Structural analysis of polyelectrolyte film absorbing metal ion by SAXS utilizing with X-ray anomalous dispersion effect

A distribution of Cu ions in polyelectrolyte film (Nafion) is directly observed with a small-angle X-ray scattering (SAXS) method utilizing an X-ray anomalous dispersion effect. A partial structure factor of the Cu ions, GAA(q), can be derived from the SAXS profiles obtained by scanning the incident X-ray energy around the Cu K absorption edge. GAA(q) has two peaks, indicating that the Cu ions hierarchically distribute in Nafion film. In addition, a standard SAXS also shows that Nafion film has a hierarchical structure. These results mean that the Cu ions locate in the domain where the hydrophilic bases aggregate.     

Highly stereoselective radical carbonylations of gem-dihalocyclopropane derivatives with CO

A couple of radical carbonylations of gem-dihalocyclopropanes 1 using CO and Bu3SnH (formylation) or Bu3Sn(CH2CH=CH2) (allylacylation) successfully proceeded to give trans and cis adducts (2 and 3) with good to excellent stereoselectivity (trans/cis = >99/1-75/25 or 17/83-1/99). The formylation of 2,3-cis-disubstituted 1,1-dihalocyclopropanes enhanced trans selectivity (trans/cis = >99/1-95/5), whereas both 2,3-cis-disubstituted and 2-monosubstituted 1,1-dihalocyclopropanes underwent allylacylation with nearly complete trans selectivity (trans/cis = >99/1). Inherently less reactive gem-dichloro- and bromochlorocyclopropanes than gem-dibromocyclopropanes served as favorable substrates. [reaction: see text].     

Catalytic hydrogenation of polar organic functionalities based on Ru-mediated heterolytic dihydrogen cleavage

This article highlights Ru complexes, which effect catalytic hydrogenation of polar organic functionalities containing C-O bonds other than aldehydes or ketones. The unique ability of Ru complexes to undergo heterolytic dihydrogen cleavage seems to play a key role in these catalyses.     

Fundamental study on subharmonic imaging by irradiation of amplitude-modulated ultrasound waves

The second harmonic and subharmonic components, the frequencies of which are twice and one half the fundamental frequency, are included in echoes from contrast agents. An imaging method, which employs a second harmonic (second harmonic imaging), is widely used in medical diagnoses. On the other hand, subharmonic is expected to provide a higher contrast between biological tissues and blood flow because echo signals are generated only from blood containing the contrast agents. However, the subharmonic component echo signal power from contrast agents is relatively low. This has resulted in little progress in the field of subharmonic imaging. In this study, a new imaging method is proposed using amplitude-modulated waves as transmitted waves combined with the pulse inversion method to enhance subharmonic echo signals. Two optimal frequencies are set, including the modulated waves, F(1) and F(2), so that the subharmonic frequency of F(1) and the second harmonic frequency of F(2) may result in the same value. This allows a more powerful signal at the frequency band because the second harmonic and subharmonic components are integrated. Furthermore, a B-mode ultrasound image of an agar phantom that imitated biological tissue and showed the effectiveness of our method was reconstructed. As a result, the echo power of the subharmonic component was enhanced by approximately 11.8 dB more than the conventional method and the signal to noise ratio showed an improvement of 7.6 dB.     

Generation of sub-two-cycle mid-infrared pulses by four-wave mixing through filamentation in air

Generation of sub-two-cycle, microjoule pulses in the mid-infrared region is demonstrated. Fundamental and second-harmonic pulses of 25 fs Ti:sapphire amplifier output were focused into the air to produce extremely broadband mid-infrared pulses by four-wave difference-frequency generation through the filamentation. The full width at half-maximum of the spectral bandwidth reaches one octave (2.5-5.5 microm), which is sufficiently broad for sub-single-cycle pulse generation. The pulse width was estimated to be 13 fs, without any compressors, by cross-correlation frequency resolved optical gating. The output energy of more than a few microjoule is sufficient for spectroscopy.     

Cryopreservation of basal stem buds of in vitro-grown mat rush (Juncus spp.) by vitrification

An optimal protocol for the cryopreservation of in vitro-grown mat rush (igusa) buds by vitrification has been successfully developed. Established multiple stemmed cultures, which were induced in liquid MS medium containing 8.9 microM BA by roller culture, were cut into small clumps, plated on solid MS medium and cultured for three weeks at 25 degree C. Clumps that grew many buds were cold-hardened at 5 degrees C, with an 8 h photoperiod, for more than 30 d. The basal stem bud (1 to 2 mm long) was dissected from the clumps and precultured at 5 degrees C for 2 d on solid MS medium containing 0.3 M sucrose. The precultured buds were placed in 2 ml plastic cryotubes and osmoprotected with 1 ml loading solution containing 2 M glycerol and 0.6 M sucrose for 30 min at 25 degree C. Then they were dehydrated in 1 ml PVS2 solution at 25 degree C for 30 min and immersed in liquid nitrogen. Using this protocol, the survival level of cryopreserved igusa 'NZ219' buds reached 87 percent. This protocol was successfully applied to 42 different lines from three Juncus species, which had relatively high survival levels ranging from 30 to 90 percent and an average of 63 percent.     

