Direct construction of bicyclic heterocycles by palladium-catalyzed domino cyclization of propargyl bromides

The palladium-catalyzed domino cyclization of propargyl bromides having two nucleophilic functional groups is described. Treatment of 1,7-diamino-5-bromohept-3-yne derivatives with catalytic Pd(PPh3)4 in the presence of NaH in MeOH gives the 2,7-diazabicyclo[4.3.0]non-5-enes in good yields. Interestingly, the regioselectivity of the reaction is completely controlled by the relative reactivity of the amine functional groups, irrespective of the position of the nucleophiles. The malonate derivative also undergoes domino cyclization to produce a hexahydroindole derivative.     

Single-crystal-to-single-crystal photocyclization of 4-(2,4,6-triisopropylbenzoyl)benzoic acid in the salt crystal with (S)-phenylethylamine

Ultraviolet irradiation of a salt crystal of 4-(2,4,6-triisopropylbenzoyl)benzoic acid with (S)-phenylethylamine promoted single-crystal-to-single-crystal photocyclization to give an enantiopure (R,R)-cyclopentenol and almost racemic cyclobutenol. The reaction paths were elucidated by X-ray crystallographic analysis of the crystal before and after irradiation.     

Fluorescence determination of N-acetylaspartic acid in the rat cerebrum homogenate using high-performance liquid chromatography with pre-column fluorescence derivatization

N-acetyl-L-aspartic acid (NAA) is an endogenous compound, and its brain concentration is suggested to be altered in neurological disorders. In the present study, a fluorescence determination method for NAA was developed by employing reversed-phase high-performance liquid chromatography (HPLC) with pre-column fluorescence derivatization using 4-N,N-dimethylaminosulfonyl-7-N-(2-aminoethyl)amino-2,1,3-benzoxadiazole (DBD-ED). Using methylsuccinic acid as the internal standard, a linear calibration curve for NAA was constructed in the range 125-1000 microM (n=3). The detection limit on the column was approximately 5.0 fmol (signal-to-noise ratio 3). The proposed HPLC method was applied to determine NAA in the rat cerebrum homogenate. Cerebrum NAA was successfully determined using 10 microL of the homogenate, and the validation data for the proposed HPLC method demonstrated satisfactory results. Intra- and inter-day precision and accuracy were within 1.1-7.0 and -8.1-6.3%, respectively. The concentration of NAA in the male rat cerebrum (13 weeks old) was 84+/-4.6 micromol/mg protein (n=3).     

Diffusion of metal complexes inside of silica-surfactant nanochannels within a porous alumina membrane

The present paper describes diffusivities of a series of metal complexes inside of silica-surfactant nanochannels (channel diameter = 3.4 nm), which were formed within a porous alumina membrane by a surfactant-templated method using cetyltrimethylammonium bromide (CTAB) as a template surfactant. The metal complexes used in this study were Fe(CN)6(3-), Ru(NH3)6(3-), ferrocenecarboxylic acid (Fc-COO-), (ferrocenylmethyl)-trimethylammonium (Fc-NMe3+), N,N-(dimethylamminomethyl)ferrocene (Fc-NMe2), and ferrocene methanol (Fc-OH). Apparent diffusion coefficients of these metal complexes were estimated by measuring their mass transports through the silica-surfactant nanochannels. The estimated apparent diffusion coefficients were on the order of 10(-11) cm2 s(-1) for Fe(CN)6(3-) and Ru(NH3)6(3-), and these values were five orders of magnitude smaller than those in a bulk aqueous solution. For the ferrocene derivatives, the apparent diffusion coefficients of charged ferrocene derivatives are almost the same (5.3 x 10(-11) cm2 s(-1) for Fc-COO- and 5.4 x 10(-11) cm2 s(-1) for Fc-NMe3+), whereas neutral ferrocene derivatives (Fc-NMe2 and Fc-OH) show faster diffusion than the charged species. In addition, the apparent diffusion coefficient of Fc-NMe2 (27 x 10(-11) cm2 s(-1)) was about three times larger than that of Fc-OH (10 x 10-11 cm2 s(-1)). The difference in these diffusion coefficients is discussed by considering the mesostructure of the silica-surfactant nanochannels, that is, an ionic interface with cationic head groups of CTA and their counteranions, a hydrophobic interior of the micellar phase, and a silica framework. As a result, it is inferred that the slow diffusivities of the charged metal complexes are due to the electrostatic interaction between the charged species and the ionic interface, whereas less interaction between neutral ferrocenes and the ionic interface causes distribution of metal complexes into the hydrophobic micellar phase, which is a less viscous medium compared to the ionic interface, resulting in the faster diffusivities of the neutral species.     

