Chelation of cadmium ions by phytochelatin synthase: role of the cysteine-rich C-terminal.

The interactions between Cd(2+) and the C-terminal region of phytochelatin (PC) synthase using recombinant wild-type and mutant PC synthase were studied. We show that site-directed mutagenesis of Cys residues at C(358)C(359)XXXC(363)XXC(366) motif decreases the number of Cd(2+) and other heavy metal ions interacting with the enzyme, and that the motif binds the metals discriminatingly. The optimum binding ratio of PC synthase to Cd(2+) was also determined. The findings indicate that Cys exists as a free SH residue and that it is involved in the regulation of PC enzyme activity by transferring the metals into closer proximity with the catalytic domain. These results are important in understanding heavy metal detoxification mechanisms in higher plants, a step towards phytoremediated-applications.     

Characterization of NIES CRM No. 23 Tea Leaves II for the determination of multielements

A candidate environmental certified reference material (CRM) for the determination of multielements in tea leaves and materials of similar matrix, NIES CRM No. 23 Tea Leaves II, has been developed and characterized by the National Institute for Environmental Studies (NIES), Japan. The origin of the material was tea leaves, which were ground, sieved through a 106-μm mesh, homogenized, and then subdivided into amber glass bottles. The results of homogeneity and stability tests indicated that the material was sufficiently homogeneous and stable for use as a reference material. The property values of the material were statistically determined based on chemical analyses by a network of laboratories using a wide range of methods. Sixteen laboratories participated in the characterization, and nine certified values and five reference values were obtained. These property values of the candidate CRM, which are expressed as mass fractions, were close to the median and/or mean values of the mass fractions of elements in various tea products. The candidate CRM is appropriate for use in analytical quality control and in the evaluation of methods used in the analysis of tea and materials of similar matrix.     

A new biisoflavonoid from the roots of Erythrina variegata

A new biisoflavonoid, biseryvarin A (1a), together with two known compounds were isolated from the roots of Erythrina variegata. The structure of biseryvarin A was established on the basis of spectroscopic evidence. Biseryvarin A is the first dimeric isoflavonoid possessing isoprenoid groups from the genus Erythrina. Biseryvarin A showed low activity against methicillin-resistant Staphylococcus aureus (MRSA).     

An analysis of Y2O3:Eu thin films for thermographic phosphor applications

A comparative study of the luminescent properties of Y₂O₃:Eu³⁺ phosphor powders and thin films sputtered from targets prepared from combustion synthesized powders is reported. Thin films of (Y_0.96Eu_0.04)₂O₃ were deposited on silicon substrates. Films deposited at 600 °C had both monoclinic and cubic phases of Y₂O₃, which developed to an oriented cubic phase after annealing. Films and powders showed a linear dependence of the intensity of the ⁵D₇→⁷F₂ (611 nm) transition with temperature in the range 26-660 °C with an average rate of change of 1.8×10⁻⁴ °C⁻¹. The rate of change appears to be dependent on the Eu³⁺ concentration. This work shows that these thin films can be used as thermographic phosphors for remote temperature measurements.     

Initial step of anthracene‐sensitized photoacid generation from diphenyliodonium hexafluorophosphate in an epoxy matrix studied by steady‐state and laser‐flash photolyses

The anthracene‐sensitized photodecomposition of diphenyliodonium hexafluorophosphate was studied in an epoxy matrix. From steady‐state photolysis, the generation of protons, which are considered to be the actual initiators of the polymerization of epoxides, was confirmed. In addition, 9‐phenylanthracene was detected as a main product from anthracene. From time‐resolved laser‐flash photolysis, a broad absorption band with a peak at about 500 nm was observed that was thought to be due to the precursor of 9‐phenylanthracene. On the basis of these results, we propose electron transfer from anthracene in the excited singlet state to the diphenyliodonium cation as the initial step of photoacid generation. This process is followed by fast chemical reactions, which generate 9‐phenylanthracene and protons, and back electron transfer from the diphenyliodine radical to the anthracene cation radical. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2937–2946, 2001     

Difference thresholds for vibration of the foot: Dependence on frequency and magnitude of vibration

