1.1-GHz continuous-wave EPR spectroscopy with a frequency modulation method

Continuous-wave EPR spectroscopy using a frequency modulation (FM) scheme was developed. An electronically tunable resonator and an automatic tuning control (ATC) system were used. Using the FM scheme instead of magnetic field modulation, we detected EPR absorption at the first derivative mode. We used a microwave frequency of 1.1 GHz in the present experiment. Similar signal-to-noise ratios were obtained with conventional field modulation and the FM method, and a low-quality factor EPR resonator was not necessary to suppress the significant microwave reflection from the resonator. The FM method with a tunable resonator may be an alternative solution to achieving phase-sensitive detection, when the side-effects of magnetic field modulation, such as microphonic noise and mechanical vibration, are detrimental for EPR detection.     

Cyclodextrin Rotaxanes of Pt Complexes and Their Conversion to Pt Nanoparticles

The cationic Pt complex (Pt(NC₆H₄-C₆H₄N-(CH₂)₁₀-O(C₆H₃-3,5-(OMe)₂)(MeN-(CH₂CH₂NMe₂)₂))⁺ was prepared by the reaction of alkylbipyridinium ligand with a nitrateplatinum(II) complex. Mixing the complex and α- and β-cyclodextrins in aqueous media produced the corresponding [2]rotaxanes with 1:1 stoichiometry. γ-Cyclodextrin and the Pt complex formed a rotaxane having components in a 1:1 or 2:1 molar ratio. The results of mass and nuclear magnetic resonance (NMR) measurements confirmed the rotaxane structures of the Pt complexes. Transmission electron microscopy (TEM) and atomic force microscope (AFM) analyses revealed the formation of micelles or vesicles. The addition of NaBH₄ to the rotaxanes in aqueous media formed Pt nanoparticles with diameters of 1.3–2.8 nm, as characterized by TEM. The aggregated size of the nanoparticles formed from the rotaxane did not change even at 70 °C, and they showed higher thermal stability than those obtained from the reduction of the cyclodextrin-free Pt complex.     

Diastereo- and enantioselective synthesis of nitroso Diels-Alder-type bicycloketones using dienamine: mechanistic insight into sequential nitroso Aldol/Michael reaction and application for optically pure 1-amino-3,4-diol synthesis

This article presents complete diastereo- and highly enantioselective synthesis of nitroso Diels-Alder-type bicycloketones using dienamine. With the hydrogen bonding of two hydroxyls in the bulky binaphthol 1c, high enantioselectivities and complete diastereoselectivity are realized in 2-oxa-3-aza-bicycloketone synthesis. On the other hand, alpha,beta-unsaturated ketone can be employed as diene precursor, utilizing readily available tetrazole catalyst 3b, to provide the 3-oxa-2-aza-bicycloketones in moderate yields with complete enantioselectivities. Investigation into the reaction utilizing 2-morpholino-4,4-diphenylcyclohexadiene 2d clearly indicated that cyclization with the bulky binaphthol 1c is involved in the sequential process, the N-nitroso aldol reaction, followed by Michael addition. In addition, optically pure 1-amino-3,4-diol is synthesized from 2-oxa-3-aza-bicycloketones. Use of p-phenoxynitrosobenzene allows access to protected amino diol via cleavage of the N-Ph bond.     

HPLC-spectrophotometric detection of trace heavy metals via ‘cascade’ separation and concentration

A cascade pre-concentration and separation system involving continuous solid-phase extraction and one-drop solvent concentration was developed to enable high-performance liquid chromatography (HPLC) determination of trace levels of Ni(II), Co(II), Cu(II), Se(IV) and Cr(VI) ions in aqueous solution via complexation with sodium diethyldithiocarbamate. The metal complexes were almost completely adsorbed on the solid phase (octadecylsilyl packed column). Ethyl acetate (eluent) containing the metal complexes was then placed in a centrifuge tube, to which a microvolume of dimethyl sulfoxide (DMSO) was added. Successful pre-concentration of the metal complexes into the DMSO phase was accomplished by removing the ethyl acetate using a compact evaporator in a water bath (40°C); 1000-fold concentration was achieved within 45 min. A portion of the residual DMSO phase was then subjected to HPLC analysis. The proposed method has high reproducibility and high sensitivity with detection limits (3σ) for Ni(II), Co(II), Cu(II), Se(IV) and Cr(VI) ions of 0.08, 0.11, 0.12, 0.44 and 0.20 µg/L, respectively. Relative standard deviations (RSDs) (n = 5) at Ni(II) 5.87 µg/L, Co(II) 5.89 µg/L, Cu(II) 6.35 µg/L, Se(IV) 7.90 µg/L and Cr(VI) 5.20 µg/L (1.0 × 10^?7 mol/L each) were 4.0%, 4.6%, 4.6%, 7.2% and 3.4%, respectively.     

