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41.
Namık Özdemir Serkan Dayan Muharrem Dinçer Nilgün Ö. Kalaycıoğlu 《Molecular physics》2013,111(6):707-723
The Schiff base compound (E)-N-{2-[(2-hydroxybenzylidene)amino]phenyl}benzenesulfonamide has been synthesized and characterized by IR, NMR and Uv-vis spectroscopies, and single-crystal X-ray diffraction technique. In addition, quantum chemical calculations employing density functional theory (DFT) method with the 6–311++G(d,p) basis set were performed to study the molecular, spectroscopic and some electronic structure properties of the title compound, and the results were compared with the experimental findings. There exists a good correlation between experimental and theoretical data. Enol-imine/keto-amine tautomerization mechanism was investigated in the gas phase and in solution phase using the polarizable continuum model (PCM) approximation. The energetic and thermodynamic parameters of the enol-imine?→?keto-amine transfer process show that the single proton exchange is thermodynamically unfavored both in the gas phase and in solution phase. However, the reverse reaction seems to be feasible with a low barrier height and is supported by negative values in enthalpy and free energy changes both in the gas phase and in solution phase. The solvent effect is found to be sizable with increasing polarity of the solvents for the reverse reaction. The predicted nonlinear optical properties of the compound are found to be much greater than those of urea. 相似文献
42.
A molecular dynamics (MD) study of α,ω-dimethoxypolyethylene glycol has been carried out under various conditions with respect to solvent composition, ionic strength, chain length, force field and temperature. A previous MD study on a 15-mer of polyethyleneglycol (PEG) suggested a helical equilibrium structure that was stabilised by hydrogen bonding and bridging water molecules. Experiments show that PEG is highly soluble in water, and indicate that clustering is not favoured. In the present study using different force fields, the GROMOS force fields 45A3 and 53A6, a variation on the latter 53A6_OE, and a force field by Smith et al. produced different results. For the GROMOS force fields 45A3 and 53A6 no helical structure was found, but formation of more or less compact random coils in aqueous solution due to hydrophobic interactions was observed. For the other two force fields used, α,ω-dimethoxypolyethylene glycol stayed flexible and more or less elongated in aqueous solution, more in agreement with experimental observations and the previous MD study. 相似文献
43.
Although there exist a number of methods, such as NMR, X-ray, e.g., which explore the hydration of phospholipid bilayers,
the solvent relaxation (SR) method has the advantage of simple instrumentation, easy data treatment and possibility of measuring
fully hydrated samples. The main information gained from SR by the analysis of recorded “time-resolved emission spectra” (TRES)
is micro-viscosity and micro-polarity of the dye microenvironment. Based on these parameters, one can draw conclusions about
water structure in the bilayer. In this review, we focus on physical background of this method, on all the procedures that
are needed in order to obtain relevant parameters, and on the requirements on the fluorescence dyes. Furthermore, a few recent
applications (the effect of curvature, binding of antibacterial peptides and phase transition) illustrating the versatility
of this method are mentioned. Moreover, limitations and potential problems are discussed. 相似文献
44.
Dielectric relaxation study of the binary mixtures of poly(vinyl pyrrolidone) (PVP) (Mw=24000, 40000 and 360000 g mol−1) with ethyl alcohol (EA) and poly(ethylene glycol)s (PEGs) (Mw=200 and 400 g mol−1) in dilute solutions of dioxane were carried out at 10.1 GHz and 35°C. The relaxation time of PVP-EA mixtures was interpreted
by the consideration of a wait-and-switch model in the local structure of self-associated ethyl alcohol molecules and also
the PVP chain length as a geometric constraint for the reorientational motion of ethyl alcohol molecules. The formation of
complexes and effect of PVP chain length on the molecular dynamics, chain flexibility and stretching of PEG molecules in PVP-PEG
mixtures were explored from the comparative values of dielectric relaxation time. Further, relaxation time values in dioxane
and benzene solvent confirm the viscosity independent molecular dynamics in PVP-EA mixtures but the values vary significantly
with the non-polar solvent environment. 相似文献
45.
Noora Virtanen Ville Nevalainen Taru Lehtinen Satu Mikkola 《Journal of Physical Organic Chemistry》2007,20(1):72-82
Transesterification of a phosphodiester bond of RNA models has been studied in various buffer solutions, under neutral and slightly alkaline conditions in H2O and D2O. The results show that imidazole is the only buffer system where a clear buffer catalysis on the cleavage of a phosphodiester bond is observed. The rate enhancement in sulphonic acid buffers is smaller, and a sulphonate base, particularly, is inactive as a catalyst. The rate‐enhancing effect of imidazole is, however, catalytic, and the catalytic inactivity of sulphonate buffers can be attributed to their structure and/or charge. The catalysis by imidazole is a complex system which, in addition to first‐order reactions, involves a process that shows a second‐order dependence in imidazole concentration. The latter reaction becomes significant in acidic imidazole buffers (pH < pKa), as the buffer concentration increases. The kinetic solvent deuterium isotope effect kH/kD, referring to first‐order catalysis by imidazole base, is 2.3 ± 0.3. That referring to second‐order catalysis is most probably much larger, but an accurate value could not be obtained. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
46.
Effect of variation of dielectric constant on the magnetic field modulation of exciplex luminescence
The effect of variation of dielectric constant on the relative magnetic field effect in singlet luminescence has been studied
using a typical exciplex system at a saturating field. The study indicates strong specificity in the perturbation of the magnetic
field effect by alcoholic solvents. In contrast to alcohols where relative singlet magnetic field effect is of the order of
2% only, the magnetic field effect in non-alcoholic medium reaches as high as 9%. Moreover, dielectric constant variation
in alcohols yields curves which are distinctly different from those in non-alcoholic media. It turns out that this dependence
of magnetic field effect on dielectric constant is similar in all non-alcoholic solvent mixtures. An analytical study based
on Hong and Noolandi’s solution of Smoluchowski equation has been made. Derived expressions can interpret experimental curves
reasonably well. 相似文献
47.
