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41.
Biosurfactant produced from Pseudomonas aeruginosa DSVP20 was evaluated for its potential to disrupt Candida albicans biofilm formed on polystyrene (PS) surfaces in this investigation. P. aeruginosa DSVP20 exhibited optimum production of biosurfactant (5.8 g?L?1) after 96 h of growth with an ability to reduce surface tension of the aqueous solution from 72 to 28 mN?m?1. Analysis of purified biosurfactant with FT-IR, 1H and 13C NMR and MALDI-TOF MS revealed it to be di-rhamnolipid (RL-2) in nature. Biofilm disrupting ability of RL-2 (0.16 mg?mL?1) on Candida cells when checked using XTT reduction assay revealed that about 50 % of the cells remain adhered to 96-well plate after 2 h of treatment, while up to 90 % reduction in pre-formed C. albicans biofilm on PS surface was observed with RL-2 (5.0 mg?mL?1) in a dose-dependent manner. Microscopic analyses (SEM and CLSM) further confirm the influence of RL-2 on disruption of Candida biofilm extracellular matrix on PS surface which can be exploited as a potential alternative to the available conventional therapies.  相似文献   
42.
Storage and separation of small (C1–C3) hydrocarbons are of great significance as these are alternative energy resources and also can be used as raw materials for many industrially important materials. Selective capture of greenhouse gas, CO2 from CH4 is important to improve the quality of natural gas. Among the available porous materials, MOFs with permanent porosity are the most suitable to serve these purposes. Herein, a two‐fold entangled dynamic framework {[Zn2(bdc)2(bpNDI)]?4DMF}n with pore surface carved with polar functional groups and aromatic π clouds is exploited for selective capture of CO2, C2, and C3 hydrocarbons at ambient condition. The framework shows stepwise CO2 and C2H2 uptake at 195 K but type I profiles are observed at 298 K. The IAST selectivity of CO2 over CH4 is the highest (598 at 298 K) among the MOFs without open metal sites reported till date. It also shows high selectivity for C2H2, C2H4, C2H6, and C3H8 over CH4 at 298 K. DFT calculations reveal that aromatic π surface and the polar imide (RNC=O) functional groups are the primary adsorption sites for adsorption. Furthermore, breakthrough column experiments showed CO2/CH4 C2H6/CH4 and CO2/N2 separation capability at ambient condition.  相似文献   
43.
    
In this article we study the thermodynamic properties of a substrate-induced graphene superlattice in the presence of uniform magnetic field B. We derive an expression for the partition function of the system with uniform magnetic field B using the zeta function approach and find all related thermodynamic functions such as Helmholtz free energy, total energy, specific heat capacity and entropy for three cases related to the sublattice potential. We also show that the Dulong-Petit law is verified for all cases in the high-temperature limit. These results may shed light on the study of graphene superlattices in the developement of thermo-electric devices.https://doi.org/10.1209/0295-5075/ace4ef  相似文献   
44.
    
Bimetallic tandem catalysts have emerged as a promising strategy to locally increase the CO flux during electrochemical CO2 reduction, so as to maximize the rate of conversion to C−C-coupled products. Considering this, a novel Cu/C−Ag nanostructured catalyst has been prepared by a redox replacement process, in which the ratio of the two metals can be tuned by the replacement time. An optimum Cu/Ag composition with similarly sized particles showed the highest CO2 conversion to C2+ products compared to non-Ag-modified gas-diffusion electrodes. Gas chromatography and in-situ Raman measurements in a CO2 gas diffusion cell suggest the formation of top-bound linear adsorbed *CO followed by consumption of CO in the successive cascade steps, as evidenced by the increasingνC−H bands. These findings suggest that two mechanisms operate simultaneously towards the production of HCO2H and C−C-coupled products on the Cu/Ag bimetallic surface.  相似文献   
45.
    
