Incorporation of CdS Nanoparticles Formed in Reverse Micelles into Mesoporous Silica

The incorporation of CdS nanoparticles, prepared in reverse micellar systems, into thiol-modified mesoporous silica, such as FM41 (functionalized MCM-41) and FM48 (functionalized MCM-48), has been investigated. The nanoparticles were immobilized in the mesopores via the incorporation of water droplets of the reverse micelles. A particle-sieving effect for FM41 having large (L-FM41, 3.8 nm) and medium (M-FM41, 3.6 nm) pore size was observed, in that the incorporation of the CdS nanoparticles was decreased with increasing particle size and with decreasing pore size of the FM41. Chemical vapor deposition treatment employed to narrow the mesopores of the CdS-FM41 enhanced the stability of CdS nanoparticles against heat treatment. The CdS-FM41 composites demonstrated photocatalytic activity for H(2) generation from 2-propanol aqueous solution, the better photocatalytic activity being obtained with the larger pore size for CdS-L-FM41. Copyright 2001 Academic Press.     

Fluorination of 2-alkyl-substituted oxanes. The synthesis and purification of perfluoro(2-alkyl-substituted oxane)s

Five kinds of 2-alkyl-substituted oxanes like 2-ethyloxane, 2-n-propyloxane, 2-iso-propyloxane, 2-n-butyloxane and 2-n-amyloxane were fluorinated electrochemically to give the corresponding perfluoro(2-alkyloxane)s. The perfluoro(2-alkyloxane)s were obtained in good yields from these starting materials together with isomeric perfluoro(2-alkyloxolane)s, perfluoro(2-alkyl-5-methyloxolane)s and perfluoro(dialkyl ether)s. The purification of the perfluoro(2-alkyloxane)s which contained small amounts of isomeric perfluoro(2-alkyloxolane)s was successfully achieved by recovering the former unreacted after treating these mixture with anhydrous aluminum chloride at 150 /sR 160 °C during /sR 48 hrs in order to convert the latter into the easy-separable perfluoro(2,5,5- trichloro-2-alkyloxolane)s. Small quantities of new perfluoro(5,5-dichloroalkanoyl chloride)s were also among the chlorination products. The spectroscopic data as well as the physical properties of these new fluorination products, and perfluoro(2,5,5-trichloro-2-alkyloxolane)s and perfluoro(5,5-dichloroalkanoyl chloride)s are presented.     

The behaviour of dyes at oil/water interfaces

Summary The adsorption of ionic dyes, the builder effect, and the interaction between ionic dyes and surface active agents were investigated by using the electrocapillarity at oil/water interfaces. The oil phase was the solution of tetra-butylammonium chloride, sodium cetylsulphate, cetylpyridinium chloride or stearylamine in methylisobutylketone, and the water phase contained various dyes in addition to the inorganic electrolyte. The interfacial tension decreased over the anodic (or cathodic) polarization range, when anionic (or cationic) dyes were added to the water phase, thus indicating the dye adsorption at the interface. The interfacial excess of dye ions was found to increase linearly with the cubic roots of dye concentration and of ionic strength of the water phase. The counterion binding took place at the oil/water interface between anionic (or cationic) dyes and positive (or negative) head groups of surface active agent ions adsorbed at the interface. It was found that the equilibrium constants of binding between anionic dyes and cationic surface active agents at the oil/water interface were of the same order of magnitude as, and a little larger than, those obtained at the water bulk phase.

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Zusammenfassung An Öl-Wasser-Grenzflächen wurde die Adsorption ionischer Farbstoffe, die Füllerwirkung und die Wechselwirkung zwischen ionischen Farbstoffen und grenzflächenaktiven Verbindungen mit Hilfe der Elektrokapillarität untersucht. Die Ölphase bestand aus einer Lösung von Tetrabutylammoniumchlorid, Natriumcetylsulfat und Cetylpyridiniumchlorid oder Stearylamin in Methylisobutylketon. Die wässerige Phase enthielt verschiedene Farbstoffe und anorganische Elektrolyte. Die Grenzflächenspannung wurde durch anodische (bzw. kathodische) Polarisation erniedrigt, wenn anionischer (bzw. kationischer) Farbstoff zur Wasserphase gegeben wurde. Dies zeigt an, daß Farbstoff an der Grenzfläche adsorbiert wird. Die Grenzflächenkonzentration des Farbstoffions nimmt linear mit der Kubikwurzel der Farbstoffkonzentration und mit der Ionenstärke zu. Als Gegenionen für die anionischen (bzw. kationischen) Farbstoffe an der Grenzfläche wirken die positiven (bzw. negativen) Endgruppen der Tenside, die ebenfalls in der Grenzschicht adsorbiert sind. Die Gleichgewichtskonstanten für die Wechselwirkung zwischen den ionischen Farbstoffen und den grenzflächenaktiven Verbindungen sind an der Öl-Wasser-Grenzfläche von der gleichen Größenordnung bzw. geringfügig größer als in der wässerigen Volumenphase.

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With 12 figures and 2 tables     

Chemo-enzymatic synthesis of 2′,3′-dideoxy-3′-fluoro-β-d-guanosine via 2,3-dideoxy-3-fluoro-α-d-ribose 1-phosphate

2,3-Dideoxy-3-fluoro-α-d-ribose 1-phosphate 2 was stereoselectively synthesized and converted to 2′,3′-dideoxy-3-fluoro-β-d-guanosine 1 by enzymatic reaction using purine nucleoside phosphorylase. This chemo-enzymatic strategy was first applied to the synthesis of 1.     

