Synthesis and biodegradation of poly(2-pyrrolidone-co-ε-caprolactone)s

Copolyesteramides of 2-pyrrolidone with ε-caprolactone were synthesized by ring-opening copolymerization. The copolymers were random-like and their melting temperature and heat of fusion were dependent on the polymer composition. Biodegradation by a polyamide 4 (PA4) degrading microorganism showed rapid degradation in the region of amide-rich polymer composition. On the contrary, enzymatic hydrolysis using a lipase resulted in a different tendency, that is, ester-rich copolymers hydrolyzed rapidly. Activated sludge makes copolymers degrade to CO₂ in wide polymer composition ratio. Copolyesteramides are expected to be applied as an environmentally-friendly plastics or bioabsorbable polymers in medical fields.     

Exhaustive syntheses of naphthofluoresceins and their functions

Naphthofluorescein and/or seminaphthofluorescein derivatives possessing the additional benzene units to one or both sides of fluorescein were exhaustively constructed through Friedel-Crafts type reactions between corresponding aroylbenzoic acids and dihydroxynaphthalenes. Compound 4 works as a one-dye pH indicator, which shows red in strong acid condition and blue in basic solution. Compound 23 (diacetate of compound 4) shows good transitivity to the HEK 293 cells and acts as a fluorescent pigment for the living cell imaging. Compounds 5, 6, and 9 show fluorescent emission in the NIR region (>700 nm) and imply the potentialities of NIR fluorescent probes.     

Further Stabilization of Leu<Superscript>155</Superscript> Mutant Thermolysins by Mutation of an Autodegradation Site

The autodegradation-resistant mutant thermolysins (TLNs), L155A (Leu¹⁵⁵ to Ala) and L155S (Leu¹⁵⁵ to Ser), were previously constructed by site-directed mutagenesis to enhance thermostability. These mutations suppressed autodegradation at position 154–155, resulting in increased thermostability. However, a new autodegradation site became apparent in these mutant TLNs, at position 155–156. In this study, further stabilization of the mutant TLNs to suppress this new autodegradation was attempted by the substitution of Ile¹⁵⁶ to Asp and Val (L155A-I156N, L155A-I156V, L155S-I156N, and L155S-I156V). SDS–PAGE analysis showed that the autodegradation at 155–156 of all double-mutant TLNs was suppressed. Thermostability at 80 °C was enhanced in all double-mutant TLNs (half-life at 80 °C: WT, 18.3 min; L155A, 25.0 min; L155S, 24.0 min; L155A-I156N, 60.8 min; L155A-I156V, 62.4 min; L155S-I156N, 93.3 min; and L155S-I156V, 40.0 min), and k _cat/K _m values were: WT, 220; L155A, 240; L155S, 123; L155A-I156N, 62; L155A-I156V, 760; L155S-I156N, 240; and L155S-I156V, 520 min⁻¹ mM⁻¹.     

Gold-catalyzed hydrofunctionalization of allenes with nitrogen and oxygen nucleophiles and its mechanistic insight

A wide range of nucleophiles, such as amines and alcohols, reacted intermolecularly with various allenes in the presence of gold catalysts to give the corresponding hydrofunctionalization products in high yields. The intermolecular hydroamination of chiral allenes with aromatic and aliphatic amines proceeded with high to good enantioface selectivities to afford the corresponding chiral allylic amines. On the other hand, in the case of the intermolecular hydroalkoxylation of chiral allenes, no chirality transfer was observed. This marked contrast on the chirality transfer indicates that the mechanisms of gold-catalysis between hydroamination and hydroalkoxylation are different.     

