOI: 10.1016/j.jnoncrysol.2010.03.02

Effects of regional and local stresses on fault slip tendency in the southern Taranaki Basin, New Zealand

© 2019 Elsevier Ltd Determining the potential for faults to slip is widely employed for evaluating fault slip potential and associated earthquake hazards, and characterising hydrocarbon seal integrity and reservoir properties. Here we use borehole and 3D seismic reflection data to estimate stress orientations and magnitudes, fault geometries and slip tendency in the southern Taranaki Basin, New Zealand. Late Cenozoic normal faults in the basin range in strike from E-W to NE-SW and are associated with stress changes from basin to borehole scales. The Maui and Maari-Manaia regions, part of the eastern mobile belt, show a strike-slip/normal stress regime (SHmax ≥ Sv > Shmin). The Tui region, part of the western stable platform, shows a normal stress regime (Sv > SHmax > Shmin). Both regions have a mean SHmax azimuth of ENE-WSW. Although the southern Taranaki basin is undergoing active deformation at plate tectonic scales, the stress magnitudes appear insufficiently high to reactivate the faults assuming a classic coefficient of friction. SHmax azimuths and SHmax:Sv magnitude ratios vary locally between boreholes and with depth. A borehole that intersects an inactive seismic-scale fault and borehole-scale faults over a 150-m interval shows SHmax to rotate by up to 30° proximal to the faults, which are favourably orientated for slip in both strike-slip and normal regimes. The small borehole-scale faults may, however, be active within the inactive seismic scale fault's damage zone. We highlight changes of slip tendency along faults resulting from local variations in the stress field and non-planar fault geometries that could not be resolved using only seismic reflection data and regional stress tensor. In the Taranaki Basin additional sub-seismic fault mapping, stress information and mechanical rock property testing are required to realise the potential of stress-based prediction of along-fault permeability and fluid migration

Fluoride-containing bioactive glasses: Effect of glass design and structure on degradation, pH and apatite formation in simulated body fluid

NOTICE: this is the author’s version of a work that was accepted for publication in Acta Biomaterialia. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Acta Biomaterialia, [VOL 6, ISSUE 8, (2010)] DOI: 10.1016/j.actbio.2010.01.04

Damaged beyond repair? Characterising the damage zone of a fault late in its interseismic cycle, the Alpine Fault, New Zealand

X-ray computed tomography (CT) scans of drill-core, recovered from the first phase of the Deep Fault Drilling Project (DFDP-1) through New Zealand\u27s Alpine Fault, provide an excellent opportunity to study the damage zone of a plate-bounding continental scale fault, late in its interseismic cycle. Documentation of the intermediate-macro scale damage zone structures observed in the CT images show that there is no increase in the density of these structures towards the fault\u27s principal slip zones (PSZs), at least within the interval sampled, which is 30 m above and below the PSZs. This is in agreement with independent analysis using borehole televiewer data. Instead, we conclude the density of damage zone structures to correspond to lithology. We find that 72% of fractures are fully healed, by a combination of clays, calcite and quartz, with an additional 24% partially healed. This fracture healing is consistent with the Alpine Fault\u27s late interseismic state, and the fact that the interval of damage zone sampled coincides with an alteration zone, an interval of extensive fluid-rock interaction. These fractures do not impose a reduction of P-wave velocity, as measured by wireline methods. Outside the alteration zone there is indirect evidence of less extensive fracture healing.DFDP-1 was funded by: GNS Science; Victoria University of Wellington; the University of Otago; the University of Auckland; the University of Canterbury; Deutsche Forschungsgemeinschaft and the University of Bremen; Natural Environment Research Council grants NE/J024449/1, NE/G524160/1 and NE/H012486/1 and the University Of Liverpool; and the Marsden Fund of the Royal Society of New Zealand.2018-07-2

Structural and spatially-resolved studies on the hardening of a commercial resin-modified glass-ionomer cement

A commercial photopolymerizable resinmodified glass-ionomer (Fuji II LC) was studied using a variety of nuclear magnetic resonance (NMR) techniques. H and F stray-field imaging (STRAFI) enabled to follow the acid–base reaction kinetics in self-cured (SC) samples. Gelation and maturation processes with 25 min and 40 h average time constants, respectively, were distinguished. In self- & photo-cured (SPC) samples, two processes were also observed, which occurred with 2 s and 47 s average time constants. H, Al and Si magic angle spinning (MAS) NMR, C cross-polarization (CP)/MAS NMR and 27Al multiple quanta (MQ)MAS NMR spectroscopy were used to obtain structural information on the glass and cements that were either SC or SPC. The presence of methacrylate groups was identified in the solid component. Unreacted hydroxyl ethylmethacrylate (HEMA) was detected in self-cured cement. Al data showed that approximately 28% and 20% of Al is leached out from glass particles in SC and SPC samples, respectively. The upfield shift detected in 25Si MAS NMR spectra of the cements is consistent with a decrease in the number of Al species in the second coordination sphere of the silicon structures. Scanning electron microscopy (SEM) showed existence of 3D shrinkage of the cement matrix in photo-cured cements.(undefined