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A multilayered microfluidic chip used for vacuum membrane distillation is designed, fabricated and tested by rectification of a water-methanol mixture.

Hybrid multilayers of phthalocyanines (Pc) and titanium oxide (TiOx) have been effectively fabricated on the surfaces of quartz and indium-tin-oxide (ITO) according to the following layer-by-layer sequence; (i) the formation of a titanium butoxide layer (Ti(OBu)m) grafted onto the substrate surface by immersion of a substrate into a solution of Ti(OBu)4, (ii) hydrolysis of Ti(OBu)m to a TiOx layer with a Ti–OH surface, (iii) dipping of the treated substrate into a solution of Pc1–Pc3 bearing four or eight (triethoxysilyl)alkoxy substituents to form a Pc layer on the TiOx surface, presumably through Ti–O–Si bonding, (iv) hydrolysis of excess Si(OEt)3 groups in the Pc layer to form a silanol surface and (v) cyclic repetition of steps (i)–(iv). Atomic force microscopy (AFM) has shown that the multilayer surfaces are smooth, with surface roughnesses similar to that of a pristine substrate. The ratios of Ti atoms/Pc molecule for three different multilayers determined by X-ray photoelectron spectroscopy (XPS) were found to be roughly constant (3.8–4.3). For hole-only diodes of ITO/N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine/Au, it has been found that the surface modification of ITO with the hybrid multilayers of Pc1 causes remarkable current enhancements at low applied biases depending on the cycle number of the layer-by-layer deposition.

A versatile automated synthesis apparatus, equipped with a chemical artificial intelligence, was developed to prepare and isolate a wide variety of compounds. The apparatus was to the synthesis of substituted N-(carboxyalkyl)amino-acids. The apparatus [1,2] is composed of units for performing various tasks,for example reagent supply, reaction, purification and separation, each linked to a control system. All synthetic processes, including washing and drying of the apparatus after each synthetic run, were automatically performed from the mixing of the reactants to the isolation of the products as powders or crystals. The reaction of an amino-acid tertbutyl ester acetic acid salt with a 2-keto acid sodium salt produces an unstable intermediate, Schiff base, which is reduced with sodum cyanoborohydride to give a substituted N-(carboxyalkyl)aminoacid tert-butyl ester sodium salt. The equilibrium and the consecutive reactions were controlled by adding sodium cyanoborohydride using the artificial intelligence software, which contained novel kinetic equations [3] and substituent effects [4].Substitued N-(carboxyalkyl)amino-acid tert-butyl esters, 90 derivatives, were automatically synthesized using the computerassisted automated synthesis apparatus. The syntheses were performed unattended 24 hours a day, except for supplying the raw materials, reagents and solvents. The apparatus is extremely valuable for synthesizing many derivatives of a particular compound. The configurations of the products were determined by circular dichroism measurements.

Solid polymer electrolyte membrane has been used as electrolyte in polymer electrolyte fuel cells (PEFC) has high electrical conductivity. The hydrogen peroxide made by the reaction in a fuel cell may degrade the conductivity in PEFC. It is necessary to investigate the degradation behavior of the membrane in the environment where the hydrogen peroxide exists. The membrane that was immersed in hydrogen peroxide was used as a sample of each measurement. The measurement of the proton diffusion rate in the membrane was performed for the measurement of a proton conductivity. The current-voltage curve measurement was performed for the investigation of a fuel cell performance. The measurement of a proton diffusion rate applied to the degradation process in the membrane was effective to evaluate the conductivity in the fuel cell.

A heavy ion beam probe (HIBP) using a 3 MV tandem accelerator was installed in Large Helical Device (LHD). It is designed to measure the electrostatic potential in the core region directly. It is calibrated and can be used to measure the electrostatic potential profiles in LHD plasmas. The radial electric field (Er) obtained from the potential profiles measured using the HIBP agrees with that measured by charge exchange spectroscopy (CXS). Er predicted by the neoclassical theory is also compared to that measured using the HIBP, and is in good agreement with the experimental results in the core region.

In order to measure the potential in Large Helical Device (LHD), we have been developing a heavy ion beam probe (HIBP). For probing beam, gold beam is used, which is accelerated by a tandem accelerator up to the energy of 6 MeV. The experiments for calibration of beam orbit were done, and experimental results were compared with orbit calculations. The experimental results coincided fairly with the calculation results. After the calibration of the beam orbit, the potential in plasma was tried to measure with the HIBP. The experimental data showed positive potential in a neutral beam heating phase on the condition of ne ? 5 × 10^18 m^-3, and the increase of potential was observed when the additional electron cyclotron heating was applied to this plasma. The time constant for this increase was about a few tens ms, which was larger than a theoretical expectation. In the spatial position of sample volume, we might have an ambiguity in this experiment.

