A practical ortho-rearrangement of silyl group of ortho-bromophenyl silyl ethers using magnesium(0)

A practical synthesis of ortho-silyl-substituted phenol from ortho-bromophenyl silyl ethers without using RLi is described. Various ortho-bromophenyl silyl ethers are treated with commercially available Mg turnings, which are easy to handle in air, and transfer of the silyl group to the ortho-position occurs in good to high yields. Selective mono-magnesiation of 2,6-dibromophenyl silyl ether is observed even in the presence of excess Mg, and ortho-bromo-6-silylphenol is obtained as the predominant product. The obtained ortho-silyl-substituted phenol is formylated with (CH₂O)_n/MgCl₂/Et₃N, and then condensation with a diamine leads to a silyl-substituted salen-type ligand in a good yield. This scheme is suitable for the large scale synthesis of silyl-substituted salen-type ligands bearing imine groups.     

Oxidation of disulfides with Selectfluor™: concise syntheses of thiosulfonates and sulfonyl fluorides

The reaction of aromatic or benzylic disulfides with 2.5 equiv of Selectfluor™ in acetonitrile/water (10:1) at room temperature efficiently produced the corresponding thiosulfonates. On the other hand, the reaction of disulfides with 6.5 equiv of Selectfluor™ in refluxing acetonitrile/water (10:1) provided sulfonyl fluoride in high yields.     

How lipid unsaturation, peroxyl radical partitioning, and chromanol lipophilic tail affect the antioxidant activity of α-tocopherol: direct visualization via high-throughput fluorescence studies conducted with fluorogenic α-tocopherol analogues

The preparation of two highly sensitive fluorogenic α-tocopherol (TOH) analogues which undergo >30-fold fluorescence intensity enhancement upon reaction with peroxyl radicals is reported. The probes consist of a chromanol moiety coupled to the meso position of a BODIPY fluorophore, where the use of a methylene linker (BODIPY-2,2,5,7,8-pentamethyl-6-hydroxy-chroman adduct, H(2)B-PMHC) vs an ester linker (meso-methanoyl BODIPY-6-hydroxy-2,5,7,8-tetramethylchromane-2-carboxylic acid, H(2)B-TOH) enables tuning their reactivity toward H-atom abstraction by peroxyl radicals. The development of a high-throughput fluorescence assay for monitoring kinetics of peroxyl radical reactions in liposomes is subsequently described where the evolution of the fluorescence intensity over time provides a rapid, facile method to conduct competitive kinetic studies in the presence of TOH and its analogues. A quantitative treatment is formulated for the temporal evolution of the intensity in terms of relative rate constants of H-atom abstraction (k(inh)) from the various tocopherol analogues. Combined, the new probes, the fluorescence assay, and the data analysis provide a new method to obtain, in a rapid, parallel format, relative antioxidant activities in phospholipid membranes. The method is exemplified with four chromanol-based antioxidant compounds differing in their aliphatic tails (TOH, PMHC, H(2)B-PMHC, and H(2)B-TOH). Studies were conducted in six different liposome solutions prepared from poly- and mono-unsaturated and saturated (fluid vs gel phase) lipids in the presence of either hydrophilic or lipophilic peroxyl radicals. A number of key insights into the chemistry of the TOH antioxidants in lipid membranes are provided: (1) The relative antioxidant activities of chromanols in homogeneous solution, arising from their inherent chemical reactivity, readily translate to the microheterogeneous environment at the water/lipid interface; thus similar values for k(inh)(H(2)B-PMHC)/k(inh)(H(2)B-TOH) in the range of 2-3 are recorded both in homogeneous solution and in liposome suspensions with hydrophilic or lipophilic peroxyl radicals. (2) The relative antioxidant activity between tocopherol analogues with the same inherent chemical reactivity but bearing short (PMHC) or long (TOH) aliphatic tails, k(inh)(PMHC)/k(inh)(TOH), is ~8 in the presence of hydrophilic peroxyl radicals, regardless of the nature of the lipid membrane into which they are embedded. (3) Antioxidants embedded in saturated lipids do not efficiently scavenge hydrophilic peroxyl radicals; under these conditions wastage reactions among peroxyl radicals become important, and this translates into larger times for antioxidant consumption. (4) Lipophilic peroxyl radicals show reduced discrimination between antioxidants bearing long and short aliphatic tails, with k(inh)(PMHC)/k(inh)(TOH) in the range of 3-4 for most lipid membranes. (5) Lipophilic peroxyl radicals are scavenged with the same efficiency by all four antioxidants studied, regardless of the nature of their aliphatic tail or the lipid membrane into which they are embedded. These data underpin the key role the lipid environment plays in modulating the rate of reaction of antioxidants characterized by similar inherent chemical reactivity (arising from a conserved chromanol moiety) but differing in their membrane mobility (structural differences in the lipophilic tail). Altogether, a novel, facile method of study, new insights, and a quantitative understanding on the critical role of lipid diversity in modulating antioxidant activity in the lipid milieu are reported.     

Third-order nonlinear optical response in double-walled carbon nanotubes

Resonant behavior and magnitudes of third-order nonlinear optical susceptibilities in double-walled carbon nanotubes (DWNTs) have been investigated by means of femtosecond pump-probe spectroscopy with different pump-photon energies. With the selective excitation of the E₂₂ exciton transition of the inner tubes labeled by the chiral vector indices (7,5) and (7,6), the imaginary part of nonlinear susceptibility Imχ⁽³⁾ has shown the resonant enhancement compared with the case of the nonresonant excitation of the specific tube. The nonlinear response signal at the E₂₂ transition energy of the (8,7) tube has been also enhanced for the excitation of the G-band phonon sideband of its E₂₂ transition. This result is consistent with the phonon-mediated nonlinear optical process observed for the E₂₂ transitions in single-walled carbon nanotubes (SWNTs). It has been also found that the values of the figure of merit Im χ⁽³⁾/α (α: absorption coefficient) of the inner tubes in DWNTs are smaller than those of the corresponding SWNTs, which is interpreted in terms of decay time shortening due to the energy relaxation between the inner and outer tubes.     