Htun T 《Journal of fluorescence》2004,14(2):217-222
A negative deviation from the normal Stern-Volmer equation shown in the fluorescence quenching of doxorubicin by adenosine 5' monophosphate is interpreted in terms of doxorubicin exists in two different conformers in the ground state. An estimate of the Stem-Volmer constant for the excited-state quenching is about 218 M(-1). The fluorescence decay of free doxorubicin is a bi-exponential in polar protic and polar aprotic solvents. In the presence of adenosine 5' monophosphate, doxorubicin shows a tri-exponential decay in water. 相似文献
48.
Solvent and electric field dependence of the photocurrent generation in donor:acceptor blend system 下载免费PDF全文
This paper reports that the blend films of poly
(2-methoxy-5-(2'-ethyl-hexyloxy)-p-phenylene vinylene) (MEH-PPV)
and N,N'-bis(1-ethylpropyl)-3,4: 9,10-perylene bis
(tetracarboxyl diimide) (EP-PDI) with the weight ratio of 1:2.5
have been prepared by spin-coating from chloroform (CF) and
chlorobenzene (CB) solutions respectively. The absorption
spectra and the morphology of the blend films show that large
crystal-like EP-PDI aggregates are formed in film prepared from
CB solution, which corresponds to a new absorption shoulder near
590nm, while there is no shoulder around 590\,nm in the
UV--Vis absorption spectra of the blend film from CF solution.
The electric-field dependence spectra of the photocurrent
generation quantum yield of the film from CB solution shows that
at weak electric field the EP-PDI aggregates act as more
efficient sensitizers, but at strong electric field the quantum
yields become almost invariable over the entire spectral range
no matter what the state of EP-PDI, monomer or aggregate. At
strong electric field, the photocurrent generation yields of
both films from CF and CB solution saturate and their yield
spectra become spectrally similar, mentioning that at strong
electric field the photoexcitons dissociate efficiently and the
free charges are collected by the electrodes almost completely. 相似文献
49.
Bishwajit Ganguly Marija Matković Nikola Basarić Kata Mlinarić‐Majerski 《Journal of Physical Organic Chemistry》2011,24(7):578-587
The hydrolysis of ethyl threo‐2‐(1‐adamantyl)‐3‐hydroxybutyrate ( 1 ) and the parent ester ethyl 3‐hydroxybutyrate ( 4 ) has been studied experimentally and computationally. In the hydrolysis of threo‐ester 1 with 2 M NaOH, predominantly retro‐aldol product was observed, whereas the hydrolyzed product was present in a minor amount. When the reaction is carried out under the same conditions with the parent ester ethyl 3‐hydroxybutyrate ( 4 ), hydrolyzed product is exclusively observed. The competitive pathways, namely hydrolysis and the retro‐aldol reaction for 1 and 4 were investigated using DFT calculations in the both gas and solvent phase. The calculated results in the solvent phase at B3LYP/6–31 + G* level revealed that the formation of retro‐aldol products is kinetically preferred over the hydrolysis of threo‐ester 1 in the presence of a base. However, the parent ester 4 showed that the retro‐aldol process is less favored than the hydrolysis process under similar conditions. The steric effect imposed by the bulky adamantyl group to enhance the activation barriers for the hydrolysis of the ethyl threo‐2‐(1‐adamantyl)‐3‐hydroxybutyrate ( 1 ) was further supported by the calculations performed with tert‐butyl group at the α‐carbon atom of ethyl 3‐hydroxybutyrate ( 7 ). Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
50.
Ricardo D. Torres Stephen L. Johnson Richard F. Haglund Jr. Jungseek Hwang Paul L. Burn Paul H. Holloway 《固体与材料科学评论》2011,36(1):16-45
For the last decade, a variant of pulsed laser ablation, Resonant-Infrared Matrix-Assisted Pulsed Laser Evaporation (RIR-MAPLE), has been studied as a deposition technique for organic and polymeric materials. RIR-MAPLE minimizes photochemical damage from direct interaction with the intense laser beam by encapsulating the polymer in a high infrared-absorption solvent matrix. This review critically examines the thermally-induced ablation mechanisms resulting from irradiation of cryogenic solvent matrices by a tunable free electron laser (FEL). A semi-empirical model is used to calculate temperatures as a function of time in the focal volume and determine heating rates for different resonant modes in two model solvents, based on the thermodynamics and kinetics of the phase transitions induced in the solvent matrices. Three principal ablation mechanisms are discussed, namely normal vaporization at the surface, normal boiling, and phase explosion. Normal vaporization is a highly inefficient polymer deposition mechanism as it relies on collective collisions with evaporating solvent molecules. Diffusion length calculations for heterogeneously nucleated vapor bubbles show that normal boiling is kinetically limited. During high-power pulsed-FEL irradiation, phase explosion is shown to be the most significant contribution to polymer deposition in RIR-MAPLE. Phase explosion occurs when the target is rapidly heated (108 to 1010 K/s) and the solvent matrix approaches its critical temperature. Spontaneous density stratification (spinodal decay) within the condensed metastable phase leads to rapid homogeneous nucleation of vapor bubbles. As these vapor bubbles interconnect, large pressures build up within the condensed phase, leading to target explosions and recoil-induced ejections of polymer to a near substrate. Phase explosion is a temperature (fluence) threshold-limited process, while surface evaporation can occur even at very low fluences. 相似文献