Interactions between spiropyrans and room-temperature ionic liquids: photochromism and solvatochromism

A series of imidazolium-based room-temperature ionic liquids (RTILs) containing anions from organic carboxylic acids were prepared. A set of dye probes, including Reichardt's dye (30), 4-nitrioaniline, and N, N-diethyl-4-nitroaniline, were used to determine the ET(30) scales and the Kamlet-Taft parameters (pi*, alpha, and beta) of the RTILs. On the basis of the polarity properties, these RTILs were categorized into three groups: group A with beta >0.9, alpha <0.9; group B with beta <0.9, alpha <0.9; and group C with beta <0.9, alpha >0.9. Interactions of these RTILs with four photochromic spiropyran derivatives (SP-I, SP-II, SP-III, and SP-IV) were investigated. It was found that the spiropyrans could present photochromism (positive or negative) or not, depending mainly on the polarity properties of the RTILs and also on the structure itself. A new spectroscopic method based on the molecular transition energy of the spiropyran probes (ESP) was proposed to determine the polarity of those protic or fluorine-containing RTILs, which were failed with the Reichardt's dye (30) probe.     

Diastereoselective Brook rearrangement-mediated [3+4] annulation: application to a formal synthesis of (+)-laurallene

The formal synthesis of (+)-laurallene, a halogenated eight-membered ring ether, was accomplished. The synthesis involves construction of a trans alpha,alpha'-disubstituted oxocene structure 16 through a Brook rearrangement-mediated [3+4] annulation using acryloylsilane 10 and 6-oxa-2-cycloheptenone 9 and its conversion into 2, which has been transformed into (+)-laurallene by Crimmins and co-workers.     

Stereocontrolled synthesis of the A/B-ring fragment of gambieric acid B: reassignment of the absolute configuration of the polycyclic ether region

Stereocontrolled synthesis of the A/B-ring fragment of the originally assigned structure of gambieric acid B and its possible diastereomers has been accomplished. Detailed comparison of their 1H and 13C NMR data with those of the corresponding moiety of the natural product culminated in a stereochemical reassignment of the absolute configuration of the polycyclic ether region of gambieric acid B.     

Cyclophane-type imidazolium salts with planar chirality as a new class of N-heterocyclic carbene precursors

Cyclophane-type imidazolium salts with planar chirality were synthesized from enantiopure 2-amino alcohols, of which the N(1) and N(3) positions were connected with a bridge. The structural profiles of the imidazolium salts and their derivative N-heterocyclic carbenes (NHCs) were investigated by means of several analyses. The chiral NHCs derived from these imidazolium salts were found to catalyze the asymmetric cross-annulation of an alpha,beta-unsaturated aldehyde with a ketone by means of the "conjugated" umpolung of the enal to give the target gamma-lactone with good to excellent enantioselectivity (up to 94% ee). Based on the expected structure of the NHCs and their intermediates, together with the absolute configuration of the products, a plausible mechanism for the stereocontrol was proposed.     

Decarbonation of MgAl-LDHs (layered double hydroxides) using acetate-buffer/NaCl mixed solution

By using acetate-buffer (sodium acetate and acetic acid)/NaCl mixed solutions, the deintercalation of carbonate ions (CO(2-)3) was conducted on MgAl--LDHs at different Mg/Al ratios-LDH2 (LDH with Mg/Al approximately 2) and LDH3 (LDH with Mg/Al approximately 3). When only an acetate-buffer solution was used, decarbonation did not take place even if the buffer solution was made acidic enough to dissolve LDH itself; however, the addition of NaCl to the buffer solution caused deintercalation of the carbonate ions from the MgAl-LDHs and the reaction was conducted without any morphological and weight change at 25 degrees C. Under the optimum conditions, full decarbonation was attained for the two MgAl-LDHs in minutes, and the obtained LDHs contained Cl(-) in the interlayer space without incorporation of any acetate anions due to their extremely low anion selectivity of acetate ion. The allowable range for the concentration of the decarbonation solution is wide, and the change in pH due to the decarbonation reaction is slight because of the buffering effect. The decarbonation was affected by the Mg/Al ratio of the LDH; i.e., the present LDH2 was slightly more difficult to decarbonate than LDH3, probably due to the higher layer-charge density of LDH2.     

