Self-assembly of liquid crystalline triphenylene-oligo(ethylene oxide)-triphenylene molecules and their complexes with lithium triflate

Mesomorphic dimeric molecules consisting of discotic triphenylene rigid units and flexible ethylene oxide spacers have been prepared. The liquid crystalline behaviour is greatly dependent on the length of the ethylene oxide chains. The miscibility and phase behaviour have been examined for mixtures of the materials with lithium triflate.     

Flow-injection analysis method for the determination of nitrite and nitrate in natural water samples using a chemiluminescence NOx monitor.

A flow-injection analysis method for the determination of nitrite and nitrate in natural water samples has been developed that consists of two systems based on their reduction to NO with hydrazine and/or ascorbic acid, followed by chemiluminescence detection. The procedure of sweeping the generated NO into an NOx monitor, by means of a gas-liquid separating coil consisting of microporous polytetrafluoroethylene (PTFE) tubing, offers practical advantages. The adjustment of the carrier gas-flow rates could yield the same calibration graphs for the two measurement systems, and the accumulation sweeping mode provides a higher sensitivity. Chemiluminescence detection allows a wide linear calibration range of 5 x 10(-8) to 5 x 10(-5) M. The detection limits for nitrate and nitrite, defined as three-times the standard deviation of measurement blanks, are 2 x 10(-8) M and 1 x 10(-8) M, respectively, and the average precision was 3.2% at ambient natural concentration levels. Recovery tests were between 94% and 106% for a variety of natural water samples. The method is relatively free from interferences from the substances normally found in natural water, and only ferric ion has an effect for the nitrite determination.     

Two Dimensional Rotational Temperature Measurement by Multiline Laser Induced Fluorescence of Nitric Oxide in Combustion Flame

Two-dimensional rotational temperature measurement was performed in a stable combustion flame of premixed butane and oxygen using multiline laser induced fluorescence (LIF) of nitric oxide molecules. Multiple rotational absorption lines of A²∑⁺Π;X²II(0,0) Q₁ and Q₂ lines were excited by laser light around 226 nm, and the LIF signal was observed by an image-intensified digital camera. Temperature was determined through least squares fitting correlation between LIF intensity and excitation rotational quantum number for the Boltzmann distribution function. The measured LIF intensity was approximated by the Boltzmann distribution with good accuracy, and the temperature obtained was between 500 K and 1800 K for the test flame. The measuring error of the temperature was evaluated and found to be 80 K, which corresponded to 8% of the measured fluorescence intensity. The two-line LIF scheme was evaluated by different pairs of excitation lines (Q₁(31.5)/Q₁(16.5) and Q₁(18.5)/Q₁(16.5)) for comparison with the multiline LIF approach. Temperature which was obtained by two-line LIF scheme corresponded well with multiline LIF results for Q₁(31.5)/Q₁(16.5) excitation. However, for Q₁(18.5)/Q₁(16.5) excitation, the obtained temperature did not agree with the multiline LIF result because the population of rotational states J=18.5 and J=16.5 is similar at high temperatures. We found that two-line LIF temperature measurement was reliable when excitation lines were suitably selected.     

Viologen-based redox-active ionic liquid crystals forming columnar phases

Viologens possessing three alkoxy chains at each terminal self-organize into columnar liquid-crystalline phases through nanophase segregation and electrostatic interactions. These viologens are redox-active and susceptible to two consecutive electrochemical reductions.     

Comparison of FAIR technique with different inversion times and post contrast dynamic perfusion MRI in chronic occlusive cerebrovascular disease

The purpose of this study was to examine the signal change occurring with different inversion times (TIs) of the flow-sensitive alternating inversion recovery (FAIR) technique and to compare with the perfusion image obtained with Gd-DTPA injection. The subjects were 11 patients with unilateral occlusive cerebrovascular disease. Two FAIR images with different TIs (800 ms and 1600 ms) were measured for each patient and dynamic perfusion MRI was performed to produce four kinds of parameter maps: mean transit time (MTT), time to peak (TTP), relative cerebral blood flow (rCBF) and relative cerebral blood volume (rCBV) maps. Asymmetry ratios (ARs) between the affected and contra-lateral vascular sides were measured in both FAIR images and the four dynamic parameter maps. The AR of the MTT map of the four parameters showed the highest correlation with that of the FAIR images, especially with that of TI = 1600 ms (r = 0.829), and the AR of the rCBV map revealed the worst correlation with the FAIR images. The AR of the FAIR image with TI = 800 ms was less correlated with that of MTT than that with TI = 1600 ms. These results suggested that the signal intensity of the FAIR image was influenced by flow transition time and the change in TI could be used to select the flow with a different transition time. Our study suggested that a longer TI in the FAIR technique might be more useful than a shorter TI for evaluating chronic occlusive cerebrovascular disease in the clinical setting.     

Sulfur K-edge XAS and DFT calculations on nitrile hydratase: geometric and electronic structure of the non-heme iron active site

The geometric and electronic structure of the active site of the non-heme iron enzyme nitrile hydratase (NHase) is studied using sulfur K-edge XAS and DFT calculations. Using thiolate (RS(-))-, sulfenate (RSO(-))-, and sulfinate (RSO(2)(-))-ligated model complexes to provide benchmark spectral parameters, the results show that the S K-edge XAS is sensitive to the oxidation state of S-containing ligands and that the spectrum of the RSO(-) species changes upon protonation as the S-O bond is elongated (by approximately 0.1 A). These signature features are used to identify the three cysteine residues coordinated to the low-spin Fe(III) in the active site of NHase as CysS(-), CysSOH, and CysSO(2)(-) both in the NO-bound inactive form and in the photolyzed active form. These results are correlated to geometry-optimized DFT calculations. The pre-edge region of the X-ray absorption spectrum is sensitive to the Z(eff) of the Fe and reveals that the Fe in [FeNO](6) NHase species has a Z(eff) very similar to that of its photolyzed Fe(III) counterpart. DFT calculations reveal that this results from the strong pi back-bonding into the pi antibonding orbital of NO, which shifts significant charge from the formally t(2)(6) low-spin metal to the coordinated NO.     

New triterpenoids from Gentiana lutea

Three new triterpenoids, 2,3-seco-3-oxours-12-en-2-oic acid, 2,3-seco-3-oxoolean-12-en-2-oic acid, and betulin 3-O-palmitate, have been isolated from the rhizomes and roots of Gentiana lutea, together with five known ones. The structures of the new compounds were determined by spectral and chemical methods.     

Garlicnin A from the fraction regulating macrophage activation of Allium sativum

Garlicnin A (1), a new stable, sulfur-containing compound isolated from a fraction of the acetone extracts of Allium sativum L. garlic bulbs, showed the potential to suppress tumor cell proliferation by inhibiting the polarization of M2 alternatively activated macrophages, and its structure was characterized as 3,4-dimethyl-5-(4,5-dithia-1E,7-octadiene)-tetrahydrothiophene-2-sulfoxide-S-oxide, on the basis of the results of spectroscopic analysis results.