Synthesis of perfluorochemicals for use as blood substitutes,part II: electrochemical fluorination of partly fluorinated compounds

Electrochemical fluorination of 2-methoxy-1,1,1-trifluoro-2-(F-methyl) octane gave the corresponding perfluorinated ether in 27% yield, along with cyclic by-products in 9%. A mixture of partly fluorinated tertiary amines, consisting of 1-dipropylamino-F-1-propene and 1-dipropylamino-2-hydryl-F-propane, did not afford a superior yield of tri(F-propyl)amine compared to the unfluorinated tripropylamine. 1-Diethylamino-2-(F-methyl)-F-1-pentene was fluorinated to give the corresponding F-tertiary amine in fairly good yields, together with 1-di(F-ethyl)amino-2-hydryl-2-(F-methyl)-F-pentane and their fragmented products. The study indicates that blocking of the α-carbon atom of an ether with F-methyl groups seems to reduce fragmentation, resulting in good yields of an unrearranged product. However, partial fluorination of a tertiary amine prior to electrochemical fluorination rather allows high yields of undesired by-products, as far as our experiments were concerned.     

The TcO4-binding to human serum albumin --the stoichiometry and characteristics of the binding equilibrium.

The stoichiometry and the characteristics of the TcO4-binding equilibrium to human serum albumin were investigated by the use of 99TcO4-. Based on the Scatchard plots, the number of binding sites and the association constants were obtained at pH 7.38,6.04, 5.10, 4.18, 2.80 and 0.65, respectively. From the parameters at pH 7.38, it was estimated that 64% of TcO4- added was bounded to human serum albumin under physiological condition. Variance in the values at pH 7.38, 6.04 and 5.10 shows that these bindings are stabilized by electrostatic forces. Below pH 4.18, the number of binding sites increased and the association constants constants diminished. These phenomena may be attributed to the conformation change of human serum albumin.     

Direct observation of MoO2 crystal growth from amorphous MoO3 film

The formation process of MoO₂ crystal from amorphous MoO₃ film has been imaged by in situ observation with a transmission electron microscope. Selective growth of flower-shaped MoO₂ crystals by heating above 673 K in vacuum was directly observed. Since the MoO₂ crystal has metallic conductivity of the order of indium oxide film containing tin (ITO film), the thin film growth of the MoO₂ phase has been discussed on the basis of a new substitute for ITO film.     

Two-photon fluorescence bioimaging with an all-semiconductor laser picosecond pulse source

We have demonstrated successful two-photon excitation fluorescence bioimaging using a high-power pulsed all-semiconductor laser. Toward this purpose, we developed a pulsed light source consisting of a mode-locked laser diode and a two-stage diode laser amplifier. This pulsed light source provided optical pulses of 5 ps duration and having a maximum peak power of over 100 W at a wavelength of 800 nm and a repetition frequency of 500 MHz.     

Chiral helicenoid diarylethene with highly diastereoselective photocyclization

A novel photochromic helicenoid diarylethene (R)-1-[1-(1-methoxymethoxyethyl)-2-naphtho[2,1-b]thienyl]-2-(2,4,5-trimethyl-3-thienyl)hexafluorocyclopentene was synthesized enantioselectively. It showed highly diastereoselective photocyclization (90% de) and a large change (950 degrees) in the specific optical rotation value at 633 nm upon UV light irradiation in ethyl acetate.     

Chiral helicenoid diarylethene with large change in specific optical rotation by photochromism

A diarylethene possessing one [4]thiaheterohelicene and one benzothiophene, the latter with a chiral methoxymethoxyethyl group on its C-3 position, was proved to work as a switch of specific optical rotation at a wavelength at which both colored and colorless forms have no absorption in solution. The difference of the specific optical rotation was 1300 degrees between the open form and the photostationary state. The specific optical rotation of one of the isolated optically active major colored forms was -4680 degrees. The conversion to the colored form was 64%, and the diastereomeric excess of photocyclization was 47%.     

