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11.
Robert Faure Jean-Pierre Galy Emile-Jean Vincent Jos Elguero 《Journal of heterocyclic chemistry》1977,14(8):1299-1304
The substituent effects on azido/tetrazole equilibrium on a series of 2-substituted thiazoles, benzothiazoles, thiadiazoles, benzoxazoles and isoxazoles has been studied by proton magnetic resonance in two solvents (DMSO-d6 and deuteriochloroform). For thiazole an excellent Hammett relationship was found, both for the 4 and 5 positions. 相似文献
12.
Product distributions and rate constants for the reaction of ground state C+ ions with O2, NO, HCl, CO2, H2S, H2O, HCN, NH3, CH4, H2CO, CH3OH, and CH3NH2 have been measured. Rate constants were obtained using ion cyclotron resonance trapped ion methods at JPL, and product distributions were obtained using a tandem (Dempster-ICR) mass spectrometer at the University of Utah. Rapid carbon isotope exchange has also been observed in C+-CO collisions. 相似文献
13.
Reipa V Mayhew MP Holden MJ Vilker VL 《Chemical communications (Cambridge, England)》2002,(4):318-319
Spectroelectrochemistry measurements are used to demonstrate that active site mutation and binding of an non-natural substrate to P450cam (CYP101) reduces the shift in the redox potential caused by substrate-binding, and thereby results in slower catalytic turnover rate relative to wild-type enzyme with the natural camphor substrate. 相似文献
14.
Anicich VG Wilson P McEwan MJ 《Journal of the American Society for Mass Spectrometry》2004,15(8):1148-1155
The results of a study of the ion-molecule reactions of N(+), N(2)(+), and HCN(+) with methane, acetylene, and ethylene are reported. These studies were performed using the FA-SIFT at the University of Canterbury. The reactions studied here are important to understanding the ion chemistry in Titan's atmosphere. N(+) and N(2)(+) are the primary ions formed by photo-ionization and electron impact in Titan's ionosphere and drive Titan's ion chemistry. It is therefore very important to know how these ions react with the principal trace neutral species in Titan's atmosphere: Methane, acetylene, and ethylene. While these reactions have been studied before the product channels have been difficult to define as several potential isobaric products make a definitive answer difficult. Mass overlap causes difficulties in making unambiguous species assignments in these systems. Two discriminators have been used in this study to resolve the mass overlap problem. They are deuterium labeling and also the differences in reactivities of each isobar with various neutral reactants. Several differences have been found from the products in previous work. The HCN(+) ion is important in both Titan's atmosphere and in the laboratory. 相似文献
15.
The crystal structure of V0.985Al0.015O2 has been refined from single-crystal X-ray data at four temperatures. At 373°K it has the tetragonal rutile structure. At 323°K, which is below the first metal-insulator transition, it has the monoclinic M2 structure, where half of the vanadium atoms are paired with alternating short (2.540 Å) and long (3.261 Å) V-V separations. The other half of the vanadium atoms form equally spaced (2.935 Å) zigzag V chains. At 298°K, which is below the second electric and magnetic transition, V0.985Al0.015O2 has the triclinic T structure where both vanadium chains contain V-V bonds, V(1)-V(1) = 2.547 Å and V(2)-V(2) = 2.819 Å. At 173°K the pairing of the V(1) chain remains constant: V(1)-V(1) = 2.545 Å, whereas that of the V(2) chain decreases: V(2)-V(2) = 2.747 Å. From the variation of the lattice parameters as a function of temperature it seems that these two short V-V distances will not become equal at lower temperatures. The effective charges as calculated from the bond strengths at 298 and 173°K show that a cation disproportionation has taken place between these two temperatures. About 20% of the V4+ cations of the V(1) chains have become V3+ and correspondingly 20% of the V4+ cations of the V(2) chains have become V5+. This disproportionation process would explain the difference between the two short V-V distances. Also it would explain why the T → M1 transition does not take at lower temperatures. 相似文献
16.
Pseudo-ternary phase diagrams have been constructed for the three-component solvent system (toluene+water+propan-2-ol) containing diblock copolymers of poly(styrene-b-2-vinylpyridine-1-oxide). Microemulsions have been shown to form on the water-rich side of the phase diagram, in the region of the phase boundary without polymer. Dynamic light-scattering experiments have led to droplet size values in the region of 100 nm, with the size depending strongly on the propan-2-ol/water concentration, as well as the amount of solubilised toluene in the core. Viscometry experiments have been carried out to measure polymer aggregation numbers in the microemulsion droplets, and interfacial tension measurements have shown that in the absence of propan-2-ol (effectively a cosurfactant) the limiting value of the oil/water interfacial tension, even an saturation adsorption of the copolymer is 20 mNm–1. However, addition of propan-2-ol reduces the interfacial tension to the very low values generall commensurate with microemulsion formation. 相似文献
17.
