Reactivity and electrochemical behavior of ruthenium dithiolene complexes with coordinatively unsaturated metal centers: cycloaddition and dimerization reactions

The novel ruthenium dithiolene complexes [(arene)Ru{S₂C₂(COOMe)₂}] (arene = C₆H₆ (1a), C₆H₄(Me)(iPr) (1b), C₆Me₆ (1c)) were synthesized. The equilibrium between complex 1a and the corresponding dimer [(C₆H₆)Ru{S₂C₂(COOMe)₂}]₂ (1a′) was confirmed in solution. The reaction of complex 1a with dimethyl- or diethylacetylene dicaboxylate gave the alkene-bridged adducts [(C₆H₆)Ru{S₂C₂(COOMe)₂}{C₂(COOR)₂}] (R = Me (2a), Et (3a)) as [2 + 2] cycloaddition products formally. The reactions of complex 1a with diazo compounds also gave the alkylidene-bridged adducts [(C₆H₆)Ru{S₂C₂(COOMe)₂}(CHR)] (R = H (4a), SiMe₃ (5a), COOEt (6a)) as [2 + 1] cycloaddition products. The electrochemical behavior of complex 1a was investigated. The reductant of complex 1a was a stable species for several minutes. The oxidant of complex 1a was very unstable; the cation 1a⁺ formed was immediately converted to the corresponding cationic dimer 1a′⁺. The cationic dimer 1a′⁺ was stable for several minutes, and it was rapidly and quantitatively converted to the neutral complex 1a when it was reduced.     

Evidence of conformational equilibrium of 1-ethyl-3-methylimidazolium in its ionic liquid salts: Raman spectroscopic study and quantum chemical calculations

Raman spectra of liquid 1-ethyl-3-methylimidazolium (EMI+) salts, EMI(+)BF4-, EMI(+)PF6-, EMI(+)CF3SO3-, and EMI(+)N(CF3SO2)2-, were measured over the frequency range 200-1600 cm(-1). In the range 200-500 cm(-1), we found five bands originating from the EMI+ ion at 241, 297, 387, 430, and 448 cm(-1). However, the 448 cm(-1) band could hardly be reproduced by theoretical calculations in terms of a given EMI+ conformer, implying that the band originates from another conformer. This is expected because the EMI+ involves an ethyl group bound to the N atom of the imidazolium ring, and the ethyl group can rotate along the C-N bond to yield conformers. The torsion energy for the rotation was then theoretically calculated. Two local minima with an energy difference of ca. 2 kJ mol(-1) were found, suggesting that two conformers are present in equilibrium. Full geometry optimizations followed by normal frequency analyses indicate that the two conformers are those with planar and nonplanar ethyl groups against the imidazolium ring plane, and the nonplanar conformer is favorable. It elucidates that bands at 241, 297, 387, and 430 cm(-1) mainly originate from the nonplanar conformer, whereas the 448 cm(-1) band does originate from the planar conformer. Indeed, the enthalpy for conformational change from nonplanar to planar EMI+ experimentally obtained by analyzing band intensities of the conformers at varying temperatures is practically the same as that evaluated by theoretical calculations. We thus conclude that the EMI+ ion exists as either a nonplanar or planar conformer in equilibrium in its liquid salts.     

Integration of gene amplification and capillary gel electrophoresis on a polydimethylsiloxane-glass hybrid microchip

We report on the development of a hybrid polydimethylsiloxane (PDMS)-glass microchip for genetic analysis by functional integration of polymerase chain reaction (PCR) and capillary gel electrophoresis (CGE), and on related temperature control systems for PCR on a PDMS-glass hybrid microchip. The microchip was produced by molding PDMS against a microfabricated master with comparatively simple and inexpensive methods. PCR was successfully carried out on the PDMS-glass hybrid microchip with 500 bp target of lambdaDNA and the amplified gene was subsequently analyzed by CGE on the same PDMS-glass microchip. The chip could be considered as an inexpensive single-use apparatus compared to glass or silicon-made microchips for the same purpose.     