The [3 + 2] cycloaddition (32CA) reaction of phenyl azide 4 with ethynylbenzene 5 in presence of ethyl magnesium bromide (EtMgBr) has been studied within the Molecular Electron Density Theory with the aim to rationalise the high-yielding direct regioselective synthesis of 1,5-disubstituted-1,2,3-triazoles. Topological analysis of the electron localisation function (ELF) of phenyl azide 4 indicates that it has a zwitterionic structure participating in zw-type 32CA reactions. Computed activation parameters along the two feasible reaction paths for this 32CA reaction makes the rationalisation of the experimental outcomes possible. Grignard reagent-mediated processes have a polar character and complete regioselectivity, which is in line with the fast, clean, and high yielding reaction experimentally observed. The reaction follows a one-step mechanism involving a high asynchronous transition state structure. Topological analysis of the ELF and calculated quantum theory of atoms-in-molecule parameters indicate that formation of new C–N single bonds does not begin exactly at the corresponding transition state structure.  相似文献   
46.
    
We demonstrate a redox-active, crystalline donor–acceptor (D-A) assembly in which the electron transfer (ET) process can be reversibly switched. This ET process, induced by a guest-responsive structural transformation at room temperature, is realized in a porous, metal–organic framework (MOF), having anthracene (D)–naphthalenediimide (A) as struts. A control MOF structure obtained by a solvent-assisted linker exchange (SALE) method, replacing an acceptor strut with a neutral one, supported the switchable electronic states in the D-A MOF. Combined investigations with X-ray diffraction, spectroscopy, and theoretical analyses revealed the dynamic metal paddle-wheel node as a critical unit for controlling structural flexibility and the corresponding unprecedented ET process.  相似文献   
47.
Abstract

A new redox system, dioxane-ascorbic acid, has been investigated for the homopolymerization of vinyl monomers. Detailed kinetic studies on the aqueous polymerization of acrylamide by this initiating system have been done iodometrically at 35 ± 0.2°C. The effect of various additives, such as organic solvents, inorganic salts, surfactants, etc., on the rate of polymerization has been studied. The retardation constants for organic solvents have been evaluated by the “intercept method.” The overall energy of activation has been found to be 8.75 kcal/deg/mol, within the temperature range 25–45°C. A suitable mechanism has been suggested. The following rate expression: Rp α [acrylamide]1.0 [dioxane]1.0 [ascorbic acid]0, has been observed.  相似文献   
48.

The tandem Cope rearrangement and [2?+?2] cycloaddition of cis-1,2-diethynyl-1,2-dihydroxycyclopropane and its mono-hetero analogues have been investigated at the B3LYP/6-31+G* level. The presence of the hydroxy group lowers the activation enthalpies for the Cope rearrangement, whereas activation enthalpies for the [2?+?2] cycloaddition are raised as compared to those for their non-hydroxy derivatives. The NBO analysis indicates that in the transition structure involved in the Cope rearrangement, lone pairs of the oxygen atoms of the hydroxy groups are transferred into the σ* C–C bond undergoing migration, as a result of which it is weakened. On the other hand, the lone pairs of the oxygen atoms interact with the π* C=C orbitals of the bis-allenic systems in the intermediate thereby stabilizing it and, thus, suppressing its driving ability for the [2?+?2] cycloaddition. In the products so formed, 6π electrons are delocalized conferring stability on them, which is further augmented by extended conjugation with the hydroxy groups. Due to high stability of these products, activation barrier for the change of enol into ketone is very high.

  相似文献   
49.
50.
    
In this article, the modified Kane-Mele Hamiltonian is derived for graphene with wedge disclination and spin orbit couplings (intrinsic and Rashba). The wedge disclination changes the flat lattice into the conical lattice and hence modifies the spin orbit couplings. The Hamiltonian is exactly solved for the intrinsic spin orbit interaction and perturbatively for the Rashba spin orbit interaction. It is shown that there exists Kramer's degenerate midgap localized spin separated fluxon states around the defect. These zero energy spin separated states occur at the external magnetic flux value Φ±ΔΦ. The external magnetic flux Φ is introduced to make the wave function periodic when the electron circulates around the defect. It is found that this separation occurs due to the effect of the conical curvature on the spin orbit coupling. Further, we find these results are robust to the addition of the Rashba spin orbit interaction which is important for the application to spintronics and nanoelectronics.https://doi.org/10.1209/0295-5075/108/57006  相似文献   
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