Simultaneous determination of tetrahydro-β-carbolines and β-carbolines

Summary Reversed-phase ion-pair HPLC with fluorimetric detectors connected in series was studied for the simultaneous determination of two tetrahydro--carbolines and two -carbolines. After additon of internal standards the samples were reacted with fluorescamine, and then subjected to serial extractions to remove their precursor (tryptamine) from the analytical system. This treatment not only suppressed the artefactual formation of tetrahydro--carbolines and -carbolines during analysis, but also effectively purified them. Under optimum conditions, using trifluoroacetic acid as counter ion, all analytes were separated within 14 min and without major interfering peaks. The quantitative ranges were 0.25–80.0 ng mL^–1 for both tetrahydro--carbolines and 0.1–30.0 ng mL^–1 for both -carbolines. Replicate spiking experiments showed that recovery from most of the samples tested was over 90% and the relative standard deviation ranged from 0.7 to 10.4% within and between assays. The proposed method was applicable to various materials such as soy sauce, vinegar, ketchup, tabasco, beer, wine, sake, whisky, brandy, cows' milk, coffee, cocoa, cheese, cigarette smoke and urine.     

Thermostability of <Emphasis Type="Italic">Cromobacterium viscosum</Emphasis> lipase in AOT/isooctane reverse micelle

The thermostability of Cromobacterium viscosum lip ase (EC 3.1.1.3) entrapped in AOT (sodium bis-[2-ethylhexyl] sulfosuccinate) reverse micelles was in creased by the addition of short-chain polyethylene glycol (PEG 400). Two different approaches were considered: (1) the determination of half-life time and (2) the mechanistic analysis of deactivation kinetics. The half-life of lipase entrapped in AOT/isooctane reverse micelles with PEG 400 at 60°C was 28h, ninefold higher than that in reverse micelles without PEG 400. The lip ase entrapped in both reverse micellar systems followed a series-type deactivation mechanism involving two first-order steps. The deactivation constant for the first step at 60°C in PEG containing reverse micelles was 0.055 h¹¹, 11-fold lower than that in reverse micelles without PEG, whereas it remained almost constant for the second step. The inactivation energy of the lip ase entrapped in reverse micelles with and without PEG 400 was 88.12 and 21.97 kJ/mol, respectively.     

Regioselective lithiation of II-(arene)chromium tricarbonyl complexes

Chromium tricarbonyl complexes of 3-methoxybenzyl alcohol and related compounds were selectively lithiated at the 4-position in contrast to the corresponding metal free arene compounds. The resulting 4-lithio complexes were converted to the 4-substituted arene compounds in moderate to excellent yields through the reactions with proper electrophiles and subsequent demetalation.     

Preparation of enol ethers by carbonyl olefination utilizing an alkoxymethyl chloride-titanocene(II) system

Aldehydes, ketones, esters and lactones are transformed into enol ethers or 1,2-dialkoxy-1-alkenes by treatment with organotitanium species prepared from alkoxymethyl chlorides and a titanocene(II) complex.     

Photophysical and (photo)electrochemical properties of a coumarin dye

A new coumarin dye, cyano-{5,5-dimethyl-3-[2-(1,1,6,6-tetramethyl-10-oxo-2,3,5,6-tetrahydro-1H,4H,10H-11-oxa-3a-aza-benzo[de]anthracen-9-yl)vinyl]cyclohex-2-enylidene}-acetic acid (NKX-2753), was prepared and characterized with respect to photophysical and electrochemical properties. It was employed as a dye sensitizer in dye-sensitized solar cells and showed efficient photon-to-electron conversion properties. The photocurrent action spectrum exhibited a broad feature with a maximum incident photon-to-electron conversion efficiency (IPCE) of 84% at 540 nm, which is comparable to that for the famous red dye RuL2(NCS)2 (known as N3), where L stands for 2,2'-bipyridyl-4,4'-dicarboxylic acid. The sandwich-type solar cell with NKX-2753, under illumination of full sun (AM1.5, 100 mW cm(-2)), produced 16.1 mA cm(-2) of short-circuit photocurrent, 0.60 V of open-circuit photovoltage, and 0.69 of fill factor, corresponding to 6.7% of overall energy conversion efficiency using 0.1 M LiI, 0.05 M I2, 0.1 M guanidinium thiocyanate, and 0.6 M 1,2-dimethyl-3-n-propyl-imidazolium iodide in dry acetonitrile as redox electrolyte. In comparison with its analogue NKX-2586 (Langmuir 2004, 20, 4205), NKX-2753 with an extra side ring on the alkene chain produced much higher IPCE values at the same conditions. The side ring acted as a spacer to efficiently prevent dye aggregation when adsorbed on the TiO2 surface, resulting in significant improvements of short-circuit photocurrent, open-circuit photovoltage, and fill factor compared with NKX-2586 that aggregated on the TiO2 surface.     

Release characteristics of a free polyunsaturated fatty acid from an oily lymphographic agent

The release profiles of a free polyunsaturated fatty acid, alpha-linolenic acid, from solutions in an oily lymphographic agent Lipiodol-Ultra-Fluid (Lipiodol), to rabbit and human plasma, phosphate buffer solution (PBS), and PBS containing bovine serum albumin (BSA) were examined in vitro. The times required for 50% release of alpha-linolenic acid from Lipiodol were about 1 and 1.5 h in the rabbit and human plasma, respectively. Although only a slight amount of alpha-linolenic acid was released from Lipiodol to PBS after 24 h incubation at 37 degrees C, release was markedly enhanced by the addition of BSA to PBS. The amount of alpha-linolenic acid released from Lipiodol into PBS containing 5% BSA increased as the alpha-linolenic acid content in Lipiodol was increased. In all experiments, the release had stopped before all alpha-linolenic acid had been released. The prolongation of alpha-linolenic acid release from Lipiodol is considered a requisite for a selective anticancer effect of Lipiodol containing a free fatty acid on liver cancer.