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21.
We report the observation and characterization of a series of stable bimetallic 18-valence-electron clusters containing a highly symmetric 12-atom icosahedral Au cage with an encapsulated central heteroatom of Group VB transition metals, M@Au(12) (-) (M=V,Nb,Ta). Electronic and structural properties of these clusters were probed by anion photoelectron spectroscopy and theoretical calculations. Characteristics of the M@Au(12) (-) species include their remarkably high binding energies and relatively simple spectral features, which reflect their high symmetry and stability. The adiabatic electronic binding energies of M@Au(12) (-) were measured to be 3.70+/-0.03, 3.77+/-0.03, and 3.76+/-0.03 eV for M=V, Nb, and Ta, respectively. Comparison of density-functional calculations with experimental data established the highly symmetric icosahedral structures for the 18-electron cluster anions, which may be promising building blocks for cluster-assembled nanomaterials in the form of stoichiometric [M@Au(12) (-)]X(+) salts. 相似文献
22.
Wei F Chen C Zhai L Zhang N Zhao XS 《Journal of the American Chemical Society》2005,127(15):5306-5307
Conventional single nucleotide polymorphism (SNP) assays, which based their detection on the stringency or temperature of the washing buffers, have encountered difficulties to distinguish a single base pair mismatch from a perfect match. In this study, scanning potential hairpin denaturation (SPHD) has been developed to detect SNP in a sensitive and reliable manner. Combined with hairpin oligonucleotide probes, scanning surface electric potential was used to induce a dissociation of double-stranded DNA around a unique "melting potential" (Vm), and it generated a high-contrast SNP recognition signal. A 21 base pair p53 gene segment was used to test this novel method. A single nucleotide mismatch to the hairpin probes caused an average of 400-800 mV difference in melting potential against the perfect match, while the error of this assay was lower than 20 mV. Experiments demonstrated that the hairpin stem was critical to the method. The concept of scanning potential hairpin denaturation could also be used extensively in different areas of nucleotide hybridization based assays. 相似文献
23.
Xiao‐Yuan Wu Quan‐Guo Zhai Li‐Juan Chen Can‐Zhong Lu 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(6):m261-m263
The title complex, poly[di‐μ3‐oxo‐hepta‐μ2‐oxo‐tetraoxobis(1,10‐phenanthroline)‐μ4‐terephthalato‐dicopper(II)tetramolybdate(VI)], [Cu2Mo4(C8H4O4)O13(C12H8N2)2], represents a novel two‐dimensional copper–molybdate compound with mixed ligands. Tetranuclear molybdenum oxide clusters are joined through corner‐sharing into a ribbon‐like chain, with [Cu(phen)]2+ (phen is 1,10‐phenanthroline) complexes grafted onto either side. The terephthalate ligand lies about an inversion centre and links these chains to form a layer via Cu—O and Mo—O bonds. Face‐to‐face π–π stacking interactions between adjacent phen ligands stabilize the structure. 相似文献
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25.
Zhai HJ Yang X Wang XB Wang LS Elliott B Boldyrev AI 《Journal of the American Chemical Society》2002,124(23):6742-6750
Although neutral and ionic O4(0/-/+) species have been observed experimentally and considered for energetic materials, O4(2-) and O5(2-) dianions have not yet been explored. O4(2-) is valent isoelectronic to the well-known ClO3- and SO3(2-) anions, and O5(2-) is valent isoelectronic to ClO4- and SO4(2-). All are stable, common anions in solutions and inorganic salts. In this article, we explore the possibility of making covalently bound O4(2-) and O5(2-) species stabilized in the forms of M+O4(2-) and M+O5(2-) (M = Li, Na, K, Cs) in the gas phase. Laser vaporization experiments using M-containing targets and an O2-seeded carrier gas yielded very intense mass peaks corresponding to MO4- and MO5-. To elucidate the structure and bonding of the newly observed MO4- and MO5- species, we measured their photoelectron spectra and then compared them with ab initio calculations and the spectra of ClO3-, Na+SO3(2-), ClO4-, and Na+SO4(2-). Careful analyses of the experimental and ab initio results showed, however, that the observed species are of the forms, O2-M+O2- and O2-M+O3-. The more interesting M+O4(2-) and M+O5(2-) species were found to be higher-energy isomers, but they are true minima on the potential energy surfaces, which suggests that it might be possible to synthesize bulk materials containing covalently bound tetra- and pentatomic oxygen building blocks. 相似文献
26.