The smallest change in vibration intensity for the change to be perceptible (i.e. intensity difference threshold) has not previously been reported for vibration of the foot. This study investigated the influence of vibration magnitude and vibration frequency on intensity difference thresholds for the perception of vertical sinusoidal vibration of the foot. It was hypothesised that relative intensity difference thresholds (i.e. Weber fractions) for 16-Hz vibration mediated by the non-Pacinian I (NPI) channel would differ from relative intensity difference thresholds for 125-Hz vibration mediated by the Pacinian (P) channel. Absolute thresholds, difference thresholds, and the locations of vibration sensation caused by vertical vibration of the right foot were determined for 12 subjects using the up-down-transformed-response method together with the three-down-one-up rule. The difference thresholds and locations of sensation were obtained at six reference magnitudes (at 6, 9, 12, 18, 24, 30 dB above absolute threshold—i.e. sensation levels, SL). For 16-Hz vibration, the median relative difference thresholds were not significantly dependent on vibration magnitude and were in the range 0.19 (at 30 dB SL) to 0.27 (at 9 dB SL). For 125-Hz vibration, the median relative difference thresholds varied between 0.17 (at 9 dB SL) and 0.34 (at 30 dB SL), with difference thresholds from 6 to 12 dB SL significantly less than those from 18 to 30 dB SL. At vibration magnitudes slightly in excess of absolute thresholds (i.e. 6-12 dB SL) there were no significant differences between Weber fractions obtained from the P channel (at 125 Hz) and the NPI channel (at 16 Hz). At 24 and 30 dB SL, the 125-Hz Weber fractions were significantly greater than the 16-Hz Weber fractions. Differences in the 125-Hz Weber fractions may have been caused by a reduction in the discriminability of the P channel at high levels of excitation, resulting in one or more NP channel mediating the difference thresholds at magnitudes greater than 18 dB SL. At high magnitudes, a change of channel mediating the Weber fractions may have been responsible for different Weber fractions with 16- and 125-Hz vibration.     

Synthesis and properties of high‐molecular‐weight stereo di‐block polylactides with nonequivalent D/L ratios

Di‐stereoblock polylactides (di‐sb‐PLA: PLLA‐b‐PDLA) having high molecular weight (M_n > 100 kDa) were successfully synthesized by two‐step ring‐opening polymerization (ROP) of L ‐ and D ‐lactides using tin(2‐ethylhexanoate) as a catalyst. By optimizing the polymerization conditions, the block sequences were well regulated at non‐equivalent feed ratios of PLLA and PDLA. This synthetic method consisted of three stages: (1) polymerization of either L ‐ or D ‐lactide to obtain a PLLA or PDLA prepolymer with a molecular weight less than 50 kDa, (2) purification of the obtained prepolymer to remove residual lactide, and (3) polymerization of the enantiomeric lactide in the presence of the purified prepolymer. Their ¹³C and ³¹P NMR spectra of the resultant di‐sb‐PLAs strongly supported their di‐stereo block structure. These di‐sb‐PLAs, having weight‐average molecular weights higher than 150 kDa, were fabricated into polymer films by solution casting and showed exclusive stereocomplexation. The thermomechanical analysis of the films revealed that their heat deformation temperature was limited probably because of their low crystallinity owing to the non‐equivalent PLLA/PDLA ratio. The blend systems of the di‐sb‐PLAs having complementary stereo‐sequences (the one with a long PLLA block and the other with long PDLA block) were also prepared and characterized to enhance the sc crystallinity. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 794–801, 2010     

Synthesis of well‐defined and end‐polymerizable star‐shaped polysulfides and their application to negative photoresist

Various star‐shaped poly(phenoxy propylene sulfide)s (PPSs) bearing curable end groups were synthesized by the functionalization of the propagating ends of star‐shaped poly(PPS) with various electrophilies. The functionalization with chloromethyl styrene proceeded quantitatively, and afforded polymers with M_n almost agreed with theoretical value and narrow M_w/M_n. The photocuring conditions were optimized, and the addition of 10 wt % of poly(ethylene glycol) diacrylate was effective to attain sufficient crosslinking. The photocuring reaction of the end‐functionalized poly(PPS) films cast on silicon wafers was conducted by UV irradiation. The cured poly (PPS)s became insoluble in THF, supporting the sufficient crosslinking. Developing of a cured polymer yielded a negative photoresist pattern. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010