Concise and stereoselective synthesis of 2,5- and 2,4-disubstituted thiazole amino acid subunits for synthesizing thiazole-containing peptides

A concise, highly stereoselective synthesis of 2,4- and 2,5-disubstituted thiazole amino acids was developed. These are important building blocks for various biologically active thiazole-containing natural peptides and their regioisomeric analogues. The fundamental reactions are diastereoselective addition of (4- or 5-bromothiazol-2-yl)lithium to N-tert-butanesulfinyl imine with subsequent Pd-catalyzed phenoxycarbonylation.     

Synthesis of a New Thiophene/Quinoxaline CT‐Type Copolymer with High Solubility and Its Basic Optical Properties

A new π‐conjugated charge‐transfer‐type copolymer of electron‐donating thiophene and electron‐accepting quinoxaline was prepared by organometallic polycondensation. The polymer was soluble in organic solvents such as tetrahydrofuran, and showed a UV‐vis peak at long wavelengths of 598 nm in chloroform and 629 nm in the film. Its film exhibited a χ⁽³⁾ peak in the resonance region with a χ⁽³⁾ value comparable to that of regioregular head‐to‐tail poly(3‐hexylthiophene‐2,5‐diyl).

     

Selective formation of [Au23(SPhtBu)17]0, [Au26Pd(SPhtBu)20]0 and [Au24Pt(SC2H4Ph)7(SPhtBu)11]0 by controlling ligand-exchange reaction

To use atomically precise metal nanoclusters (NCs) in various application fields, it is essential to establish size-selective synthesis methods for the metal NCs. Studies on thiolate (SR)-protected gold NCs (Au_n(SR)_m NCs) revealed that the atomically precise Au_n(SR)_m NC, which has a different chemical composition from the precursor, can be synthesized size-selectively by inducing transformation in the framework structure of the metal NCs by a ligand-exchange reaction. In this study, we selected the reaction of [Au₂₅(SC₂H₄Ph)₁₈]⁻ (SC₂H₄Ph = 2-phenylethanethiolate) with 4-tert-butylbenzenethiol (^tBuPhSH) as a model ligand-exchange reaction and attempted to obtain new metal NCs by changing the amount of thiol, the central atom of the precursor NCs, or the reaction time from previous studies. The results demonstrated that [Au₂₃(SPh^tBu)₁₇]⁰, [Au₂₆Pd(SPh^tBu)₂₀]⁰ (Pd = palladium) and [Au₂₄Pt(SC₂H₄Ph)₇(SPh^tBu)₁₁]⁰ (Pt = platinum) were successfully synthesized in a high proportion. To best of our knowledge, no report exists on the selective synthesis of these three metal NCs. The results of this study show that a larger variety of metal NCs could be synthesized size-selectively than at present if the ligand-exchange reaction is conducted while changing the reaction conditions and/or the central atoms of the precursor metal NCs from previous studies.

This study succeeded in obtaining three new thiolate protected metal nanoclusters by changing the ligand-exchange condition from previous studies.     

Caged bulky organic dyes in a polyaromatic framework and their spectroscopic peculiarities

Host–guest structures and properties have been widely studied using relatively small dyes (<1 nm) without bulky groups, due to their smooth incorporation, efficient host–guest interactions, and high analytical accessibility. In this report, on the other hand, three types of sterically demanding organic dyes trapped by a polyaromatic cage were investigated by spectroscopic analyses on the basis of supramolecular interactions. Coumarins with two bulky substituents are bound by the cage in aqueous solution. The resultant caged dyes show unusual emission enhancement, depending on the difference of a single heteroatom in their substituents. The color of perylene bisimides with two bulky substituents is remarkably changed from yellow to red upon caging. This peculiarity stems from the twist of the substituents in the cage, revealed by the combination of absorption and theoretical studies. Furthermore, tetrasubstituted, bulky porphyrins are caught by the cage in aqueous solution. The caged bulky dyes also display altered color and absorption properties, which remain intact even under acidic conditions. In contrast to typical covalent functionalization and previous host–guest studies toward small and non-bulky dyes, the unusual, non-covalent spectroscopic modulation of the large and bulky dyes can be accomplished for the first time by the present cage, featuring a prolate polyaromatic framework with four openings.

Here we report that the open large cavity of an M₂L₄ polyaromatic cage can efficiently bind sterically demanding organic dyes with coumarin, perylene bisimide, and porphyrin cores in aqueous solution. The spectroscopic properties of the caged dyes are largely modulated in the cavity.     

High-spin states in148Tb

High spin states of¹¹⁷Xe have been investigated by means of in-beam γ-ray spectroscopy using the reaction⁹²Mo(²⁸Si, 2pn) at beam energies of 100 to 120 MeV. The previously known νh_11/2 bands are confirmed and the νg_7/2 favored-signature band is extended up to 47/2⁺, in which two band crossings are observed at ?ω=0.33 and 0.44 MeV, respectively. Two new positive-parity bands have been established, one of which is most likely the νg_7/2 unfavored-signature band. A new transition cascade with irregular level spacings is also observed.