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151.
The behavior of hydrogen near a platinum-surface-adsorbed carbon monoxide molecule is described using a potential energy term constructed from density functional theory. A clear nonattractive interaction of hydrogen with CO is confirmed, most notably with oxygen, which retains its strong H-repulsive traits in the Pt-bound CO case. Inhibiting effects of CO greater than what is expected from simple adsorption site exclusion are discussed with regard to adsorption/desorption and mobility on platinum, as well as possibilities of COH and HCO formation. 相似文献
152.
Mitsunori Fukaya Shota Nagamine Dr. Taro Ozaki Yaping Liu Miina Ozeki Taro Matsuyama Dr. Kazunori Miyamoto Prof. Dr. Hirokazu Kawagishi Prof. Dr. Masanobu Uchiyama Prof. Dr. Hideaki Oikawa Dr. Atsushi Minami 《Angewandte Chemie (International ed. in English)》2023,62(44):e202308881
Mushroom terpenoids are biologically and chemically diverse fungal metabolites. Among them, melleolides are representative sesquiterpenoids with a characteristic protoilludane skeleton. In this study, we applied a recently established hot spot knock-in method to elucidate the biosynthetic pathway leading to 1α-hydroxymelleolide. The biosynthesis of the sesquiterpene core involves the cytochrome P450 catalyzing stepwise hydroxylation of the Δ6-protoilludene framework and a stereochemical inversion process at the C5 position catalyzed by short-chain dehydrogenase/reductase family proteins. The highlight of the biosynthesis is that the flavoprotein Mld7 catalyzes an oxidation-triggered double-bond shift accompanying dehydration and acyl-group-assisted substitution with two different nucleophiles at the C6 position to afford the Δ7-protoilludene derivatives, such as melleolide and armillarivin. The complex reaction mechanism was proposed by DFT calculations. Of particular importance is that product distribution is regulated by interaction with the cell membrane. 相似文献
153.
Fukui H Kishi R Minami T Nagai H Takahashi H Kubo T Kamada K Ohta K Champagne B Botek E Nakano M 《The journal of physical chemistry. A》2008,112(36):8423-8429
Hybrid density functional theory method is applied for investigating the diradical character dependence of the second hyperpolarizability (gamma) of square planar nickel complexes involving several types of bidentate ligands [o-C6H4XY, where X = Y = O, NH, S, Se, and PH as well as (X, Y) = (NH, NH2) and (S, NH2)]. It is found that, as a function of the donor atoms, the diradical character of these complexes varies from 0.0 to 0.884 and is associated with substantial variations of gamma ranging from 14 x 10(3) to 819 x 10(3) au. In particular, the largest gamma values are associated with intermediate diradical characters in good agreement with the structure-property relationship obtained for pure hydrocarbon systems. Increasing the electronegativity of the X and Y donor groups of the ligands leads to larger diradical characters as a result of the enhancement of the double bond nature of the C=X(Y) bonds, which further stabilizes the diradicals on both-end benzene rings. This demonstrates that the electronegativities of the donor atoms of the ligands become a tuning parameter of the diradical character and then of the gamma values of these complexes. 相似文献
154.
Dr. Yu Harabuchi Dr. Hiroki Hayashi Dr. Hideaki Takano Prof. Tsuyoshi Mita Prof. Satoshi Maeda 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2023,135(1):e202211936
Systematic reaction path exploration revealed the entire mechanism of Knowles's light-promoted catalytic intramolecular hydroamination. Bond formation/cleavage competes with single electron transfer (SET) between the catalyst and substrate. These processes are described by adiabatic processes through transition states in an electronic state and non-radiative transitions through the seam of crossings (SX) between different electronic states. This study determined the energetically favorable SET path by introducing a practical computational model representing SET as non-adiabatic transitions via SXs between substrate's potential energy surfaces for different charge states adjusted based on the catalyst's redox potential. Calculations showed that the reduction and proton shuttle process proceeded concertedly. Also, the relative importance of SET paths (giving the product and leading back to the reactant) varies depending on the catalyst's redox potential, affecting the yield. 相似文献
155.