Reversible size of shear-induced multi-lamellar vesicles

We have investigated the reversibility in the shear-induced multi-lamellar vesicle (MLV) size during stepwise cycling of the shear rate by employing common rheometry, polarized light microscopy and rheo-optic techniques. We thus address the question whether there is a true MLV steady state, irrespective of history. The system studied, was the nonionic surfactant triethylene glycol decyl ether (C₁₀E₃) with a concentration of 40 wt.% in D₂O and a constant temperature of 25°C. It was found that the MLV size varies reversibly with varying shear rate, and hence there exists a true steady state in the presence of shear flow. The experimental observations of reversibility are however restricted to higher shear rates. Because the transformation of the size results from the shear strain, the process is very slow at lower shear rates, where the steady state cannot be reached within a reasonable experimental time.     

Phenomenological analysis of elongational flow birefringence in semidilute solutions of hydroxypropylcellulose

The relaxation time of a polymer chain in an elongational flow field was investigated for hydroxypropylcellulose (HPC) semidilute solution systems by two methods: phenomenological analysis of elongational flow-induced birefringence, and dynamic light scattering (DLS) and rheological measurements. To understand the relaxation time of an entangled semiflexible polymer solution in an elongational flow field, scaling analysis of the elongational flow-induced birefringence curve was performed. The results of both temperature and concentration scaling analyses showed that birefringence curves at different temperatures and at several HPC concentrations were described well by a universal birefringence–strain rate curve. This scaling behavior was compared with the "fuzzy cylinder" model. The critical strain rate corresponded to the correlation time of the slow relaxation mode determined by DLS measurement and the relaxation spectrum obtained by dynamic viscoelasticity measurement. The elongational flow-induced birefringence observed in an HPC semidilute solution was concluded to be attributed to the orientation of the HPC segment in the entangled molecular system, because the dominant relaxation mode is found to be the concentration fluctuation of an entangled molecular cluster in a quiescent state.     

Quantitative estimation of NH3 partial pressure in H2 desorbed from the Li-N-H system by Raman spectroscopy

The partial pressure of NH3 gas estimated by Raman spectroscopy indicates that approximately 0.1% NH3 inevitably contaminates the H2 desorbed from a hydrogen storage material composed of LiH and LiNH2 at any temperature up to 400 degrees C in a closed system.     

Preparation of rapidly disintegrating tablet using new types of microcrystalline cellulose (PH-M series) and low substituted-hydroxypropylcellulose or spherical sugar granules by direct compression method

To decrease the sensation of roughness when a tablet, which is rapidly disintegrated by saliva (rapidly disintegrating tablet), is orally taken, we prepared rapidly disintegrating tablets using microcrystalline cellulose (Avicel PH-M series), a new type of pharmaceutical excipient that is spherical and has a very small particle size (particle size, 7-32 microm), instead of conventional microcrystalline cellulose (PH-102) used in the formulation of tablets containing acetaminophen or ascorbic acid as model drugs for tableting study. Tablets (200 mg) prepared using spherical microcrystalline cellulose, PH-M-06, with the smallest particle size (mean value, 7 microm) had sufficient crushing tolerance (approximately, 8 kg) and were very rapidly, disintegrated (within 15 s) when the mixing ratio of PH-M-06 to low-substituted hydroxypropylcellulose (L-HPC) was 9:1. Sensory evaluation by volunteers showed that PH-M-06 was superior to PH-102 in terms of the feeling of roughness in the mouth. Consequently, it was found that particle size is an important factor for tablet preparation using microcrystalline cellulose. It is possible to prepare drugs such as acetaminophen and ascorbic acid (concentration of approximately 50%) in the tablet form using PH-NM-06 in combination with L-HPC as a good disintegrant at a low compression force (1-6 kN). To solve the problem of poor fluidity in the preparation of these tablets, we investigated the use of spherical sugar granules (Nonpareil, NP-101 (sucrose and starch, composition ratio of 7:3), NP-103 (purified sucrose), NP-107 (purified lactose) and NP-108 (purified D-mannitol)). Rapidly disintegrating tablets can be prepared by the direct compression method when suitable excipients such as fine microcrystalline cellulose (PH-M-06) and spherical sugar granules (NP) are used.     