Synthesis of organic phenothiazine-based molecular glasses and effect of racemic/homochiral aliphatic chain on near-infrared photorefractive property

Organic near-infrared photorefractive molecular glasses with a phenothiazine moiety are designed and synthesized through the introduction of linear, racemic/homochiral asymmetrically branched aliphatic chains into photorefractive chromophore as an auxiliary group. The compounds are characterized with ¹H-NMR, IR, FAB-MS, UV–vis, TG, DSC, etc. The effect of different aliphatic chains on the absorption and thermal properties is investigated in detail. The molar absorption coefficiency at the absorption maximum wavelength showed that the homochiral asymmetrically branched aliphatic chain has a strong hypochromic effect in the dilute solution when it is introduced into photorefractive chromophore. The DSC measurement indicated that the introduction of asymmetrically branched aliphatic chain is the key issue to design organic molecular glasses whether it is racemic or homochiral. The effect of racemic/homochiral asymmetrically branched aliphatic groups on photorefractive property is investigated carefully with poly(N-vinylcarbazole) (PVK) as a photoconductor and with (2,4,7-trinitro-9-fluorenylidene) malononitrile (TNFM) as a photosensitizer. The results suggested that the racemic group is more beneficial to the improvement of photorefractive performance than the homochiral when the homochiral cannot induce rigid photorefractive chromophore to be much more ordered.     

Synthesis and redox properties of trinuclear ruthenium-acetylide complexes with tri(ethynylphenyl)amine bridge

Novel trinuclear ruthenium complexes have been prepared by using tri(4-ethynylphenyl)amine as a bridging ligand. Cyclic voltammetry of the trinuclear ruthenium complexes revealed stepwise quasi-reversible redox behavior of three ruthenium-acetylide species and the central triphenylamine unit, whereas the mononuclear analog showed two sequential quasi-reversible redox waves. The spectroelectrochemical UV-VIS spectral studies suggested that the 1e- oxidized triruthenium species was stable and showed a characteristic absorption at lambda(max) = 505 nm. Chemical oxidation of the triruthenium complex with ferrocenium hexafluorophosphate led to the isolation of the 1e- oxidized complex, the near-IR spectrum of which revealed an intervalence charge transfer band due to the electronic coupling among three ruthenium species. The 1e(-) oxidized triruthenium complexes can be classified as class II mixed-valence compounds.     

Four novel gelsenicine-related oxindole alkaloids from the leaves of Gelsemium elegans benth

[reaction: see text] New types of four gelsenicine-related oxindole alkaloids were isolated from the leaves of Gelsemium elegans Benth. Gelsedilam (1) and 14-acetoxygelsedilam (2) are the first examples of 18,19-nor-type monoterpenoid indole alkaloids. Gelsefuranidine (3) and gelseiridone (4) have, respectively, an additional furan residue or an iridoid unit on the gelsenicine-related monoterpenoid indole alkaloid.     

Some relations on Miyazawa's virtual knot invariant

Y. Miyazawa defined a polynomial invariant for a virtual link by using magnetic graph diagrams, which is related with the Jones-Kauffman polynomial. In this paper we show some relations of this polynomial for a virtual skein triple.     

A Fluorescent Probe for Rapid,High-Contrast Visualization of Folate-Receptor-Expressing Tumors In Vivo

Folate receptors (FRs) are membrane proteins involved in folic acid uptake, and the alpha isoform (FR-α) is overexpressed in ovarian and endometrial cancer cells. For fluorescence imaging of FRs in vivo, the near-infrared (NIR) region (650–900 nm), in which tissue penetration is high and autofluorescence is low, is optimal, but existing NIR fluorescent probes targeting FR-α show high non-specific tissue adsorption, and require prolonged washout to visualize tumors. We have designed and synthesized a new NIR fluorescent probe, FolateSiR-1 , utilizing a Si-rhodamine fluorophore having a carboxy group at the benzene moiety, coupled to a folate ligand moiety through a negatively charged tripeptide linker. This probe exhibits very low background fluorescence and afforded a tumor-to-background ratio (TBR) of up to 83 in FR-expressing tumor-bearing mice within 30 min. Thus, FolateSiR-1 has the potential to contribute to the research in the field of biology and the clinical medicine.