The freezing point of mixtures of H216O with H217O was measured as a function of the molal concentration. The freezing points rose linearly with increasing molal concentration above that of pure ordinary water, H216O, at 273.15 K. This confirms Kiyosawa's previous conclusion [K. Kiyosawa, J. Solution Chem.20, 583 (1991).], drawn from findings on changes in the freezing point of mixtures of H216O with H218O or D216O that even a difference in the number of neutrons in the hydrogen or oxygen atoms of water molecules makes them behave as different entities with respect to the colligative properties of solutions. This has been confirmed to also occur in mixtures of H216O with H217O. 相似文献
A new P-chiral phosphine ligand, (R,R)-2,3-bis(tert-butylmethylphosphino)quinoxaline, has been prepared by the reaction of enantiomerically pure tert-butylmethylphosphine-borane with 2,3-dichloroquinoxaline. This ligand, in contrast to most of the previously reported P-chiral ligands, is an air-stable solid and exhibits excellent enantioselectivities in both Rh-catalyzed asymmetric hydrogenations and Rh- or Pd-catalyzed carbon-carbon bond-forming reactions. 相似文献
We have developed a real-time radioisotope imaging system (RRIS) that can nondestructively trace 14C-labeled chemicals in plants. In an experiment, after feeding 14CO2 to a plant, the plant was fixed inside a box where lighting was regulated, and beta rays emitted from the 14C in the plant were intermittently imaged using the developed system. As a first step, using a series of standard sources of 14C, the data depth and detection limits of the 14C images captured by the RRIS were evaluated for various integral times. As a result, the linearity between the 14C activity and signal intensity was determined for the range 103. Next, the linearity was validated using plant (Arabidopsis thaliana) organs, resulting that the linearity was shown in the case of young leaf, but was not maintained in the thick organs, such as a flower, mature leaf, siliques, and stem. Considering the good correlation between the intensity by RRIS and the PSL value by an imaging plate (IP) as well as the relative low energy of beta rays emitted from 14C, the thickness of the organs would easily affect the quantitativity of the RRIS as well as an IP. Our findings prove that sequential images of 14C in a living plant sample in a regulated light and air environment can be nondestructively analyzed using the developed system, whose quantitativity is similar to that of an IP. 相似文献
We have investigated the thermal annealing effects of hydrocarbon species on the methane-plasma exposed silicon surface, investigated by in situ infrared absorption spectroscopy (IRAS) in multiple internal reflection (MIR) geometry. The proportion of types of hydrocarbon species is not remarkably changed in the hydrocarbon network that consists of sp-, sp2- and sp3-CHX species by annealing at moderate temperatures. On the other hands, the proportion is drastically changed in the network that is mainly composed of sp3-CHX species by annealing at moderate temperatures. It suggests that excess CH3 species in the film is not stable against thermal annealing and would be converted to sp3-CH1-2 species by annealing at moderate temperatures. And the data also show that sp2-CH species is more stable against the thermal annealing than sp3-hydrocarbon species. 相似文献
The present study aimed at maximizing cellulase production by Penicillium funiculosum using sequential experimental design methodology for optimizing the concentrations of nitrogen sources. Three sequential experimental designs were performed. The first and the second series of experiments consisted of a 24 and a 23 factorial designs, respectively, and in the third one, a central composite rotational design was used for better visualizing the optimum conditions. The following nitrogen sources were evaluated: urea, ammonium sulfate, peptone, and yeast extract. Peptone and ammonium sulfate were removed from the medium optimization since they did not present significant statistical effect on cellulase production. The optimal concentrations of urea and yeast extract predicted by the model were 0.97 and 0.36 g/L, respectively, which were validated experimentally. By the use of the desirability function, it was possible to maximize the three main enzyme activities simultaneously, which resulted in values for FPase of 227 U/L, for CMCase of 6,917 U/L, and for β-glucosidase of 1,375 U/L. These values corresponded to increases of 3.3-, 3.2-, and 6.7-folds, respectively, when compared to those obtained in the first experimental design. The results showed that the use of sequential experimental designs associated to the use of the desirability function can be used satisfactorily to maximize cellulase production by P. funiculosum. 相似文献