Zhang R Seki A Ishizone T Yokoyama H 《Langmuir : the ACS journal of surfaces and colloids》2008,24(10):5527-5533
Reduction of hydrophobic interaction in water is important in biological interfaces. In our previous work, we have found that poly(styrene- b-triethylene glycol methyl ether methacrylate) (PS-PME3MA) segregates the PME3MA block to the surface in hydrophobic environment, such as in air or in a vacuum, and shows remarkable resistance against adsorption or adhesion of proteins, platelets, and cells in water. In this paper, we report that atomic force microscopy (AFM) with hydrophobic probes can directly monitor the reduced hydrophobic interaction of the PS surfaces modified by poly(styrene- b-origoethylene glycol methyl ether methacrylate) (PS-PME NMA), where N is the number of ethylene glycol units. The pull-off forces between the hydrophobic probes that are coated with octyltrichlorosilane (OLTS) and the PS-PME NMA modified polystyrene (PS) surfaces in water were measured. The absolute spring constants and tip-curvatures of the AFM cantilevers were measured to compute the work of adhesion by the Johnson, Kendall, and Roberts (JKR) theory, which relates the pull-off force at which the separation occurs between a hemisphere and a plane to the work of adhesion. The hydrophobic interactions between the hydrophobic tip and polymer surfaces in water were greatly reduced with the segregated PME NMA blocks. The hydrophobic interactions decrease with increasing N of the series of PS-PME NMA and show a correlation with the amount of protein adsorbed. 相似文献
156.
Takechi H Adachi K Monjushiro H Watarai H 《Langmuir : the ACS journal of surfaces and colloids》2008,24(9):4722-4728
The apparent circular dichroism (CD) and the linear dichroism (LD) spectra of the aggregates of achiral zinc(II)-5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine (ZnTPyP), formed at the toluene/water interface in a centrifugal liquid membrane (CLM) cell, were investigated by comparison with the microscopic CD and LD spectra of a single interfacial aggregate of ZnTPyP about 100 mum in length, measured by a microscope-spectropolarimeter. The interfacial ZnTPyP aggregate showed two types of flat trapezoidal shapes, one had a seedlike core at an edge (type I) and another a needlelike core at an edge (type II). The microscopic CD and LD spectra were observed by varying the angle between the parallel axis of the trapezoidal aggregate and the perpendicular axis of a polarized light for LD. The plot of the CD intensity against the LD intensity for a single aggregate, observed at a given wavelength, showed a rotated elliptical shape with a long axis through the origin, when the orientation angle was changed. From these results, it was concluded that the apparent CD spectra observed by the CLM-CD method were mainly due to the large linear dichroism of the aggregate. Both type I and type II structures showed two transition dipole moments, parallel and perpendicular to the long axis of the structure, but suggesting a more developed J-aggregate in type II structure. AFM measurements showed that the interfacial ZnTPyP aggregate had a multilayer structure, in which the unit monolayer thickness was 1.58 +/- 0.23 nm. Finally, the orientation angle of the interfacial aggregate in the CLM cell was estimated as 41 degrees -44 degrees to the rotating axis of the cell. 相似文献
157.
Preparation of poly(N-isopropylacrylamide) emulsion gels and their drug release behaviors 总被引:1,自引:0,他引:1
Stimuli-sensitive drug delivery systems (DDSs) have attracted considerable attention in medical and pharmaceutical fields; thermosensitive DDS dealing with poly(N-isopropylacrylamide) (poly(NIPA)) have been widely studied. Novel NIPA emulsion gels, i.e., NIPA hydrogels containing distributed oil (oleyl alcohol) microdroplets, were synthesized by means of an emulsion-gelation method in which the polymerization of hydrogels in an aqueous phase in an oil-in-water (O/W) emulsion and the loading of a lipophilic drug (indomethacin) dissolved in an oil phase were accomplished simultaneously. The pulsatile (on-off) drug release from the NIPA emulsion gel loading indomethacin to a phosphate buffered saline (PBS) solution was successfully controlled by a temperature swing between 25 degrees C (release off) and 40 degrees C (release on). The mechanism of the pulsatile drug release was discussed in relation to the diffusion rate, distribution ratio, solvent exchange of NIPA hydrogels, and drug release from an NIPA organogel. The mechanism was as follows: the solvent exchange occurred within the NIPA emulsion gel (the NIPA gel-network absorbed oleyl alcohol with indomethacin) at temperatures above the LCST, and the diffusion rate of indomethacin through the solvent-exchanged gel was higher at 40 degrees C than at 25 degrees C. 相似文献
158.
