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181.
Bartolomei M Carmona-Novillo E Hernández MI Campos-Martínez J Hernández-Lamoneda R 《The Journal of chemical physics》2010,133(12):124311
Completely ab initio global potential energy surfaces (PESs) for the singlet and triplet spin multiplicities of rigid O(2)((3)Σ(g)(-))+O(2)((3)Σ(g)(-)) are reported for the first time. They have been obtained by combining an accurate restricted coupled cluster theory with singles, doubles, and perturbative triple excitations [RCCSD(T)] quintet potential [Bartolomei et al., J. Chem. Phys. 128, 214304 (2008)] with complete active space second order perturbation theory (CASPT2) or, alternatively, multireference configuration interaction (MRCI) calculations of the singlet-quintet and triplet-quintet splittings. Spherical harmonic expansions, containing a large number of terms due to the high anisotropy of the interaction, have been built from the ab initio data. The radial coefficients of these expansions are matched at long range distances with analytical functions based on recent ab initio calculations of the electric properties of the monomers [M. Bartolomei, E. Carmona-Novillo, M. I. Hernández, J. Campos-Martínez, and R. Hernández-Lamoneda, J. Comput. Chem. (2010) (in press)]. The singlet and triplet PESs obtained from either RCCSD(T)-CASPT2 or RCCSD(T)-MRCI calculations are quite similar, although quantitative differences appear in specific terms of the expansion. CASPT2 calculations are the ones giving rise to larger splittings and more attractive interactions, particularly in the region of the absolute minima (in the rectangular D(2h) geometry). The new singlet, triplet, and quintet PESs are tested against second virial coefficient B(T) data and, their spherically averaged components, against integral cross sections measured with rotationally hot effusive beams. Both types of multiconfigurational approaches provide quite similar results, which, in turn, are in good agreement with the measurements. It is found that discrepancies with the experiments could be removed if the PESs were slightly more attractive. In this regard, the most attractive RCCSD(T)-CASPT2 PESs perform slightly better than the RCCSD(T)-MRCI counterpart. 相似文献
182.
Marta Worzakowska 《Journal of Thermal Analysis and Calorimetry》2010,102(2):745-750
The influence of the structure of succinic or glutaric anhydride modified linear unsaturated (epoxy) polyesters on the course
of the cure reaction with styrene initiated by benzoyl peroxide (BPO) or the mixture of benzoyl peroxide/tetrahydrophthalic
anhydride (BPO/THPA) or benzoyl peroxide/maleic anhydride, as well as viscoelastic properties and thermal behavior of their
styrene copolymers have been studied by DSC, DMA, and TGA analyses. Additionally, mechanical properties: flexural properties
using three-point bending test and Brinell’s hardness for studied copolymers were evaluated. It was confirmed that the structure
of used polyesters had a considerable influence on the course of the cure reaction with styrene, viscoelastic, thermal, and
mechanical properties of prepared styrene copolymers. Generally, one or two asymmetrical peaks for the cure reaction of succinic
or glutaric anhydride modified linear unsaturated epoxy polyesters with styrene were observed. They were connected with various
cure reaction, e.g., copolymerization of carbon–carbon double bonds of polyester with styrene, thermal curing of epoxy groups,
polyaddition reaction of epoxy to anhydride groups in dependence of used curing system. In addition, only one asymmetrical,
exothermic peak attributed to the copolymerization process of succinic or glutaric anhydride modified linear unsaturated polyesters
with styrene was visible. Moreover, the obtained styrene copolymers based on succinic or glutaric anhydride modified linear
unsaturated epoxy polyesters were characterized by higher values of
E20 °\textC¢ E_{{20\,^{\circ}{\text{C}}}}^{\prime} , T
g, E″, ν
e, E
mod, F
max, hardness, IDT, FDT but lower ε − F
max compared to those values observed for styrene copolymers prepared in the presence of succinic or glutaric anhydride modified
linear unsaturated polyesters. This supported to the production of stiffer and more thermally stable polymeric structure of
copolymers based on unsaturated epoxy polyesters. Moreover, the copolymers prepared in the use of glutaric anhydride modified
linear unsaturated (epoxy) polyesters were described by lower values of
E20 °\textC¢ E_{{20\,^{\circ}{\text{C}}}}^{\prime} , T
g, E″, ν
e, E
mod, F
max, hardness, IDT, FDT but higher ε − F
max than those based on succinic anhydride modified linear unsaturated (epoxy) polyesters. The presence of longer aliphatic chain
length in polyester’s structure leads to produce more flexible network structure of styrene copolymers based on glutaric anhydride
modified linear unsaturated (epoxy) polyesters than those based on succinic anhydride modified linear unsaturated (epoxy)
polyesters. 相似文献
183.