Le polymere amphiphile, azoaromatique est prepare par introduction d'un groupe azobenzene dans la chaine laterale de polymethacrylate d'hydroxyethyle

The syntheses of disodium 6-(2-phenyl-2-sulfoacetamido-1-14C) peniaillanate (IV) and 6-(2-isobutyl-β,γ- 3H2-sulfo-2-phenyl-acetamido-1-14C) penicillanic acid (XII) are described. The optically active D(-)-IV was obtained by the fractional crystallization of diastereoisomeric mixture which was prepared from phenylacetia acid-1-14C (I). The compound double labelled with 3H and 14C, XII, was synthesized by the reaction of trimethylsilyl 6-aminopenicillanate with 2-isobutyl-β,γ-3H2- sulfo-2-phenylacetyl chloride-1-14C (XI) which was prepared from isobutanol-2,3-3H2 and I. The overall radiochemical yields of XII, at the specific activities of 9 mCi (3H)/mmole and 2 mCi (14C)/mmole, were 34% yield based on isobutanol-2,3-3H2 and 17% yield based on I respeatively.

[N-methylene-3H]Thiamine 1-adamantyl trisulfide hydrochloride (VII) was synthesized. Both the γ-radiolysis of thiamine 1-adamantyl trisulfide hydrochloride (VIII) in ethanol and the self-radiolysis of VII in the crystalline state containing 17 molepercent of ethanol have been studied. G(-VII) in the crystalline state by the gross effects of self-irradiation was 3.4, and the four decomposition products were found. The self-radiolysis products yielded from VII in the crystalline state were the same as those products isolated from the γ-radiolysis of VIII in ethanolic solution and determined the structures as di-(1-adamantyl)tetrasulfide, 2-dihydro-3-(4-amino-2-methyl-5-pyrimidinylmethyl)-5-(1-adamantyl dithio)-3a-methylperhydrofuro[2,3-d]thiazole, 2-(1-hydroxyethyl)-3-(4-amino-2-methyl-5-pyrimidinyl-methyl)-5-(1-adamantyl dithio)-3a-methylperhydrofuro-[2,3-d]thiazole and thiamine chloride hydrochloride respectively.

A versatile automated apparatus, equipped with an artificial intelligence has been developed which may be used to prepare and isolate a wide variety of compounds. The prediction of the optimum reaction conditions and the reaction control in real time, are accomplished using novel kinetic equations and substituent effects in an artificial intelligence software which has already reported [1]. This paper deals with the design and construction of the fully automated system, and its application to the synthesis of a substituted N-(carboxyalkyl)amino acid. The apparatus is composed of units for perfoming various tasks, e.g. reagent supply, reaction, purification and separation, each linked to a control system. All synthetic processes including washing and drying of the apparatus after each synthetic run were automatically performed from the mixing of the reactants to the isolation of the products as powders with purities of greater than 98%. The automated apparatus has been able to run for 24 hours per day, and the average rate of synthesis of substituted N-(carboxyalkyl)amino acids has been three compounds daily. The apparatus is extremely valuable for synthesizing many derivatives of one particular compound structure. Even if the chemical yields are low under the optimum conditions, it is still possible to obtain a sufficient amount of the desired product by repetition of the reaction. Moreover it was possible to greatly reduce the manual involvement of the many syntheses which are a necessary part of pharmaceutical research.

The effect of regucalcin, a calcium-binding protein isolaetd from rat liver cytosol, on (Ca2+-Mg2+)-adenosine triphosphatase (ATPase) activity in the plasma membranes of rat liver was investigated. 125I-Regucalcin bound to the plasma membranes in the presence or absence of 0.1 mM Ca2+. Regucalcin (0.35 μM) increased the plasma membrane (Ca2+-Mg2+)-ATPase activity about 15% (p M), glucagon (10-6 and 10-5M) or norepinephrine (10-7-10 M), suggesting that the regucalcin effect is not linked to guanosine triphosphate (GTP)-binding protein in the plasma membranes. Vanadium (10 and 10 μM), which inhibits the phosphorylation of liver plasma membrane (Ca2+-Mg2+)-ATPase, decreased the enzyme activity about 20% (p