Biosensor immunoassay for the screening of dioxin-like polychlorinated biphenyls in retail fish

Dioxin-like polychlorinated biphenyls (DL-PCBs) often make up the majority of the toxic equivalent (TEQ) contribution of dioxins found in fish samples. For the purpose of making risk assessments, it is therefore important to develop screening methods for determining TEQ concentrations of DL-PCBs in retail fish. We have developed a rapid biosensor immunoassay (BIA) for DL-PCBs that uses a surface plasmon resonance sensor (Biacore 3000). The BIA is highly specific for 2,3',4,4',5-pentachlorobiphenyl (PCB 118) that is generally the most abundant DL-PCB isomer found in fish. The fish extracts were first cleaned up on a multilayer silica gel column followed by an alumina column, then subjected to the assay. The quantitative limit of the assay was 1 ng PCB 118 per gram of tested sample. Dilution and recovery tests using purified fish extracts suggested that the matrix effect was minimized in the assay by diluting the analyzed samples. The assay results for retail fish samples (n=7) agreed well with those obtained by an enzyme-linked immunoassay (ELISA) using the same monoclonal antibody: ELISA has been already validated for determining DL-PCBs in fish samples, so BIA performs well in this analysis. Finally, BIA results for the TEQ concentrations of DL-PCBs in retail fish samples (n=10) correlated well with those obtained by high-resolution gas chromatography coupled to high-resolution mass spectrometry (r=0.89). Our method is therefore useful for screening retail fish to determine the TEQ concentrations of DL-PCBs.     

Differences between collisionally activated and electron-transfer dissociations found for CH(2)X(2)(X = Cl, Br, and I) by using alkali-metal targets

High-energy collisionally activated dissociation (HE-CAD) and high-energy electron- transfer dissociation (HE-ETD) on collisions with alkali-metal targets (Cs, K, and Na) were investigated for CH(2)X(2) (+) (X = Cl, Br, and I) ions by tandem mass spectrometry (MS/MS). In the HE-CAD spectra observed, peaks associated with CH(2)X(+) ions formed by a loss of a halogen atom are always predominant regardless of precursor ions and target metals. The observation of the predominant CH(2)X(+) ions is explained by the lowest energy levels of the fragments of CH(2)X(+) + X among the possible fragment energy levels and internal-energy distribution in HE-CAD. In the charge-inversion spectra, relative peak intensities of the negative ions formed by HE-ETD strongly depend on the precursor ions and the target metals. While the CHCl(2) (-) ion was predominant in the spectra of CH(2)Cl(2) (+) regardless of target species, the most intense peaks in those of CH(2)Br(2) (+) and CH(2)I(2) (+) were ascribed to either Br(-) or CH(2)Br(-) and either I(-) or I(2) (-), respectively, depending on the target metals. The dependence of the relative intensities of the fragment ions by HE-ETD on the precursor ions and target species are discussed on the basis of the energy levels of the neutral fragments and the narrow internal-energy distribution resulting from the near-resonant neutralization. It was demonstrated that HE-ETD using the alkali-metal targets provided rich information on the dissociation of the neutral species.     

High-spin isomer in 93Mo

The high-spin states of ⁹³Mo have been studied by a ⁸²Se( ¹⁶O, 5n) ⁹³Mo reaction at a beam energy of 100 MeV using techniques of in-beam -ray spectroscopy. Measurements of -t, --t coincidences, -ray angular distributions and -ray linear polarizations were performed. The high-spin isomer was found as a (39/2^-) state at about 9.7 MeV. The near-yrast states in ⁹³Mo were interpreted using the weak-coupling picture of a d_5/2 neutron to a neutron magic core nucleus ⁹²Mo.     

Poly(N-isopropylacrylamide) microparticles produced by radiation pressure of a focused laser beam: a structural analysis by confocal Raman microspectroscopy combined with a laser-trapping technique

We developed a confocal Raman microspectroscopy system combined with a laser trapping technique and applied it to aqueous solutions (H(2)O and D(2)O) of poly(N-isopropylacrylamide) (PNIPA), which is well-known as a representative thermo-responsive polymer, i.e., phase transition/separation between coiled and globular states. By introducing a near-infrared (1064 nm) laser beam into a microscope, PNIPA microparticles were produced at the focused spot of the laser beam, both in H(2)O and D(2)O. By using the present system, we succeeded in obtaining the Raman spectra of PNIPA in the coiled and globular states over a wide wavenumber region (800-3500 cm(-1)) for the first time. For the D(2)O solutions (in which the photothermal effect is negligible and hence the microparticles should be produced purely by the effect of radiation pressure), some significant differences were observed in the Raman spectra for the coiled state, in the globular state, and for laser induced microparticles. By analyzing these spectra in detail, we revealed that the structure of the laser-induced microparticles was analogous to that in the globular state. We also discuss the fundamental mechanism underlying the transformation of the higher order structure of a polymer by radiation pressure.