Nakamura S Nakashima H Sugimoto H Sano H Hattori M Shibata N Toru T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(7):2145-2152
Enantioselective C--C bond formation to 2-pyridinesulfonylimines afforded products with good enantioselectivity. Dynamic induction of chirality on the sulfur by coordination of a chiral Lewis acid to the pyridine nitrogen and one of the prochiral sulfonyl oxygens induces enantioselectivity. Since the 2-pyridinesulfonyl group can easily be removed after the reaction, it acts not only as an activating group but also as an efficient stereocontroller. 相似文献
159.
Preparation and mechanical properties of bacterial cellulose nanocomposites loaded with silica nanoparticles 总被引:3,自引:0,他引:3
Shoichiro Yano Hideaki Maeda Megumi Nakajima Toshiki Hagiwara Takashi Sawaguchi 《Cellulose (London, England)》2008,15(1):111-120
Bacterial cellulose (BC), which is produced by Gluconacetobacter xylinus (Ga. xylinus) in culture, is made up of a three-dimensional network of ribbon-shaped bundles of cellulose microfibrils. In the current
studies, we used two processes to prepare nanocomposites of BC filled with silica particles. In Process I, Ga. xylinus was incubated in medium containing silica sol Snowtex 0 (ST 0, pH 2–4) or Snowtex 20 (ST 20, pH 9.5–10.0). The elastic modulus
at 20 °C was improved by keeping the amount of silica in the nanocomposites below 4% when ST 20 was used and below 8.7% when
ST 0 was used. This process allowed incorporation of 50% silica in BC. Inclusion of higher amounts of silica reduced the modulus
at 20 °C and the strength of the nanocomposites below that of BC. X-ray diffraction measurements revealed that the silica
particles disturb the formation of ribbon-shaped fibrils and affect the preferential orientation of the (
) plane. We also produced BC-silica nanocomposites by Process II, wherein the BC hydrogel was immersed in different concentrations
of silica sols, allowing silica particles to diffuse into the BC hydrogel and lodge in the spaces between the ribbon-shaped
fibrils. This method increased the modulus at 20°C and the strength compared to the BC matrix, but it was difficult to load
the BC with more than 10% silica in this way. 相似文献
160.
Nojima H Takeda-Shitaka M Kanou K Kamiya K Umeyama H 《Chemical & pharmaceutical bulletin》2008,56(5):635-641
Class I major histocompatibility complex (MHC) molecules have three domains, a platform domain and two membrane-proximal immunoglobulin-like domains, an alpha3 domain and a beta2-immunoglobulin (beta2m). To understand the dynamic interactions among the three domains, we simulated the behavior of a partial model deficient in beta2m and another model deficient in the alpha3 domain, by normal mode analysis. As a result, the partial model deficient in beta2m was more flexible in interdomain conformation than the other model. The lowest frequency modes (<2 cm(-1)) observed for the simulations of the partial model deficient in beta2m showed clear interdomain motions as if each domain moved like a rigid body. Such low frequencies and clear interdomain motions were not observed for the simulations of the other model, therefore the interdomain flexibility of the partial model deficient in beta2m may be due to the lowest frequency modes (<2 cm(-1)). These results suggest that beta2m contributes to maintaining the interdomain conformation of class I MHC molecules more than the alpha3 domain does, and may offer convincing evidence to support the notion that the alpha3 domain and beta2m do not have an equal influence on the structural stability of class I MHC molecules. 相似文献