Chemo- and Enantioselective Oxidative α-Azidation of Carbonyl Compounds

We report high-performance I⁺/H₂O₂ catalysis for the oxidative or decarboxylative oxidative α-azidation of carbonyl compounds by using sodium azide under biphasic neutral phase-transfer conditions. To induce higher reactivity especially for the α-azidation of 1,3-dicarbonyl compounds, we designed a structurally compact isoindoline-derived quaternary ammonium iodide catalyst bearing electron-withdrawing groups. The nonproductive decomposition pathways of I⁺/H₂O₂ catalysis could be suppressed by the use of a catalytic amount of a radical-trapping agent. This oxidative coupling tolerates a variety of functional groups and could be readily applied to the late-stage α-azidation of structurally diverse complex molecules. Moreover, we achieved the enantioselective α-azidation of 1,3-dicarbonyl compounds as the first successful example of enantioselective intermolecular oxidative coupling with a chiral hypoiodite catalyst.     

Electron Spin Resonance Spectroscopy of Gamma-Irradiated Glucose Polymers

Using electron spin resonance (ESR) spectroscopy, we revealed the irradiation-induced radicals in cellulose and starch. Before gamma-ray irradiation, no ESR signals were observed in both the glucose polymers. However, after gamma-ray irradiation, a singlet at g = 2.0 was observed, and a pair of side signals appeared simultaneously. The side signals were found at the symmetric field positions at both sides of the singlet signal. The side signals were visible in cellulose but not in starch. The side signals are found to be a precise indicator for irradiation effects in cellulose. They are originated from neither the peroxide radical of glucose polymer nor the so-called cellulosic radicals. By the simulation method, we found that the side signals are originated from a triplet due to a hyperfine interaction with two protons. By the theoretical simulation, we revealed that the signal undergo the rotational motions rather than rigid limit state (or no motion).     

Power-law analysis of surface-plasmon-enhanced electromagnetic field dependence of blinking SERS of thiacyanine or thiacarbocyanine adsorbed on single silver nanoaggregates

Blinking statistics in surface-enhanced Raman scattering (SERS) of thiacyanine or thiacarbocyanine adsorbed on single Ag nanoaggregates were analyzed by a power law. A power law reproduces the probability distributions of both the bright and dark SERS occurrences against their duration times. As the localized surface plasmon resonance (LSPR) wavelength of a single Ag nanoaggregate approached the excitation wavelength or the excitation laser intensity increases, the power-law exponents were close to -1.5, a value derived from a one-dimensional random walk model. When the LSPR wavelength left the excitation wavelength or the excitation laser intensity decreases, the power-law exponents deviated from -1.5. The decrease in the power-law exponents in the bright SERS, which indicates a decrease in the probabilities of the long-lived bright SERS, and the increase in the power-law exponents in the dark SERS coincide with the increasing shallowness and narrowing of a optical trapping potential well due to a surface-plasmon-enhanced electromagnetic field around a junction of the Ag nanoaggregates excited at a wavelength apart from the LSPR wavelength or under the low laser intensity, i.e., the low original electromagnetic field, respectively.     

Analysis of excitation laser intensity dependence of blinking SERRS of thiacarbocyanine adsorbed on single silver nanoaggregates by using a power law with an exponential function

In blinking SERRS, probability distributions of the dark events against their duration were mostly reproduced by a power-law with the same exponential function under various excitation laser intensities, although they were given by a power-law with the different exponential functions at other excitation wavelengths.     

Global minimum structure search in Li(x)CoO(2) composition using a hybrid evolutionary algorithm

The global minimum structures for Li(x)CoO(2) compositions where 0 ≤ x ≤ 1 were probed by using a hybrid evolutionary algorithm with an underlying ab initio structural relaxation scheme. The method successfully predicted experimentally observed variants of layered configurations at various degrees of lithiation and the spinel (Fd3[combining macron]m) phase at x = 1/2. New low-energy non-layered host structures at x < 1/2 were also revealed. These structures can be formed from the usual layered configuration through coherent stacking faults along the c-axis and the migration of Co ions into the Li-poor intercalation layer.     

Shotgun Proteomics Revealed Preferential Degradation of Misfolded In Vivo Obligate GroE Substrates by Lon Protease in Escherichia coli

The Escherichia coli chaperonin GroEL/ES (GroE) is one of the most extensively studied molecular chaperones. So far, ~80 proteins in E. coli are identified as GroE substrates that obligately require GroE for folding in vivo. In GroE-depleted cells, these substrates, when overexpressed, tend to form aggregates, whereas the GroE substrates expressed at low or endogenous levels are degraded, probably due to misfolded states. However, the protease(s) involved in the degradation process has not been identified. We conducted a mass-spectrometry-based proteomics approach to investigate the effects of three ATP-dependent proteases, Lon, ClpXP, and HslUV, on the E. coli proteomes under GroE-depleted conditions. A label-free quantitative proteomic method revealed that Lon protease is the dominant protease that degrades the obligate GroE substrates in the GroE-depleted cells. The deletion of DnaK/DnaJ, the other major E. coli chaperones, in the ∆lon strain did not cause major alterations in the expression or folding of the obligate GroE substrates, supporting the idea that the folding of these substrates is predominantly dependent on GroE.