Synthesis and structure of dawson polyoxometalate-based, multifunctional, inorganic-organic hybrid compounds: organogermyl complexes with one terminal functional group and organosilyl analogues with two terminal functional groups

Four novel multifunctional polyoxometalate (POM)-based inorganic-organic hybrid compounds, [α(2)-P(2)W(17)O(61){(RGe)}](7-) (Ge-1, R(1) = HOOC(CH(2))(2(-)) and Ge-2, R(2) = H(2)C═CHCH(2(-))) and [α(2)-P(2)W(17)O(61){(RSi)(2)O}](6-) (Si-1, R(1) and Si-2, R(2)), were prepared by incorporating organic chains having terminal functional groups (carboxylic acid and allyl groups) into monolacunary site of Dawson polyoxoanion [α(2)-P(2)W(17)O(61)](10-). In these POMs, new modification of the terminal functional groups was attained by introducing organogermyl and organosilyl groups. Dimethylammonium salts of the organogermyl complexes, (Me(2)NH(2))(7)[α(2)-P(2)W(17)O(61)(R(1)Ge)]·H(2)O MeN-Ge-1 and (Me(2)NH(2))(7)[α(2)-P(2)W(17)O(61)(R(2)Ge)]·4H(2)O MeN-Ge-2, were obtained as analytically pure crystals, in 22.8% and 55.3% yields, respectively, by stoichiometric reactions of [α(2)-P(2)W(17)O(61)](10-) with separately prepared Cl(3)GeC(2)H(4)COOH in water, and H(2)C═CHCH(2)GeCl(3) in a solvent mixture of water/acetonitrile. Synthesis and X-ray structure analysis of the Dawson POM-based organogermyl complexes were first successful. Dimethylammonium salts of the corresponding organosilyl complexes, (Me(2)NH(2))(6)[α(2)-P(2)W(17)O(61){(R(1)Si)(2)O}]·4H(2)O MeN-Si-1 and (Me(2)NH(2))(6)[α(2)-P(2)W(17)O(61){(R(2)Si)(2)O}]·6H(2)O MeN-Si-2, were also obtained as analytically pure crystalline crystals, in 17.1% and 63.5% yields, respectively, by stoichiometric reactions of [α(2)-P(2)W(17)O(61)](10-) with NaOOC(CH(2))(2)Si(OH)(2)(ONa) and H(2)C═CHCH(2)Si(OEt)(3). These complexes were characterized by elemental analysis, thermogravimetric and differential thermal analyses (TG/DTA), FTIR, solid-state ((31)P) and solution ((31)P, (1)H, and (13)C) NMR, and X-ray crystallography.     

The LHCf experiment at LHC

The LHCf experiment will be installed in 2007 on the LHC collider in the forward direction at ±140m from the ATLAS interaction point. The purpose of LHCf is to precisely measure the pion production cross section near zero degrees through the measurement of the photons produced in neutral pion decay. This measurement is crucial for the simulation of the showers induced in the atmosphere by very high energy cosmic rays; the 14 TeV energy available in the center of mass frame corresponds in fact to an equivalent energy of 10¹⁷ eV in the laboratory system. The paper focus on the proposed experiment and on the physics results that we expect from it.     

Preparation of telechelic oligomers by thermal degradation of propylene copolymers

The reactive end groups of nonvolatile oligomers obtained by controlled thermal degradation of poly(propylene-ran-ethylene) and poly(propylene-ran-1-butene) were determined by ¹H and ¹³C NMR spectroscopy. The molar ratio of unsaturated to saturated end groups was found to be about 9:1. The average number of unsaturated end groups per molecule was between 1.6 and 1.8, indicating that 60–80 mol% of the oligomer molecules were telechelic, having two terminal unsaturated end groups. These oligomers had a lower polydispersity than the raw material, despite their lower molecular weight and melting temperature. Although the end groups resulting from each monomer unit could be detected by ¹³C NMR, the end group composition differed from that of the main chains of the raw materials. The end group composition was satisfactorily explained by the differences in bond dissociation energy and activation energy of elementary reactions that occurred during thermal degradation, based on the monomer composition of the raw materials.     

