Structural characterization of ionomer glasses by multinuclear solid state MAS-NMR spectroscopy

In the present study we report the results of ²⁹Si, ²⁷Al, ³¹P and ¹⁹F magic angle spinning nuclear magnetic resonance spectroscopy (MAS-NMR) of 4.5SiO₂-3Al₂O₃-1.5P₂O₅-(5−z)CaO-zCaF₂ glasses with z = 0-3 to elucidate the effect of fluoride content on the glass structure. The ²⁹Si MAS-NMR spectra gave a chemical shift of about −90 ppm corresponding to Q³(3Al) and Q⁴(3Al). The ²⁷Al MAS-NMR showed a large broad central peak around 50 ppm, which is assigned to four-coordinated Al linked via oxygen to P. A shoulder around 30 ppm and a small peak at about 0 to −10 ppm appeared in the ²⁷Al MAS-NMR spectra of the glasses on increasing the fluoride content assigned to five-coordinated and six-coordinated Al species, respectively. The ³¹P MAS-NMR spectra indicated the presence of Al-O-P bonds. The ³¹P chemical shift decreased with increasing fluoride content as a result of calcium being complexed with fluoride. This resulted in a reduction of the number of available cations to charge balance non bridging oxygens in phosphorus and an increase in the number of Al-O-P bonds being formed, instead. The ¹⁹F spectra indicated the presence of Al-F-Ca(n) and F-Ca(n) species in all the glasses containing fluoride as well as an additional Si-F-Ca(n) species in the glasses with higher fluoride content.     

Cytosolic Cysteine Synthase Switch Cysteine and Mimosine Production in <Emphasis Type="Italic">Leucaena leucocephala</Emphasis>

In higher plants, multiple copies of the cysteine synthase gene are present for cysteine biosynthesis. Some of these genes also have the potential to produce various kinds of β-substitute alanine. In the present study, we cloned a 1275-bp cDNA for cytosolic O-acetylserine(thiol)lyase (cysteine synthase) (Cy-OASTL) from Leucaena leucocephala. The purified protein product showed a dual function of cysteine and mimosine synthesis. Kinetics studies showed pH optima of 7.5 and 8.0, while temperature optima of 40 and 35 °C, respectively, for cysteine and mimosine synthesis. The kinetic parameters such as apparent K_m, k_cat were determined for both cysteine and mimosine synthesis with substrates O-acetylserine (OAS) and Na₂S or 3-hydroxy-4-pyridone (3H4P). From the in vitro results with the common substrate OAS, the apparent k_cat for Cys production is over sixfold higher than mimosine synthesis and the apparent K_m is 3.7 times lower, suggesting Cys synthesis is the favored pathway.     

Poecillastrin E,F, and G,cytotoxic chondropsin-type macrolides from a marine sponge Poecillastra sp.

Poecillastrin E (1), F (2), and G (3) were isolated from a marine sponge Poecillastra sp. as the cytotoxic constituents. Their planar structures were determined by analyzing the MS and NMR spectra. They are closely related to the known poecillastrin C (4). The absolute configuration of the β-hydroxyaspartic acid (OHAsp) residue was determined to be D-threo by Marfey's analysis of the hydrolysate. The mode of lactone ring formation of OHAsp residue in 1–3 was determined by selective reduction of the ester linkage followed by acid hydrolysis.     

Solvent effect on conical intersections in excited-state 9H-adenine: radiationless decay mechanism in polar solvent

The ground- and excited-state free energy minima and the conical intersections among these states of 9H-adenine in aqueous and acetonitrile solutions are studied theoretically to elucidate the mechanism of radiationless decay. We employ the recently proposed linear-response free energy (LRFE) to locate the energy minima and conical intersections in solution. The LRFE is calculated by using the reference interaction site model self-consistent field method. The geometry optimizations are carried out at the complete active space self-consistent field level, and the dynamic electron correlation energies are estimated by the multireference M?ller-Plesset method. We find that the conical intersection between the (1)L(a) and (1)L(b) states in aqueous solution occurs at a wide area of the free energy surface, indicating a strong vibronic coupling between them. On the other hand, the (1)npi(*) state is largely blue-shifted at planar geometries in solution, which suggests that the nonadiabatic transition to this state is suppressed. The importance of the (1)pisigma(*) channel is also examined in both the gas phase and solution. Based on the free energy characteristics obtained by the calculations, we intend to explain the experimental observations that the excited state of 9H-adenine decays monoexponentially with shorter lifetimes in polar solvents than that in the gas phase.     