Edward Mikuli Marta Liszka-Skoczylas Joanna Hetmańczyk Janusz Szklarzewicz 《Journal of Thermal Analysis and Calorimetry》2010,102(3):889-897
[Mn(NH3)6](NO3)2 crystallizes in the cubic, fluorite (C1) type crystal lattice structure (Fm \( \overline{3} \) m) with a = 11.0056 Å and Z = 4. Two phase transitions of the first-order type were detected. The first registered on DSC curves as a large anomaly at T C1 h = 207.8 K and T C1 c = 207.2 K, and the second registered as a smaller anomaly at T C2 h = 184.4 K and T C2 c = 160.8 K (where the upper indexes h and c denote heating and cooling of the sample, respectively). The temperature dependence of the full width at half maximum of the band associated with the δs(HNH)F1u mode suggests that the NH3 ligands in the high temperature and intermediate phase reorientate quickly with correlation times in the order of several picoseconds and with activation energy of 9.9 kJ mol?1. In the phase transition at T C2 c probably only a some of the NH3 ligands stop their reorientation, while the remainders continue to reorientate quickly with activation energy of 7.7 kJ mol?1. Thermal decomposition of the investigated compound starts at 305 K and continues up to 525 K in four main stages (I–IV). In stage I, 2/6 of all NH3 ligands were seceded. Stages II and III are connected with an abruption of the next 2/6 and 1/6 of total NH3, respectively, and [Mn(NH3)](NO3)2 is formed. The last molecule of NH3 per formula unit is freed at stage IV together with the simultaneous thermal decomposition of the resulting Mn(NO3)2 leading to the formation of gaseous products (O2, H2O, N2 and nitrogen oxides) and solid MnO2. 相似文献
184.
Marta Worzakowska 《Journal of Thermal Analysis and Calorimetry》2010,100(2):599-605
In pseudo bi-component separated-stage model (PBSM), the effect of the TG value at separation points on the kinetic parameters is studied by residual and theoretical analysis. Simultaneously, a new method to determine the point that is the end of 1st reaction or the initial of 2nd reaction is developed. The investigations have improved the calculation procedure of PBSM. We performed thermogravimetry (TG) analysis on oil tea wood with two-step consecutive model and parallel model. Comparison between the results of the two models and improved PBSM shows well agreements. The influence of different separation points on kinetic parameters is presented. 相似文献
185.
Fic E Kedracka-Krok S Jankowska U Pirog A Dziedzicka-Wasylewska M 《Electrophoresis》2010,31(21):3573-3579
Sample preparation is a fundamental step in proteomic methodologies. The quality of the results from a proteomic experiment is dependent on the nature of the sample and the properties of the proteins. In this study, various pre-treatment methods were compared by proteomic analysis; we analysed various rat brain structures after chloroform/methanol, acetone, TCA/acetone and TCA protein precipitation procedures. The protein content of the supernatant was also examined by 2-DE. We found that for four of the rat brain structures, precipitation with chloroform/methanol and acetone delivered the highest protein recovery for top-down proteomic analysis; however, TCA precipitation resulted in good protein separation and the highest number of protein spots in 2-DE. Moreover, TCA precipitation also gave high efficiency of protein recovery if prior sonication procedure was performed. 相似文献
186.
Joanna Luszczyn Marta E. Plonska‐Brzezinska Dr. Amit Palkar Dr. Alina T. Dubis Dr. Agneta Simionescu Dr. Dan T. Simionescu Dr. Beata Kalska‐Szostko Dr. Krzysztof Winkler Prof. Dr. Luis Echegoyen Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(16):4870-4880
Small carbon nano‐onions (CNOs, 6–8 shells) were prepared in high yield and functionalized with carboxylic groups by chemical oxidation. After functionalization these nanostructures were soluble in aqueous solutions. 3‐(4,5‐dimethylthiazol‐2‐yl)‐5‐(3‐carboxymethoxyphenyl)‐2‐(4‐sulfophenyl)‐2 tetrazolium (MTS) tests showed excellent cytocompatibility of all CNOs analyzed at 30 and 300 μg mL?1, so these carbon nanostructures can be safely used for biological applications. The first covalent functionalization of oxidized CNOs (ox‐CNOs) with biomolecules, by using biotin–avidin interactions is reported here. Multilayers were prepared on a gold surface by layer‐by‐layer assembly and the process was monitored by surface plasmon resonance (SPR) spectroscopy and atomic force microscopy (AFM). Covalent binding of molecules to the short amine‐terminated organosulfur monolayers was assessed by Fourier transform infrared spectroscopy using total attenuated reflactance mode (FT‐IR/HATR). 相似文献
187.