Alkali-cation affinities of polyoxyethylene dodecylethers and helical conformations of their cationized molecules studied by electrospray mass spectrometry

Relative alkali-cation affinity of polyoxyethylene (POE) dodecylethers in gas phase was studied by electrospray ionization (ESI) mass spectrometry using dodecylether-poly-ethoxylate (C(12)EO:n, "n" denotes ethyleneoxide unit number) nonionic surfactants, and possible helical conformations of the cationized molecules were demonstrated. The alkali-cation affinity highly depended on the cation diameters. The mass spectra of C(12)EO:8 cationized by alkali-metal ions were dominated by potassiated molecules. The results indicated that the POE moiety could have specific affinity to K(+) ions based on a host-guest interaction between POE helix and potassium ions. This is very similar to the relationships between 18-crown-6 and K(+). The ESI mass spectra exhibited the multiply cationized C(12)EO:n in addition to the singly cationized molecules. The critical EO unit numbers necessary for producing the multiply-charged cationized molecules also depended on the cation diameters. In addition, the POE surfactants highly preferred alkali cations to proton. The results were strongly supported by molecular mechanics/dynamics calculations. A helical conformation of the POE moiety of C(12)EO:15 including two K(+) ions gave a potential minimum, while a lowest energy structure of the protonated molecule took irregular conformations due to the formation of local hydrogen bonds.     

Syntheses, characterization, and photo-hydrogen-evolving properties of tris(2,2'-bipyridine)ruthenium(II) derivatives tethered to a cis-Pt(II)Cl2 unit: insights into the structure-activity relationship

The photo-hydrogen-evolving activity (activity to enhance the photochemical EDTA-reduction of water into molecular hydrogen) was evaluated for three different Ru(II)Pt(II) dimers with a general formula of [(bpy)2Ru(micro-bridge)PtCl2]2+(bpy = 2,2'-bipyridine; bridge = 4,4'-bis(N-(3-aminopropyl)carbamoyl)-2,2'-bipyridine (L1), 2,3-bis(2-pyridyl)pyrazine (L2), and 4,4'-bis(N-(4-pyridyl)methylcarbamoyl)-2,2'-bipyridine (L3); EDTA = ethylenediaminetetraacetic acid disodium salt). A new Ru(II)Pt(II) complex, [(bpy)2Ru(micro-L3)PtCl2]2+, was synthesized and characterized. It was confirmed that all three compounds are ineffective towards photochemical H2 production. In each case, an acetate-buffer solution (pH = 5) containing the Ru(II)Pt(II) dimer and EDTA was photolysed using a 350-W Xe lamp under an Ar atmosphere, during which the amount of H2 evolved was analysed by gas chromatography. Additional photolysis experiments were carried out by adding [Ru(bpy)3]2+ and methylviologen (N,N'-dimethyl-4,4'-bipyridinium) to the photolysis solutions described above to test the H2-evolving activity of the Pt(II) unit involved in these Ru(II)Pt(II) dimers. As a result, the Pt(II) units involved in the L1 and L2 compounds were found to be active as an H2-evolving catalyst, while that of the L3 compound was found to show no activity at all. The extent of intramolecular electron-transfer quenching from the 3MLCT excited state of the [Ru(bpy)3]2+ derivative to the tethering Pt(II) catalyst centre was investigated by comparison of the luminescence spectra of these compounds, together with the related compounds. The results showed that the quenching of the 3MLCT luminescence is not at all enhanced in either the L1 or the L3 compounds. On the other hand, the L2 compound is strongly quenched as previously reported. In addition to the above studies, the H2-evolving activity of some Pt(II) monomers, cis-PtCl2(NH3)2, PtCl2(en)(en = ethylenediamine), cis-PtCl2(4-methylpyridine)2, PtCl2(2,2'-bipyrimidine), PtCl2(4,4'-dicarboxy-2,2'-bipyridine), and [PtCl(terpy)]+(terpy = 2,2':6',2'-terpyridine), were similarly investigated in the presence of EDTA, [Ru(bpy)3]2+ and methylviologen, since they were regarded as structural analogues of the Pt(II) units involved in the L1-L3 compounds. The compounds having a cis-Pt(II)Cl2 unit were generally found to show high H2-evolving activity. This was interpreted in terms of the ligation of negatively charged chloride anions leading to the destabilization of the Pt(II) dz2 orbital responsible for the hydrogenic activation. Importantly, cis-PtCl2(4-methylpyridine)2 exhibited relatively high activity as an H2-evolving catalyst, suggesting the importance of the flexible rotation of the pyridyl ligands for efficient hydrogenic activation at the axial site of the Pt(II) ion. The DFT calculations also showed the validity of the structure-activity relationship discussed above for the L3 compound.