The chloride effect on the photobleaching process of iodopsin, a chicken red-sensitive cone visual pigment, was studied in detail by time-resolved low-temperature spectroscopy at -40 degrees C to -10 degrees C. Decay-associated difference spectra obtained by kinetic analysis using the singular value decomposition method were composed of spectra of BL-iodopsin, lumiiodopsin, metaiodopsin I, metaiodopsin II and metaiodopsin III, essentially identical to those at room temperature. In each conversion step however, iodopsin was partially regenerated, which is not observed in the bleaching process for other visual pigments or iodopsin at room temperature. Moreover, iodopsin was slowly regenerated from the bleached species. The reverse reactions were completely suppressed by substitution of lyotropic NO(3)(-) for Cl(-), suggesting that Cl(-) binding to iodopsin interferes with light-induced cis-trans isomerization of the chromophore. It is likely that the water molecule hydrating Cl(-) forms the additional hydrogen bond(s), by which the protein conformational change necessary to release this steric hindrance becomes enthalpic. As progress of the bleaching process is a consequence of protein conformational change, it is suppressed at low temperatures, resulting in thermal back-isomerization. 相似文献
The cooperative catalysis of copper, silver, and Brønsted acid is presented as a new strategy for olefin functionalization. The catalytic direct carbohydroxylation of arylalkenes with allylic alcohols provided a straightforward and efficient approach for preparing 4,5‐unsaturated alcohols. Synthetically useful functional groups, such as Cl, Br, carbonyl, and chloromethyl, remained intact during the functionalization reaction. 相似文献
This study aimed to characterize and evaluate the cytotoxicities of ellagitannins from S. praecox fruit. Fractionation of an acetone extract of the fruit led to isolation of five new ellagitannins—stachyuranin D (15), stachyuranin E (16), stachyuranin F (17), stachyugluconin (18), and stachyuglyconin (19)—along with seven ellagitannins previously isolated from S. praecox leaves and seven known ellagitannins isolated from Stachyuraceae for the first time. Two-dimensional NMR and other spectroscopic methods enabled complete elucidation of the structures of the new compounds. Structure of flavanoellagitannin (16) was confirmed by 1H NMR comparison with synthetic analogs. The configuration of stachyuglyconin (19) with a C8-aldonic acid core was established with the aid of density functional theory calculations. A MTT assay revealed 5-desgalloylpterocarinin A (11) and hippophaenin B (9) had the highest cytotoxicities among the compounds against HeLa (IC50 = 35.35 μM) and HepG2 (IC50 = 60.00 μM) cells, respectively. 相似文献
The cooperative catalysis of copper, silver, and Brønsted acid is presented as a new strategy for olefin functionalization. The catalytic direct carbohydroxylation of arylalkenes with allylic alcohols provided a straightforward and efficient approach for preparing 4,5‐unsaturated alcohols. Synthetically useful functional groups, such as Cl, Br, carbonyl, and chloromethyl, remained intact during the functionalization reaction. 相似文献
We have commenced a project to develop a beyond-1 GHz solution NMR spectrometer using a HTS coil. Due to a small residual resistance present in the HTS conductor and joint resistance between conductors, a stable persistent current sufficient for NMR measurements is unlikely. Therefore, a current has to be supplied to the HTS coil from an external power supply. The ripple of an external power supply causes a field fluctuation which must be stabilized. In this study we show results of NMR measurements using a 500-600 MHz NMR in such an external current mode: the field fluctuations are stabilized by an internal 2H lock. The field fluctuation from the external power supply comprises a major field fluctuation component at low frequencies, 0.003-0.005 Hz, and superimposed minor field ripples at 2 Hz and 50 Hz. The former limits the time interval of the internal 2H lock, while the latter generates sidebands in the NMR spectrum. Sideband and baseline noise are controlled by appropriate selection of the feedback loop parameters of the lock. The quality of the 1D-solution NMR spectra observed in external current mode is equivalent to that obtained in persistent current mode. However, if the feedback loop time is as short as the gradient pulse width, refocusing of the NMR signal is lost and NMR peaks disappear. The 2D-NOESY and the 2D-HSQC spectra of ubiquitin in an external current mode have been acquired. The quality of the 2D spectra is equivalent to those obtained in persistent current mode; i.e. the internal 2H lock operates stably over an experimental time interval of 40-50 min. To realize a beyond-1 GHz NMR spectrometer, further investigations must be made of (i) the long term stability of a DC power supply, (ii) the enhancement of the compensation field limit for the internal 2H lock, (iii) the extension of the helium refill time interval, and (iv) a method to correct the field homogeneity in the external current mode. 相似文献
An IR laser of 940 nm wavelength induced photochromic reaction in acrylate that contained both spirobenzopyran and rare-earth doped oxide (Gd(2)O(2)S:YbEr). The rare-earth elements were excited by two 940 nm photons and emitted a 550 nm photon, which caused photochromic isomerization of spirobenzopyran. This acrylate turned to its original orange color by either thermal relaxation or ultraviolet irradiation, and was bleached again by IR laser irradiation. 相似文献
Secondary ion species from plasma-enhanced chemical vapor deposited (PECVD) SiO2 films have been investigated using time-of-flight secondary ion mass spectrometry (TOF-SIMS). Comparative studies of PECVD SiO2 films prepared using a mixture of SiH4/N2O reaction gas at 400 °C with thermally oxidized SiO2 films grown at 900 °C were carried out in the mid-range mass spectra from 95 to 165 amu. Small amounts of ion species containing nitrogen atoms, including Si2O2N+, Si3O2N+and Si3O3N+, were detected in the SiO2 bulk from the PECVD SiO2 films. Furthermore, large amounts of Si3O2N+ and Si2O3N− were found at the interface between silicon and the SiO2 films. Depth analysis showed that the intensity peak shapes of these ion species containing nitrogen atoms at the interface were closely coincident with those of Si3O3+ corrected by subtracting the influence of the SiO2 matrix. The variation in the spectra of these ion species clearly indicates that two types of structures of oxynitride exist for the PECVD SiO2 films in the SiO2 bulk films and at the interface. These are likely produced by the reaction of reactive gas with SiO2 and silicon surfaces where dangling bonds of silicon may exist in the different form. 相似文献
Polybutadienes (PBs) are found to form inclusion complexes with cyclodextrins (CDs) stereoselectively to give crystalline compounds in bulk. These complexes have been isolated and characterized by means of 1H NMR and 13C CP/MAS NMR spectroscopy, and X‐ray diffraction. Although α‐CD did not form inclusion complexes with any kinds of PBs in aqueous solutions, α‐CD did form inclusion complexes with PBs having 1,4‐cis‐ and 1,4‐trans‐butadiene units in bulk by heating at 100 °C. On the other hand, PB having 79% of a 1,2‐structure did not form inclusion complexes with α‐CD. The yield of the inclusion complexes increases with an increase in the content of the 1,4‐cis‐structure of PB and decreases with the molecular weights of the PBs.
Detailed studies of ac velocity V_{ac} and T dependence of torsional oscillator responses of solid 4He are reported. A characteristic onset temperature T_{0} approximately 0.5 K is found, below which a significant V_{ac}-dependent change occurs in the energy dissipation for the samples at approximately 32 bar and for one at 49 bar. A V_{ac} dependence of the so-called "nonclassical rotational inertia" fraction also appears below approximately T_{0}. The log(V_{ac}) linear dependence, which suggests involvement of quantized vorticies, was examined in the nonclassical rotational inertia fraction. We find a common 1/T;{2} dependence for this linear slope change in all of the samples for 30相似文献