Facile conversion of CF3-containing propargylic alcohol derivatives via the corresponding allenes

Empirical information on the acidity of the propargylic proton from our previous work allowed us to develop novel synthetic transformations of readily available terminally trifluoromethylated propargylic alcohols 1 into the corresponding allenyl tosylates 3a, 1-tosyloxy- or 1-acyloxy-4,4,4-trifluorobutan-2-ones 4, and 2-(2,2,2-trifluoroethyl)prop-2-en-1-ones 5, which was enabled by such common bases as NaOH and tertiary amines for affecting ready abstraction of this proton.     

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.     

Synthesis of Au-based porous magnetic spheres by selective laser heating in liquid

We report the synthesis of Au-based submicrometer-sized spherical particles with uniform morphology/size and integrated porosity-magnetic property in a single particles. The particles are synthesized by a two-step process: (a) selective pulsed laser heating of colloidal nanoparticles to form particles with Au-rich core and Fe-rich shell and (b) acid treatment which leads to formation of porous architecture on particle surface. The simple, fast, inexpensive technique that is proposed demonstrates very promising perspectives for synthesis of composite particles.     

Failure diagnosis of organic photovoltaic using electro-optic probe

This paper describes the measurement of an organic photovoltaic using an electro-optic probe. We verify the validity of the electro-optic probe by comparing it with a conventional electric probe. The electric field distribution of the organic photovoltaic is examined on the basis of results of the test board measurement using the electro-optic probe and results of the test board simulation using an electromagnetic field simulator. We succeed in failure diagnosis of the organic photovoltaic in three failure modes. We found that the organic photovoltaic has a failure cell, and the electro-optic probe is successfully applied to failure diagnosis of organic photovoltaic.     

Lewis acid-promoted reactions of ethenetricarboxylates with γ-CF3-substituted propargyl alcohols

The Lewis acid-promoted reaction of an ethenetricarboxylate derivative (1) with CF₃-substituted propargyl alcohols has been examined. Reaction of γ-CF₃ propargyl alcohols in the presence of zinc bromide gave five-membered CF₃-containing tetrahydrofurans in 66-85% yield. The CF₃ group activates alkyne as an electron-withdrawing group. On the other hand, reaction of γ-trifluoromethyl-α-aryl propargyl alcohols 2 with 1 in the presence of 1 equiv of SnCl₄ gave cyclobutane derivatives 6 in 29-49% yield. Formation of cyclobutane 6a arises from the [2+2] cycloaddition between ethenetricarboxylate 1 and chloroallene 8, which is produced by the reaction of propargyl alcohol 2a and SnCl₄.     

Acid catalyzed monodehydro-2,5-diketopiperazine formation from N-α-ketoacyl amino acid amides

We have developed a new synthetic method for monodehydro-2,5-diketopiperazines (monodehydroDKPs), which is based on an acid catalyzed cyclization of N-α-ketoacyl amino acid amides. Using this cyclization reaction, monodehydroDKP was formed with no or slight racemization in case that N-α-ketoacyl amino acid amides with β-aliphatic-α-ketoacyl groups and sterically unhindered N-substituting groups at the C-terminal amide nitrogen were used in the presence of catalytic amount of p-TsOH (3-5 mol %) or 10% TFA. In the case of β-aryl-α-ketoacyl amino acid derivatives, in which an enol form predominantly exists by conjugation with the aromatic ring, racemization could be minimized by optimizing the reaction conditions (5 mol % p-TsOH, reflux for 6 h), although the chemical yield could not be dramatically improved. However, this reaction condition was successfully applied to the synthesis of a tubulin depolymerization agent, (−)-tert-butyl-oxa-phenylahistin, with no racemization.     

Fusaric acid as a novel proton-affinitive derivatizing reagent for highly sensitive quantification of hydroxysteroids by LC-ESI-MS/MS

A highly sensitive derivatization method for liquid chromatography (LC)-electrospray ionization (ESI) tandem mass spectrometry of dehydroepiandrosterone (DHEA), testosterone (T), pregnenolone (P5), and 17α-OH-pregnenolone (17-OHP5) was developed based on the use of fusaric acid as a reagent. DHEA, P5, and 17-OHP5 were rapidly and quantitatively converted to the 3-fusarate esters by treatment with fusaric acid and 2-methyl-6-nitrobenzoic anhydride. The positive ESI-mass spectra of the fusarate esters of each steroid were dominated by the appearance of [M + H]⁺ as base peaks. The fusarate derivatization of these steroids showed 17.6-fold (DHEA), 11.9-fold (P5), 3.3-fold (17-OHP5), and 1.8-fold (T) higher sensitivity to those of the corresponding picolinate derivatives in LC-selected reaction monitoring.     