Polymeric adsorbents containing an azobenzene moiety as a ligand were prepared, and the photoinduced adsorption behavior of proteins to the adsorbent was studied. This method regulates by light the adsorption/desorption of proteins in hydrophobic chromatography. In the dark, the amount of protein adsorbed onto the adsorbent increased with increasing hydrophobicity of either adsorbent or protein. On irradiation with UV light, the amount of protein adsorbed decreased. Such a photoinduced change of the adsorption of protein was considered to be caused by the change of the hydrophobic interaction between the adsorbent and the protein due to the photoisomerization of the azobenzene moiety accompanying the polarity change of the adsorbent. It is also found that the desorption of protein was dependent on the balance of the hydrophobicity between the adsorbents and proteins. When column chromatography was carried out, the proteins were adsorbed in the dark and could be eluted after photoirradiation, with water as the single solvent. Furthermore, mixture of proteins could be separated by using a hydrophobic gradient column which was constituted by two polymeric adsorbents having different hydrophobicity.

A first synthesis of ascidiacyclamide, a cytotoxic cyclic peptide from ascidian, has been achieved through the cyclodimerization with diphenyl phosphorazidate(DPPA), which has unambiguously determined the absolute configuration of ascidiacyclamide as 1 .

Radiation-induced reaction of thiamine monochloride with di-1-adamantyl tetrasulfide gave two products, 3-(4-amino-2-methyl-5-pyrimidinylmethyl)-6a-(1-adamantyldithio)-3a-methylperhydrofuro[2,3-d]thiazole and 2-(1-hydroxymethyl)-3-(4-amino-2-methyl-5-pyrimidinylmethyl)-6a-(1-adamantyldithio)-3a-methylperhydrofuro[2,3-d]thiazole.

Total synthesis of ulithiacyclamide, a strong cytotoxic cyclic peptide from marine tunicates, has been achieved by the use of diphenyl phosphorazidate(DPPA) and diethyl phosphorocyanidate(DEPC). Two different cyclization processes were applied to the construction of this unique cyclic peptide having a disulfide bridge.

8-Chloro-6-phenyl-4H-s-triazolo [4,3-a] [1,4] benzodiazepine (D-40TA)-1-14C (V-14C) was synthesized by the reaction of formic acid-14C with 7-chloro-2-hydrazino-5-phenyl-3H-1, 4-benzodiazepine in the presence of N,N′-carbonylbis (2-methylimidazole). The overall radio-chemical yield from formic acid-14C was 57.8%.

To control the swelling of polymer membrane by photoirradiation amphiphilic azoaromatic polymer membranes were prepared and a photoinduced change in the swelling degree of water was investigated. The azobenzene moiety in the side chain of the polymer was isomerized from trans form to cis form by ultraviolet (UV) irradiation and reverse isomerization was found by visible light irradiation. The swelling degree of the polymer membrane for water in the dark was decreased by UV radiation, and when visible light irradiation was carried out in the polymer membrane the degree of swelling recovered to the original level. The swelling degree decreased with an increase in the mole fraction of the azobenzene moiety in the dark and under UV irradiation. The deswelling degree of the polymer membrane by UV irradiation also decreased with an increase in the mole fraction of the azobenzene moiety. This reversible change in the swelling degree was considered to be caused by the photoisomerization of the azobenzene moiety in the polymer membrane.

Der Bildungsmechanismus von 4-Amino-5-aminomethyl-2-methylpyrimidin (3) aus 3-Athoxy-2-(diathoxymethyl)propionitril (5) und Acetamidin wurde mittels markiertem 5, das die C ≡ 15N-, 14C ≡ N- bzw. die 14CH(OC2H5)2-Gruppe enthielt, untersucht. Das markierte 3 wurde einer Reihe von Abbaureaktionen unterworfen. Aus der Verteilung der Isotope ergibt sich, das der Stickstoff der C ≡ N-Gruppe in 3-Stellung oder in die 4-Aminogruppe von 3 mit einer Wahrscheinlichkeit von ca. 1 : 1 eingebaut wird. Der Kohlenstoff in 6-Stellung leitet sich aus HCO2R ab. Die Bildung von 3 verlauft wahrscheinlich auf den Wegen c und d. Mechanism of the Formation of 4-Amino-5-aminomethyl-2-methylpyrimidine from 2-(Diethoxymethyl)-3-ethoxypropionitrile and Acetamidine The mechanism of the formation of 4-amino-5-aminomethyl-2-methylpyrimidine (3) from 2-(diethoxymethyl)-3-ethoxypropionitrile (5) and acetamidine has been investigated by means of labelled compounds 5 which contained the C ≡ 15N, 14C ≡ N, and 14CH(OC2H5)2, respectively. The labelled 3 was subjected to a series of degradation reactions. From the distribution of the isotopes it has been proved as follows: The nitrogen of the C ≡ N group is incorporated either into the 3-position or into the amino group at the 4-position of 3 in a ratio of ca. 1 : 1. The carbon atom at 6-position originates from HCO2R. The formation of 3 probably proceeds through the routes c and d.