Dipolar 1:1 Adducts from the Reaction of 3-Amino-2H-azirines with 1,3,4-Oxadiazol- and 1,3,4-Thiadiazol-2(3H)-ones 3-Amino-2H-azirines 1 react with 5-(trifluoromethyl)-1,3,4-oxadiazol-2(3H)-one ( 2 ) as well as with different 5-substituted 1,3,4-thiadiazol-2(3H)-ones ( 5a–e ) in 2-propanol at room temperature to give dipolar 1:1 adducts of type 3 and 6 , respectively, in reasonable-to-good yields (Schemes 3 and 6, Tab. 1 and 2). The structure of two of these dipolar adducts, 6a and 6e , which are formally donor-acceptor-stabilized azomethin imines, have been elucidated by X-ray crystallography (Figs. 1-4). In the reaction of 2 and sterically crowded 3-amino-2H-azirines 1c–e with a 2-propyl and 2-propenyl substituent, respectively, at C(2), a 4,5-dihydro-1,2,4-triazin-3(2H)-one of type 4 is formed as minor product (Scheme 3 and Table 1). Independent syntheses of these products proved the structure of 4 . Several reaction mechanisms for the formation of compounds 3 and 4 are discussed, the most likely ones are described in Scheme 4: reaction of 2 as an NH-acidic compound leads, via a bicyclic zwitterion of type A , to 3 as well as to 4 . In the latter reaction, a ring-expanded intermediate B is most probable. 相似文献
18.
Thorbjrn Vincent Snderby Zahra Najarzadeh Daniel Erik Otzen 《Molecules (Basel, Switzerland)》2022,27(13)
Functional amyloid is produced by many organisms but is particularly well understood in bacteria, where proteins such as CsgA (E. coli) and FapC (Pseudomonas) are assembled as functional bacterial amyloid (FuBA) on the cell surface in a carefully optimized process. Besides a host of helper proteins, FuBA formation is aided by multiple imperfect repeats which stabilize amyloid and streamline the aggregation mechanism to a fast-track assembly dominated by primary nucleation. These repeats, which are found in variable numbers in Pseudomonas, are most likely the structural core of the fibrils, though we still lack experimental data to determine whether the repeats give rise to β-helix structures via stacked β-hairpins (highly likely for CsgA) or more complicated arrangements (possibly the case for FapC). The response of FuBA fibrillation to denaturants suggests that nucleation and elongation involve equal amounts of folding, but protein chaperones preferentially target nucleation for effective inhibition. Smart peptides can be designed based on these imperfect repeats and modified with various flanking sequences to divert aggregation to less stable structures, leading to a reduction in biofilm formation. Small molecules such as EGCG can also divert FuBA to less organized structures, such as partially-folded oligomeric species, with the same detrimental effect on biofilm. Finally, the strong tendency of FuBA to self-assemble can lead to the formation of very regular two-dimensional amyloid films on structured surfaces such as graphite, which strongly implies future use in biosensors or other nanobiomaterials. In summary, the properties of functional amyloid are a much-needed corrective to the unfortunate association of amyloid with neurodegenerative disease and a testimony to nature’s ability to get the best out of a protein fold. 相似文献
19.
20.
Pierre Beaujean Lionel Sanguinet Vincent Rodriguez Frdric Castet Benoît Champagne 《Molecules (Basel, Switzerland)》2022,27(9)
This contribution employs quantum chemistry methods to describe the variations of the second nonlinear optical responses of molecular switches based on benzazolo-oxazolidine (BOX) units, connected by π-linkers, along their successive opening/closing. Under the fully closed forms, all of them display negligible first hyperpolarizability (β) values. When one BOX is opened, which is sketched as C→O, a push–pull π-conjugated segment is formed, having the potential to enhance β and to set the depolarization ratio (DR) to its one-dimensional-like value (DR = 5). This is observed when only one BOX is open, either for the monoBOX species (C→O) or for the diBOX (CC→CO) and triBOX (CCC→CCO) compounds, i.e., when the remaining BOXs stay closed. The next BOX openings have much different effects. For the diBOXs, the second opening (CO→OO) is associated with a decrease of β, and this decrease is tuned by controlling the conformation of the π-linker, i.e., the centrosymmetry of the whole compound because β vanishes in centrosymmetric compounds. For the triBOXs, the second opening gives rise to a Λ-shape compound, with a negligible change of β, but a decrease of the DR whereas, along the third opening, β remains similar and the DR decreases to the typical value of octupolar systems (DR = 1.5). 相似文献