Cyclic esters of aliphatic diacids with pyrocatechol and hydroquinone

Cyclic esters of adipic acid, suberic acid and sebacic acid were prepared by reaction of the acid dichlorides and pyrocatechol or hydroquinone in benzene under high dilution conditions. While only the cyclic dimers could be obtained from hydroquinone, pyrocatechol formed cyclic monomers as well as cyclic dimers (and also a cyclic dimer with succinic acid). The structure of all compounds was confirmed by¹H-NMR- and mass spectra. The crystal structures of the pyrocatechol esters were determined by single crystal X-ray analysis.

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Cyclische Ester aliphatischer Dicarbonsäuren mit Brenzcatechin und Hydrochinon

Zusammenfassung Es wurden cyclische Ester von Adipinsäure, Korksäure und Sebacinsäure durch Reaktion der entsprechenden Säure-Dichloride mit Brenzcatechin oder Hydrochinon bei hoher Verdünnung hergestellt. Während mit Hydrochinon lediglich die cyclischen Dimeren erhalten werden konnten, wurden mit Brenzcatechin sowohl cyclische Monomere als auch cyclische Dimere erhalten (ebenfalls das cyclische Dimer mit Bernsteinsäure). Die Strukturen wurden mittels¹H-NMR und Massenspektren gesichert. Die Kristallstrukturen der Brenzcatechin-Ester wurden mittels Röntgenstrukturanalyse bestimmt.

     

Multiple fluorescence spectra and stable encapsulation of 7-hydroxy-4-methylcoumarin and rhodamine 6g in silicate glasses by the sol-gel method

7-Hydroxy-4-methylcoumarin(4-methylumbelliferone, HMC) and Rhodamine 6G(R6G) were encapsulated into silicate polymeric glass prepared by the sol-gel method under acidic, basic, and neutral conditions from tetraethyl orthosilicate. The fluorescence spectra of these molecules encapsulated into the xerogel state depend on the used catalysts. Three types of fluorescence emissions having peak wavelengths of ca. 390 nm, 470 nm, and 550 run, respectively, were observed simultaneously in the xerogel state composed of HMC and R6G which were prepared by acid catalysts. The encapsulated HMC remains stable for more than one year in the prepared xerogel. The results open the way to the development of simultaneous three-band laser emissions. The observation of the fluorescence spectrum of HMC is useful for a molecular level photophysical probe elucidating the structural changes oftetraethyl orthosilicate during sol to gel to xerogel transitions.     

Imaging of the bronchial blood flow usingg RI-angiography--study on its procedure and application of dual radioisotope technique (author's transl)

RI-angiography with 99mTcO4- was carried out using a scintillation camera with a digital minicomputer for the purpose of imaging of bronchial blood flow in various lung diseases, and as application of dual radioisotope techniques, other imagings such as tumor imaging with 197HgCl2 or 67Ga-citrate and/or perfusion imaging with 99mTc-MAA, were performed simultaneously in patients remaining the same position, too. The image as a iso-count map extracted out of the image of 197HgCl2, 67Ga-citrate or 99mTc-MAA, was superimposed to the brightness image of RI-anigogram (aortic phase). By these procedures, the image of bronchial blood flow were obtained in some patients with lung cancer, pulmonary tuberculosis, lung abscess, and chronic bronchitis. The dual radioisotope techniques using RI-angiography and the other imaging were useful to make isotope diagnosis of lung diseases more reliable, and the image superimposition methods using RI-angiogram and the image of tumor or perfusion, were useful to improve anatomic orientation of the former.