Lamas JP Sanchez-Prado L Garcia-Jares C Lores M Llompart M 《Journal of chromatography. A》2010,1217(52):8087-8094
A new method based on solid phase dispersion-pressurized liquid extraction (PLE) followed by gas chromatography-mass spectrometry (GC-MS) has been developed for the determination of 26 suspected fragrance allergens (all the regulated in the EU Cosmetics Directive amenable by GC, as well as pinene and methyleugenol) in cosmetic samples. The effects of the temperature, extraction time and solvent, and dispersing sorbent, affecting the whole proposed procedure, have been evaluated using a multifactor strategy. The optima conditions after the analysis of main and second order effects entailed the extraction at 120°C for 15 min, using hexane/acetone as solvent, and florisil as dispersing sorbent. The method performance has been studied, showing good linearity (R≥0.996) as well as good precision (RSD≤10%). Detection limits (S/N=3) ranged from 0.000001 to 0.0002% (w/w), values far below the established restrictions as regard labelling in the European Cosmetics Regulation. Reliability was demonstrated through the quantitative recoveries of all the studied compounds. The absence of matrix effects allowed quantification of the compounds by calibration with standard solutions. The analysis of 10 samples (several moisturizing and anti-wrinkle creams and lotions, hand creams, and sunscreen and after-sun creams), covering very different matrices, showed the presence of suspected allergens in all the analyzed samples; in fact, half of the samples contained an elevated number of them. Although the ubiquity of these compounds was demonstrated, labelling was in all cases in consonance with the European Cosmetics Regulation. 相似文献
188.
We propose a luminance adaptation model (LAM) to increase the dynamic range of an imaging system when scenes containing areas of low and high illumination are imaged. The LAM that we developed is based on capturing images at different exposure times to obtain digital levels within the linear response zone for all the pixels in the image. The levels are subsequently transformed to a reference exposure time that is common to all pixels. We use a linear transformation whose coefficients are determined by the digital levels obtained for a set of flat-spectrum samples. In this study, the LAM is applied to a multispectral imaging system that is based on a CCD camera used for color measurements and spectral reconstructions. It is shown to be a very useful method for increasing the dynamic range of the system, whilst maintaining its accuracy. 相似文献
189.
Marcella Reale Antonia Patruno Maria A De Lutiis Mirko Pesce Mario Felaco Massimo Di Giannantonio Marta Di Nicola Alfredo Grilli 《BMC neuroscience》2011,12(1):13
Background
The exact cause of schizophrenia is not known, although several aetiological theories have been proposed for the disease, including developmental or neurodegenerative processes, neurotransmitter abnormalities, viral infection and immune dysfunction or autoimmune mechanisms. Growing evidence suggests that specific cytokines and chemokines play a role in signalling the brain to produce neurochemical, neuroendocrine, neuroimmune and behavioural changes. A relationship between inflammation and schizophrenia was supported by abnormal cytokines production, abnormal concentrations of cytokines and cytokine receptors in the blood and cerebrospinal fluid in schizophrenia. Since the neuropathology of schizophrenia has recently been reported to be closely associated with microglial activation we aimed to determined whether spontaneous or LPS-induced peripheral blood mononuclear cell chemokines and cytokines production is dysregulated in schizophrenic patients compared to healthy subjects. We enrolled 51 untreated first-episode schizophrenics (SC) and 40 healthy subjects (HC) and the levels of MCP-1, MIP-1α, IL-8, IL-18, IFN-γ and RANTES were determined by Elisa method in cell-free supernatants of PBMC cultures. 相似文献190.
Michael Heck Klaus Blaum R. Burcu Cakirli Daniel Rodr??guez Lutz Schweikhard Stefan Stahl Marta Ubieto-D??az 《Hyperfine Interactions》2011,199(1-3):347-355
Dipolar and single-phase two-electrode quadrupolar detection schemes have been investigated at a Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) setup built for the KATRIN experiment at the Max-Planck-Institute for Nuclear Physics (MPIK) in Heidelberg. We present first experimental results of 7Li?+? signals from a cylindrical Penning trap configuration for both detection schemes. While the prominent signal of the conventional dipolar detection scheme marks the reduced cyclotron frequency, the main signal for the quadrupolar detection appears at the sum of the reduced cyclotron frequency and the magnetron frequency. For ideal trapping fields, this sum frequency equals the ion cyclotron frequency ?? c ?=?qB/(2??m). Sidebands due to the combined motions of the cyclotron mode and magnetron mode are observed by quadrupolar detection which allows the determination of the respective combinations of eigenfrequencies. 相似文献