Reversible wettability of a chemical vapor deposition prepared ZnO film between superhydrophobicity and superhydrophilicity 总被引:4,自引:0,他引:4
Liu H Feng L Zhai J Jiang L Zhu D 《Langmuir : the ACS journal of surfaces and colloids》2004,20(14):5659-5661
A superhydrophobic ZnO thin film was fabricated by the Au-catalyzed chemical vapor deposition method. The surface of the film exhibits hierarchical structure with nanostructures on sub-microstructures. The water contact angle (CA) was 164.3 degrees, turning into a superhydrophilic one (CA < 5 degrees) after UV illumination, which can be recovered through being placed in the dark or being heated. The film was attached tightly to the substrate, showing good stability and durability. The surface structures were characterized by scanning electron microscopy and atomic force microscopy. 相似文献
27.
Fine particle superacidic sulfated zirconia (SO42−/ZrO2, S-ZrO2) was synthesized by ameliorated method, and composite membranes with different S-ZrO2 contents were prepared by a recasting procedure from a suspension of S-ZrO2 powder and Nafion solution. The physico-chemical properties of the membranes were studied by ion exchange capacity (IEC) and liquid water uptake measurements, scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis, thermogravimetry–mass spectrometry (TG–MS) and Fourier transform infrared (FT-IR) spectroscopy. The results showed that the IEC of composite membrane increased with the content of S-ZrO2, S-ZrO2 was compatible with the Nafion matrix, the incorporation of the S-ZrO2 could increase the crystallinity and also improve the initial degradation temperature of the composite membrane. The performance of single cell was the best when the S-ZrO2 content was 15 wt.%, and achieved 1.35 W/cm2 at 80 °C and 0.99 W/cm2 at 120 °C based on H2/O2 and at a pressure of 2 atm, the performance of the single cell with optimized S-ZrO2 was far more than that of the Nafion at the same condition (e.g. 1.28 W/cm2 at 80 °C, 0.75 W/cm2 at 120 °C). The 15 wt.% S-ZrO2/Nafion composite membrane showed lower fuel cell internal resistance than Nafion membranes at high temperature and low relative humidity (RH). 相似文献
28.
Novel HPLC methods were developed for the analytical and semipreparative resolution of new antidepressant drug mirtazapine enantiomers. At analytical scale, the separation of the mirtazapine enantiomers was investigated using both cellulose and amylose tris(3,5-dimethylphenylcarbamate) (CDMPC and ADMPC) chiral stationary phases under normal-phases and polar organic modes. Good baseline enantioseparation was achieved using cellulose tris(3,5-dimethylphenylcarbamate) chiral stationary phases under both normal-phases and polar organic modes. Furthermore, the elution order of mirtazapine enantiomic pairs was found reversed by changing the stationary phase from the amylose-based ADMPC–CSPs to its cellulose-based counterpart, CDMPC–CSPs. The validation of the analytical methods including linearity, limit of detection (LOD), limit of quantification (LOQ), recovery and precision, together with the semipreparative resolution of mirtazapine racemate were carried out using cellulose tris(3,5-dimethylphenylcarbamate) chiral stationary phases and methanol as mobile phase without any basic additives under polar organic mode. At analytical scale, the elution times of both enantiomers were less than 6 min at normal temperature and 1.0 ml/min, with the separation factor () 1.99 and the resolution factor (Rs) 3.56. Then, the analytical methods were scaled up to semipreparative loading to obtain small quantities of both mirtazapine enantiomers. At semipreparative scale, about 16 mg/h enantiomers could be isolated and elution times of both enantiomers were less than 10 min at 2.0 ml/min. To increase the throughput, the technique of boxcar injections was used. One enantiomer ((−)-(R)-mirtazapine) was isolated with purity of >99.9% e.e. and >98.0% yield and another ((+)-(S)-mirtazapine) was isolated with purity of >97.0% e.e. and >99.0% yield. In addition, optical rotation and circular dichroism (CD) spectroscopy of both mirtazapine enantiomers isolated were also investigated. 相似文献
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