Diffusion-weighted echo-planar imaging of the head and neck using 3-T MRI: Investigation into the usefulness of liquid perfluorocarbon pads and choice of optimal fat suppression method

Purpose

To investigate whether image quality can be improved using liquid perfluorocarbon pads (Sat Pad) and clarify the optimal fat-suppression method among chemical shift selective (CHESS), water excitation (WEX), and short TI inversion recovery (STIR) methods in diffusion-weighted imaging (DWI) of the head and neck using 3-T magnetic resonance imaging. Correlations between results of visual inspection and quantitative analysis were also examined.

Material and Methods

This study was approved by our Institutional Review Board and informed consent was waived. DWI was performed on 25 subjects with/without Sat Pad and using three fat-suppression methods (6 patterns). Image quality was evaluated visually (4-point scales and lesion-depiction capability) and by quantitative analysis (signal-to-noise ratio (SNR) and contrast-to-noise ratio (CNR)). Two-way repeated-measures analysis of variance (ANOVA) was used to detect significant differences in scores of visual evaluation, SNR, and CNR.

Results

Mean visual evaluation scores were significantly higher with Sat Pad using STIR than without Sat Pad for all fat-suppression methods (P < 0.05). DWI with Sat Pad using STIR tended to be useful for depicting lesions. DWI using STIR showed reduced W-SNR (W: whole area of depicted structure) and CNR (between semispinalis capitis muscle and subcutaneous fat) due to fewer artifacts and uniform fat suppression.

Conclusion

Combining Sat Pad with STIR provides good image quality for visual inspections. When numerous artifacts are present and fat suppression is insufficient, higher SNR and CNR do not always provide good diagnostic image quality.     

Cervical spondylosis: Evaluation of microstructural changes in spinal cord white matter and gray matter by diffusional kurtosis imaging

Introduction

We investigated microstructural changes in the spinal cord, separately for white matter and gray matter, in patients with cervical spondylosis by using diffusional kurtosis imaging (DKI).

Methods

We studied 13 consecutive patients with cervical myelopathy (15 affected sides and 11 unaffected sides). After conventional magnetic resonance (MR) imaging, DKI data were acquired by using a 3 T MR imaging scanner. Values for fractional anisotropy (FA), apparent diffusion coefficient (ADC), and mean diffusional kurtosis (MK) were calculated and compared between unaffected and affected spinal cords, separately for white matter and gray matter.

Results

Tract-specific analysis of white matter in the lateral funiculus showed no statistical differences between the affected and unaffected sides. In gray matter, only MK was significantly lower in the affected spinal cords than in unaffected spinal cords (0.60 ± 0.18 vs. 0.73 ± 0.13, P = 0.0005, Wilcoxon’s signed rank test).

Conclusions

MK values in the spinal cord may reflect microstructural changes and gray matter damage and can potentially provide more information beyond that obtained with conventional diffusion metrics.     

Point spread function measurement of an X‐ray beam focused by a multilayer zone plate with narrow annular aperture

The experimental procedure for obtaining the point spread function (PSF) of a focusing beam generated using an X‐ray multilayer zone plate (MZP) with a narrow annular aperture has been developed. It was possible to reconstruct the PSF by applying the tomographic process to the measured dataset consisting of line spread functions (LSFs) in every radial direction on the focal plane. The LSFs were measured by a knife‐edge scanning method of detecting scattered intensity. In the experimental work, quasi‐monochromatic undulator radiation with a first harmonic energy of 20 keV was directly focused without a monochromator by the MZP, and the PSF was measured using this procedure. As a result, a near diffraction‐limited focused beam size of 46 nm full width at half‐maximum was obtained.     

Periodic nanostructures self-formed on silicon and silicon carbide by femtosecond laser irradiation

Laser-induced periodic surface structures (LIPSS) were formed on Si and SiC surfaces by irradiations with femtosecond laser pulses in air. Different kinds of self-organized structures appeared on Si and SiC at laser fluences slightly higher than the damage threshold, which was measured by confocal laser scanning microscope. The characteristic spatial periodicity of every observed structure was estimated reading the peak values of the 2D Fourier transform power spectra obtained from SEM images. The evolution of the spatial periodicity was finally studied with respect to both the laser fluence and the number of laser pulses. As already observed for metals, the behavior of the spatial periodicity on laser fluence can be related to the parametric decay of laser light into surface plasma waves. Our results suggest a wide applicability of the parametric decay model on different materials, making the model a useful tool in view of different applications of LIPSS.