Infrared frequency upconverter for high-sensitivity imaging of gas plumes

A remote methane detection system has been developed using a single-frequency tunable optical parametric oscillator at 3.4 microm infrared wavelength. The infrared received light is converted by a frequency upconverter with a strong pump beam to near-infrared wavelength at 0.81 microm and detected by a sensitive photomultiplier. The conversion efficiency of the upconverter was 40% for the backscatter signal from a topographic target, and the detector sensitivity was 11 times higher than that of the cooled InAs detector. By raster scanning the infrared beam, imaging was realized for the methane gas plume with an accuracy of 20 parts in 10(6)m at the range of ~2m.     

Halo- and azidodediazoniation of arenediazonium tetrafluoroborates with trimethylsilyl halides and trimethylsilyl azide and sandmeyer-type bromodediazoniation with Cu(I)Br in [BMIM][PF6] ionic liquid

Reaction of [ArN(2)][BF(4)] salts immobilized in [BMIM][PF(6)] ionic liquid (IL) with TMSX (X = I, Br) and TMSN(3) represents an efficient method for the preparation of iodo-, bromo-, and azido-derivatives via dediazoniation. The reactions can also be effected starting with ArNH(2) by in situ diazotization with [NO][BF(4)] followed by reaction with TMSX or TMSN(3). Depending on the substituents on the benzenediazonium cation, competing fluorodediazoniation (ArF formation) and hydrodediazoniation (ArH formation) were observed. Dediazoniation with TMSN(3) and with TMSI generally gave the highest chemoselectivity toward ArN(3) and ArI formation. The IL was recycled and reused up to 5 times with no appreciable decrease in the conversions. Multinuclear NMR monitoring of the interaction of [ArN(2)][BF(4)]/TMSX, [BMIM][PF6]/TMSX, and [BMIM][PF(6)]/TMSX/[ArN(2)][BF(4)] indicated that TMSF is formed primarily via [ArN(2)][BF(4)]/TMSX, generating [ArN(2)][X] in situ, which gives ArX on dediazoniation. Competing formation of ArF in Sandmeyer-type bromodediazoniation of [ArN(2)][BF(4)] with Cu(I)Br immobilized in the IL points to significant involvement of heterolytic dediazoniation.     

Biochemical sniffer with choline oxidase for measurement of choline vapour

An enzyme-based gas sensor (bio-sniffer) for choline vapour was fabricated and tested. The bio-sniffer was constructed using a Clark-type dissolved oxygen electrode and an enzyme (choline oxidase) immobilized membrane. This bioelectronic device measures choline concentration by the oxygen consumption induced by an enzyme reaction of choline oxidase. As the assessment of sensor performances, the calibration curves for choline in the liquid and gas phases were investigated, respectively. The responses of the bioelectronic device to choline solutions of various concentrations were related within a range from 5.00 to 700 μmol·L⁻¹ with a correlation coefficient of 0.999. On the other hand, the bio-sniffer for choline vapour was placed into a gas-measuring chamber and calibrated using gas detection tubes. The calibration range was 1.00–30.0 ppm (correlation coefficient: 0.996). The response time for choline vapour was approximately 15% slower than that of biosensor for choline solution. These results indicate that the bio-sniffer is useful to monitor colourless and odourless choline gas released from coating compositions including choline. Correspondence: Kohji Mitsubayashi, Department of Biomedical Devices and Instrumentation, Institute of Biomaterials and Bioengineering, Tokyo Medical and Dental University, 2-3-10 Kanda-Surugadai, Chiyoda-ku, Tokyo 101-0062, Japan     

Regio- and π-facial selective Lewis acid interceded Diels-Alder reactions of α-dienyl-β-lactams: an indepth analysis

The regio-, diastereo-, and π-facial selective Lewis acid mediated Diels-Alder reactions of cis/trans-3-butadienyl-2-azetidinones with unsymmetrical dienophiles viz. methyl acrylate, dimethyl fumarate, and acrolein leading to the synthesis of diastereomerically pure and biologically potent 1,3,4-trisubstituted-2-azetidinones are reported. Theoretical calculations at HF/6-31G^∗∗ and 6-31G^∗∗/DFT levels have been performed to support the observed π-facial selectivity. The formation of diastereomerically pure ‘endo’ adducts is supported by the X-ray diffraction studies.