Poly(N,N‐diethylaminoethyl methacrylate)‐graft‐poly(ethylene glycol) (PEAMA‐g‐PEG) has previously been used as a novel additive to improve the heat resistance of lysozyme, which has a positive net charge and a negatively charged active site. In the present study, we show that PEAMA‐g‐PEG prevents heat inactivation of ribonuclease A (RNase A), which has a positive net charge and a positively charged active site. After treatment at 98 °C for 10 min, the enzymatic activity of RNase A complexed with PEAMA‐g‐PEG was maintained at up to 75% of the level of the native RNase A. The extents of inactivation of RNase A and the complex of RNase A with PEAMA‐g‐PEG were strongly dependent upon the heating temperature and incubation time. Circular dichroism (CD) spectral analysis revealed that heat‐induced irreversible inactivation was largely suppressed when RNase A was complexed with PEAMA‐g‐PEG. These findings suggest that the heat resistance of RNase A is improved by the external addition of PEAMA‐g‐PEG.
The design of a new class of fluorophores is presented. Some push-pull chromophores (D-pi-A) containing polyphenylethynyl units and a phosphane oxide moiety were efficiently prepared from common intermediates. Straightforward syntheses gave novel one-armed, rod-shaped and three-armed, star-shaped fluorophores. The optical properties of the resulting star-shaped derivatives were evaluated, showed high fluorescence quantum yields, and their excitation induces very efficient charge redistribution. Moreover, thanks to their push-pull character, the molecules exhibited significant second-order NLO properties with good transparency, up to 67x10(-30) esu at 1907 nm, with an absorption lambdamax at 369 nm. The effect of the donor group and of the number of phenylethynyl arms have been studied in this work. 相似文献
In combination with abasic site (AP site)-containing DNAs, potential use of a biotic fluorescence compound, Vitamin B2 (riboflavin), is demonstrated for the fluorescence detection of the thymine (T)-related single-nucleotide polymorphisms. Our method is based on construction of the AP site in DNA duplexes, which allows small ligands to bind to target nucleotides accompanied by fluorescence signaling: an AP site-containing probe DNA is hybridized with a target DNA so as to place the AP site toward a target nucleobase, by which hydrophobic microenvironments are provided for ligands to recognize target nucleotides through stacking and hydrogen-bonding interactions. In 10 mM sodium cacodylate buffer solutions (pH 7.0) containing 100 mM NaCl and 1.0 mM EDTA, Vitamin B2 is found to selectively bind to T (K11 = 1.8 × 106 M−1 at 5 °C) over other nucleobases, and this is accompanied by significant quenching of its fluorescence. While the sensing functions depend on the flanking sequences to the AP site, Vitamin B2 is applicable to the detection of T/C (cytosine), T/G (guanine) and T/A (adenine) mutation sequences of the CYP2A6 gene, where the flanking nucleobases are guanines in both positions (-GXG-, X = AP site). 相似文献
The photochemical C,C-bond cleavage of N-benzyl β-aziridinylacrylonitrile 1 and acrylate 2 and the subsequent [3+2] cycloaddition with electron-deficient alkenes afforded head-to-head adducts selectively and efficiently. Irradiation of N-phenyl aziridine 3 with acrylonitrile gave adducts, but photoreaction of N-benzoyl aziridine 4 and thermal reactions of 3 and 4 with alkenes yielded C(γ),N-cleaved products instead of cycloadducts. N-trityl aziridine 5 also reacted with electron-deficient alkenes, affording 2,3-cis-pyrrolidine derivatives exclusively. A formal synthesis of a pyrrolizidine alkaloid, isoretronecanol (27), starting from 5 was achieved in a convenient manner. 相似文献