Nonlinear optical detection of proteins based on localized surface plasmons in surface immobilized gold nanospheres

A new nonlinear optical method is presented to detect proteins binding to a gold surface without using fluorescent-dye labeling. After exposure of the protein-binding surface to a gold nanosphere solution, the nanospheres are immobilized above a gold surface with a nanogap supported by the protein. The gold nanospheres immobilized on the gold surface show strong localized surface plasmon (LSP) resonance, and the formation of this structure results in a marked increase in the optical second harmonic (SH) activity of the gold surface arising from a large enhancement of the electric field localized adjacent to the nanospheres on the LSP resonance. The SH image, therefore, gives a high contrast ratio, 7.0:1, of protein-binding spots to control spots. The contrast ratio is much greater than those obtained by linear reflectivity imaging.     

Highly beta-selective O-glucosidation due to the restricted twist-boat conformation

[reaction: see text] Ethyl 1-thio-2,3,4,6-tetrakis-O-triisopropylsilyl-beta-d-glucopyranoside, ethyl 6-O-benzyl-1-thio-2,3,4-tris-O-triisopropylsilyl-beta-d-glucopyranoside, and ethyl 6-O-pivaloyl-1-thio-2,3,4-tris-O-triisopropylsilyl-beta-d-glucopyranoside induced highly beta-selective O-glucosidations. Among them, the 6-O-pivaloylated substrate provided the best selectivity up to alpha/beta = 3:97 with cyclohexylmethanol, and the substrate was used for glucosidations with secondary and tertiary alcohols in a highly beta-selective manner. The selectivity would be caused by the twist-boat conformation of the pyranose; this is the first beta-selective O-glucosidation based on conformational control of the pyranose ring.     

Simultaneous anomalous reflection and quartz-crystal microbalance measurements of protein bindings on a gold surface

Protein bindings onto a gold surface were detected simultaneously by QCM (delta F(water)) and anomalous reflection (deltaR) of gold on the same surface in aqueous solutions; the obtained delta F(water)/deltaR values correlated with surface areas and viscosity of proteins.     

Anionic Sublattices in Halide Solid Electrolytes: A Case Study with the High-Pressure Phase of Li3ScCl6

The Li₃MX₆ compounds (M=Sc, Y, In; X=Cl, Br) are known as promising ionic conductors due to their compatibility with typical metal oxide cathode materials. In this study, we have successfully synthesized γ-Li₃ScCl₆ using high pressure for the first time in this family. Structural analysis revealed that the high-pressure polymorph crystallizes in the polar and chiral space group P6₃mc with hexagonal close-packing (hcp) of anions, unlike the ambient-pressure α-Li₃ScCl₆ and its spinel analog with cubic closed packing (ccp) of anions. Investigation of the known Li₃MX₆ family further revealed that the cation/anion radius ratio, r_M/r_X, is the factor that determines which anion sublattice is formed and that in γ-Li₃ScCl₆, the difference in compressibility between Sc and Cl exceeds the ccp r_M/r_X threshold under pressure, enabling the ccp-to-hcp conversion. Electrochemical tests of γ-Li₃ScCl₆ demonstrate improved electrochemical reduction stability. These findings open up new avenues and design principles for lithium solid electrolytes, enabling routes for materials exploration and tuning electrochemical stability without compositional changes or the use of coatings.     

Quantification of local oxygen defects around Yttrium ions for yttria-doped ceria–zirconia ternary system

Local coordination structure around Yttrium ions in CeO₂–Y₂O₃ binary and [(CeO₂)_x(ZrO₂)_1?x]_0.8(YO_1.5)_0.2 (x = 0.0 ~ 1.0) ternary system has been investigated by ⁸⁹Y MAS-NMR. NMR spectra are found to be consisted of multiple peaks that can be assigned to 6-, 7- and 8-oxygen coordinated Yttrium ions. Compositional dependence of the spectrum was observed and compared with the previous results for ZrO₂–Y₂O₃ binary system. The present investigation suggested the degree of localization of the oxygen vacancy around the cation is in the order of Zr⁴⁺ > Y³⁺ > Ce⁴⁺. The degree of the oxygen vacancy preference for each cation was quantitatively determined for CeO₂–ZrO₂–Y₂O₃ ternary system the first time.     

On extensions of some Flugede–Putnam type theorems involving (p,k)‐quasihyponormal,spectral, and dominant operators

A Hilbert space operator S is called (p, k)‐quasihyponormal if S *^k ((S *S)^p – (SS *)^p )S^k ≥ 0 for an integer k ≥ 1 and 0 < p ≤ 1. In the present note, we consider (p, k)‐quasihyponormal operator S ∈ B (H) such that SX = XT for some X ∈ B (K,H) and prove the Fuglede–Putnam type theorems when the adjoint of T ∈ B (K) is either (p, k)‐quasihyponormal or dominant or a spectral operator (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)