Aromatization of enamines promoted by a stoichiometric amount of palladium(II) salts: a novel method for the synthesis of aromatic amines.

Enamines (1a-r) prepared from cyclohexanones, cyclohexane-1,3-diones, or tetralones led to arylamines (2a-r) in one pot when treated with a stoichiometric amount of palladium salts [PdCl2-(MeCN)2] in acetonitrile in the presence of triethylamine at room temperature or at elevated temperature, in some cases for 5 min to 2 h. The initial electrophilic attack of palladium chloride on the beta-carbon of the enamines led to a sigma-palladium species (8) which triggered a series of reactions (-->9-->10-->11-->12) destined for aromatization to give 2a-r in good yields. The intervention of such a sigma-palladium species has been attested by a trapping experiment. On the basis of this reaction mechanism, we have developed another new process capable of transforming acyclic compounds having 6-en-2-one frameworks (16, 23, 25) to arylamines (2s-u) when their enamines were treated under the similar conditions as above, featuring again the formation of sigma-palladium species such as 8 as the initial key intermediate.     

彩色胶片与数字照相的成像效率分析及对其未来的预测

本文作者曾经通过评估成像效率的当前状态和理论极限之间的差距以及分析产生此差距的原因预测过卤化银照相材料的未来发展.本文描述了采用上述的方法来评估和分析彩色胶片与数字照相的现状.经预测在未来前者成像效率的改进余地会远大于后者.     

Postgel properties in the statistical crosslinking of heterochains. II. Free‐radical crosslinking copolymerization

The heterochain crosslinking theory is applied to postgel behavior in the free‐radical crosslinking copolymerization of vinyl and divinyl monomers. In this context, the crosslinked polymer formation can be viewed as a system in which the primary chains formed at different times are combined in accordance with the statistical chain‐connection rule governed by the chemical reaction kinetics. Because the primary chains are formed consecutively, the number of chain types N must be extrapolated to infinity, N → ∞. Practically, such extrapolation can be conducted with the calculated values for only three different N values. The analytical expressions for the weight fraction and average molecular weights of the sol fraction are derived for the general primary chain length distribution function in free‐radical polymerization. Illustrative calculations show that the obtained results agree with those from the Monte Carlo method, and that the postgel properties in free‐radical crosslinking copolymerization systems could be significantly different from those in randomly crosslinked systems. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2342–2350, 2000     

Reaction of 2-aminobenzamide analogs and 2-aminothiophenol with ethyl 3-ethoxymethylene-2,4-dioxovalerate. Synthesis of pyrrolo[1,2-α]quinazoline and pyrrolo[1,2-a]benzothiazoline derivatives

The reaction of ethyl 3-ethoymethylene-2,4-dioxovalerate (EMDV) ( 1 ) with 2-aminobenzamide ( 2 ), 2-aminobenzthioamide ( 3 ), 2-aminobenzmethylamide ( 4 ) and 3-amino-2-methyl- or phenylpyrazole-4-carbox-amides ( 6 and 7 ) produced ethyl 3-aminomethylene-2,4-dioxovalerates ( 10, 15, 16, 18 and 19 ), which led to pyrrolo[1,2-a]quinazoline-1,5-diones ( 11, 22 and 23 ) and pyrrolo[1,2-a]pyrazolo[4,3-e]pyrimidine-1,5-diones ( 24 and 25 ) under the acidic condition, respectively. Analogously, 2-aminothiophenol reacted with 1 to give 21 , which was subsequently derived to pyrrolo[1,2-a]benzothiazolin-l-one ( 26 ) under the neutral condition. Furthermore, we prepared the heterocyclic steroidal molecules ( 41, 43, 45, 47, 49 and 51 ) by condensation of 11 and 26 with hydrazine, methylhydrazine and phenylhydrazine.     

Flow-injection determination of L-histidine with an immobilized histidine oxidase from Brevibacillus borstelensis KAIT-B-022 and chemiluminescence detection.