Studies on thermal degradation of acrylonitrile–butadiene–styrene copolymer (ABS-Br) containing brominated flame retardant

The thermal degradation of acrylonitrile-butadiene-styrene copolymer (ABS-Br; 10 g) containing brominated flame retardant (Br: 9.59 wt.%) was carried out at 450 °C using a semi batch operation using two different temperature programs. The heating rate was found to affect the quality of the degradation oil and yield of products (liquid, gas and residue). Data on the effect of the temperature program on the accumulation of liquid products was presented. It was found that the majority of the bromine was concentrated in the carbon residue and while majority of the nitrogen accumulates in the liquid products irrespective of degradation mode. The use of a one step constant heating rate process (I) produced a higher liquid yield (39%), than a two step process (29%). Differences were also noted in the Br and N contained in the liquids produced by the two processes.     

Two-dimensional optoelectronic devices for future optical switching and information processing

Recent progress is reviewed in surface-normal optoelectronic devices primarily for use in optical switching and information processing. A type of optoelectronic integrated circuit (OEIC), the surface-normal two-dimensional array, is fabricated using these devices. This improves on first-generation OEICs by featuring large-scale integration in a small area, which results in a higher production yield. It also has structures which can easily be integrated with electronic circuits and can meet multichannel requirements. This approach supports optoelectronic progress towards optical information processing.     

Multi-Terabit Long-Haul Transmission System Utilizing Distributed Raman Amplification Technologies

Here we summarize multi-terabit long-haul transmission experiment and distributed Raman amplification (DRA) technologies. As well, we investigate the configuration of dispersion-managed fibers for the DRA-based system from the viewpoint of the fiber non-linear effect and required pumping power.     

Photoluminescence characteristics of nitrogen atomic-layer-doped GaAs grown by MOVPE

Nitrogen atomic-layer-doped and uniformly doped GaAs were grown by MOVPE using dimethylhydrazine on a (001) plane. They showed several sharp photoluminescence lines with a full width at half maximum less than 1 meV at 8 K. Compared with uniformly doped GaAs, the photoluminescence intensity of the nitrogen-related line at the longest wavelength is enhanced in nitrogen atomic-layer-doped GaAs, suggesting that it is easier to form nitrogen pairs during atomic layer doping. To investigate the sharp nitrogen-related lines, we also grew GaAs with double atomic-layer-doped planes and varied the distance between the two planes. When the two planes are brought close to 1 nm, two new lines, NN_C and NN_D, appear between the two nitrogen-related lines, NN_A and NN_B, observed in a single nitrogen atomic-layer-doped GaAs. The NN_C and NN_D lines are also observed in uniformly doped GaAs. Therefore, NN_A and NN_B originate from excitons bound to pairs of nitrogen atoms, both of which are in the (001) plane, while NN_C and NN_D originate from those bound to pairs of nitrogen atoms, of which pairing directions are not included in the (001) plane. From the photoluminescence characteristics, distances between nitrogen atoms of a pair are estimated for each line.     

Bayesian analysis of lymphatic spreading patterns in cancer of the thoracic esophagus

For the treatment of patients with cancer of the thoracic esophagus, lymphatic spreading is one important factor to infer how advanced their cancer is. We introduced a one-dimensional scale based on lymphatic spreading patterns, the stage of cancer, to express how advanced their cancer is, and we proposed a method to infer each patient's stage from his lymphatic spreading pattern by applying a Bayesian model. Our Bayesian model was built based on the assumption that lymphatic spreading in cancer could be explained as what was brought about by the advance of stage. In the modeling, we introduced the probability of what stage each patient was in as a prior distribution. We also introduced distribution functions of Weibull distributions to express the relation between the advance of stage and the increase of the probability of metastasis. Our model was applied to the data of nodal involvement obtained from 103 patients with cancer of the thoracic esophagus and the parameters were estimated with the maximum likelihood method. AIC was used to check that the data had enough information to be divided into the stages of a clinically reasonable number. With the estimated parameters, we inferred the probability of metastasis to each lymph node in each stage and calculated by Bayes' theorem with 31 new patients the probability of what stage they were in. The results well represented some characteristics of the lymphatic spreading and suggested the appropriateness of our approach.The present study was carried out under the ISM Cooperative Research Program (91-ISM·CRP-18).