Preparation of Mg–Al layered double hydroxides intercalated with 1,3,6-naphthalenetrisulfonate and 3-amino-2,7-naphthalenedisulfonate and assessment of their selective uptake of aromatic compounds from aqueous solutions

Mg–Al layered double hydroxides (Mg–Al LDHs) intercalated with 1,3,6-naphthalenetrisulfonate (NTS^3?) and 3-amino-2,7-naphthalenedisulfonate (ANDS^2?) ions were prepared by coprecipitation and were characterized by X-ray diffraction and chemical analyses. Based on X-ray diffraction patterns, the naphthalene rings of NTS^3? and ANDS^2? were most likely oriented parallel to the brucite-like host layers of the Mg–Al LDH, midway between layers. The prepared Mg–Al LDHs were able to selectively take up aromatics from aqueous solutions, and the order of percentage uptake was as follows: 1,3-dinitrobenzene > nitrobenzene > benzaldehyde > N,N-dimethylaniline > anisole > 1,2-dimethoxybenzene. The differences in the extent of π–π stacking interactions occurring between the benzene rings of the aromatics and the naphthalene ring of the intercalated NTS^3? and ANDS^2? probably resulted in these differences among the absorbed quantities of the various aromatics.     

N-(3,5-dihydroxybenzoyl)-6-hydroxytryptamine as a novel human tyrosinase inhibitor that inactivates the enzyme in cooperation with l-3,4-dihydroxyphenylalanine

N-(3,5-Dihydroxybenzoyl)-6-hydroxytryptamine (2) was a novel inhibitor of L-3,4-dihydroxyphenylalanine (DOPA) oxidase activity of human HMV-II melanoma tyrosinase. The IC?? values for 2 and three reference compounds, N-(3,5-dihydroxybenzoyl)serotonin, 6-hydroxyindole, and kojic acid, were 9.1, 842, 22, and 310 μM, respectively, indicating that the 6-hydroxyindole moiety was more effective than 5-hydroxyindole as the pharmacophore of polyphenolic tyrosinase inhibitors and that the inhibitory activity of 6-hydroxyindole was strengthened by the link with a resorcinol group. Furthermore, compound 2 exhibited a unique property of inactivating the human tyrosinase in the presence of low concentrations of DOPA. This inactivation was attenuated by high concentrations of DOPA and for the most part was irreversible as confirmed by activity stain in native polyacrylamide gel electrophoresis and by removal of 2 and DOPA using gel permeation chromatography. Tyrosinase is the enzyme that oxidizes tyrosine to DOPA and further oxidizes DOPA to the melanin precursor dopaquinone. A compound such as 2 that inactivates the enzyme in the presence of a small amount of DOPA is therefore attractive as a new type of tyrosinase inhibitor. Unfortunately, 2 hardly suppressed the melanogenesis in melanoma cell culture. However, the above strong inhibitory activity and the unique property in the combination with DOPA suggest that this compound is a useful lead in designing new antimelanogenic agents.     

Efficient energy transfer via the cyanide bridge in dinuclear complexes containing Ru(II) polypyridine moieties

We report the synthesis, structure and properties of the cyanide-bridged dinuclear complex ions [Ru(L)(bpy)(μ-NC)M(CN)(5)](2-/-) (L = tpy, 2,2';6',2'-terpyridine, or tpm, tris(1-pyrazolyl)methane, bpy = 2,2'-bipyridine, M = Fe(II), Fe(III), Cr(III)) and the related monomers [Ru(L)(bpy)X](2+) (X = CN(-) and NCS(-)). All the monomeric compounds are weak MLCT emitters (λ = 650-715 nm, ? ≈ 10(-4)). In the Fe(II) and Cr(III) dinuclear systems, the cyanide bridge promotes efficient energy transfer between the Ru-centered MLCT state and a Fe(II)- or Cr(III)-centered d-d state, which results either in a complete quenching of luminescence or in a narrow red emission (λ ≈ 820 nm, ? ≈ 10(-3)) respectively. In the case of Fe(III) dinuclear systems, an electron transfer quenching process is also likely to occur.