The photocurrents of the substituted anthracenes, 1, 5-diacetylanthracene (2), 1-acetylanthracene (3), 9-acetylanthracene (4), 1, 5-dichloroanthracene(5), 1, 5-diethylanthracene (6), 1, 5-dimethoxyanthracene (7), 9-cyanoanthracene (8) and anthracene (1), were measured by using their "surface-type" cells in nitrogen. The compounds of (1), (5), (6), (7)and (8) showed the photocurrent spectra which corresponded to the absorption spectra of their evaporated films (Fig.1). In the cases of (2) and (3), however, the anomalous photocurrent apPeared in the threshold region of their absorption spectra. Especially, the anomalous photocurrent of (2) became larger (Fig.2). The appearance of the anomalous photocurrent was characteristic of anthracenes having the acetyl group at 1- and/or 5-position. The magnitude of the photocurrents of the 1, 5-disubstituted anthracenes was similar to that of (1). On the other hand, the photocurrents of the monosubstituted anthracenes were smaller than that of (1). Among the monosubstituted anthracenes, the compound (4) showed no photocurrent under the same conditions. Contrary to the results obtained in the cases of phenazines, the photoconductivities of the anthracene derivatives became better in air.

It was found that benzenesulfinic acid reacted with N-substituted maleimides in aqueous ethanol to give sulfoneimides in good yields. The rate for the reaction was determined by the use of the neutralization titration, the effect of a substituent in N-substituted maleimides on the rate was studied, and the reaction route of benzenesulfinic acid with N-substituted maleimide was deduced.

The effect of γ irradiation on hydrated crystal of disodium α-sulfobenzylpenicillin (I) in solid state has been studied in relation to the radiation sterilization. From the decomposition products, at least two processes can be recognized during γ radiolysis of (I). One leads to CSO 3 Na scission, giving benzylpenicillin (III), and the second to hydrolysis of the β-lactam in (I), giving α-sulfobenzylpenicilloic acid (II). The studies show that radiation sterilization of (I) is feasible.

It was found that benzenesulfinic acid reacted with N-substituted maleimides in aqueous ethanol to give sulfoneimides in good yields. The rate for the reaction was determined by the use of the neutralization titration, the effect of a substituent in N-substituted maleimides on the rate was studied, and the reaction route of benzenesulfinic acid with N-substituted maleimide was deduced.

2019

Steady-state and time-resolved fluorescence behavior of 4-cyano-4‘-pentylbiphenyl (5CB) in polymer-dispersed liquid crystal (PDLC) films sandwiched between two quartz substrates was characterized by the surface-limited excitation (SLE) and through-film excitation (TFE) methods, which were used to discriminate the emissions from the interface layer with the substrate and from the interior domain. Although PDLC films showed both the monomer and excimer emissions of 5CB, SLE gave a substantially greater contribution of the former in the fluorescence than TFE. By contrast, a neat nematic film of 5CB showed exclusively the excimer emission independently of the excitation methods. Time-resolved analysis of the excimer emission from PDLC films revealed double-exponential decay profiles with shorter-lived (1.5−1.8 ns) and longer-lived (12−17 ns) components, in which the former is dominant for the excimer emission obtained by SLE, while the latter takes a major part for that obtained by TFE. By contrast, the excim...

The effects of hetero atoms and substituents on the photocurrents of the parent compounds were investigated by comparison of the photocurrents of 52 specimens of the aza-benzenoid and oxa-benzenoid compounds.

(S)-Alanyl-(R)-2-bromoabryl-(R)-β-tyrosine found in jaspamide(1) was conveniently synthesized as its protected derivative 2 in good yield.

The first direct X-ray crystal structure determination of a cytotoxic cyclic peptide from ascidian, ascidiacyclamide, has shown a molecular conformation responsible for its biological activity.