A chemiluminometric flow injection analytical system for the quantitation of L-histidine is described. Histidine oxidase (EC 1.4.3.-) from Brevibacillus borstelensis KAIT-B-022 was immobilized on tresylated poly(vinyl alcohol) beads and packed into a stainless-steel column. The hydrogen peroxide produced was detected chemiluminometrically by a flowthrough sensor containing immobilized peroxidase (EC 1.1 1.1.7). The maximum sample throughput was 10 h(-1). The calibration graph was linear from 0.05 to 5 mM; the detection limit (signal to noise ratio = 3) was 0.01 mM. The activity of immobilized histidine oxidase reduced to 65% of the initial value after 350 injections. The system was applied to the determination of L-histidine in fish meat, such as salmon, tunny, bonito, and mackerel.     

740 Gbit/s (37 x 20 Gbit/s) DWDM Transmission Experiment Using Er3+-Doped Tellurite Fiber Amplifiers and Distributed Raman Amplification

We demonstrate 740 Gbit/s (37 × 20 Gbit/s) DWDM recirculating transmission experiment with 59 nm continuous bandwidth over 300 km by employing Er3+-doped tellurite fiber amplifiers. The use of Raman amplification is effective to increase the transmission bandwidth.     

Photoluminescence behaviors of single CdSe/ZnS/TOPO nanocrystals: Adsorption effects of water molecules onto nanocrystal surfaces

We report here the distinctive modifications of photoluminescence (PL) behaviors in single CdSe/ZnS/TOPO nanocrystals depending on their environments. Long-time traces of PL intensity from single nanocrystals have been obtained in both vacuum and a wet nitrogen atmosphere. While all of the nanocrystals in both environments exhibit PL blinking behaviors, i.e. on-off intermittency of PL intensity, as usual, some of the nanocrystals in the wet nitrogen atmosphere show significant increase in duration time of on-events. As for the duration time of blinking off-events, it is for the moment associated with the occasional events of carrier capturing at trap sites on or near the nanocrystal surfaces. We propose a model in which adsorbed water molecules at the trap sites on the nanocrystal surfaces transform them under light irradiation, which eventually decreases the occurrence of the trapping events due to their inactivation. It in turn increases the PL on-times. In addition to the drastic modification of the blinking profile, we also found that in the PL time traces some kinds of undulated behaviors, i.e. continuous and rather low frequency fluctuation of PL intensity, appear during each on-event in vacuum while they disappear totally in the wet nitrogen atmosphere. These results are also described on the basis of the inactivation model of the trap sites introduced above.     

Isolation of (E)-9,10-dihydroxy-2-decenoic acid from royal jelly and determination of the absolute configuration by chemical synthesis

(E)-9,10-Dihydroxy-2-decenoic acid 1 was isolated as a new compound from royal jelly. The planar structure was deduced by spectroscopic analyses, whereas the absolute configuration was established by chemical synthesis of both enantiomers of 1. The natural product was revealed to be ca. 3.5:1 mixture of (R)- and (S)-acids by comparison of 1 with authentic samples.     

Selective formation of a stable micro-peroxo ferric heme-Cu(II) complex from the corresponding micro-oxo Fe(III)-Cu(II) species with hydrogen peroxide

An oxo-bridged ferric heme-copper(II) complex, obtained by thermal transformation of the corresponding peroxo-bridged complex, was reacted with an equimolar amount of H2O2 to regenerate the micro-peroxo complex by a ligand exchange from oxo to peroxo, without the formation of a ferryl-oxo species or heme degradation as are observed in general ferric heme-H2O2 reactions.     

Terabit all-optical logic based on ultrafast two-dimensional transmission gating

Terabit all-optical complementary logic is proposed using two successive time slots to represent a unique logical status. An organic molecular thin film is used as an array of optically controlled optical switches. By utilizing the planar structure of the film and its ultrafast optical response, proof-of-principle fully optical NOT and AND logic operations were demonstrated with 400-fs interval pulses.