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101.
Martin V. Day 《Journal of Dynamics and Differential Equations》1996,8(4):573-601
We discuss the phenomenon of cycling for noise induced escape to a unstable periodic orbit. The presence of cycling is shown to follow from qualitative properties of two quasipotential functions. A method of numerically evaluating these quasipotential functions is described, and applied to the Van der Pol oscillator as an example. Figures resulting from these calculations reveal that nonconvergent cycling of exit measures does occur for the Van der Pol example. 相似文献
102.
Guochuan Yin Suparna Baksi Roy Andrew M. Danby Victor Day John Carter William M. Scheper Daryle H. Busch 《Journal of inclusion phenomena and macrocyclic chemistry》2011,71(3-4):311-318
On the basis of mass spectral studies alone, the relatively new manganese complex, Mn(Et2EBC)Cl2 (Et2EBC = 4,11-diethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane), a homolog of the well proven, peroxide-based laundry bleach, Mn(Me2EBC)Cl2, has been reported to undergo a sequence of 2-electron oxidation steps, ultimately converting its ethyl groups into chelated ethoxo and methylene carboxylato groups, [MnIV{(?OCH2CH2)(?O2CCH2)}EBC)](PF6)2. We report here the isolation and characterization of that unusual product, and provide insight into the remarkable catalytic pathway to its formation. At temperatures above 0 °C, oxidation by aqueous H2O2 reliably transforms Mn(Et2EBC)Cl2 into [MnIV{(?OCH2CH2)(?O2CCH2)}EBC)]2+. The experimental data for this intramolecular ethyl group transformation is consistent with oxygen insertion into a methyl C?CH moiety of the ethyl group, ?CNCH2C(?CH)H2, by the MnIV?COOH functional group. 相似文献
103.
Bonnel D Longuespee R Franck J Roudbaraki M Gosset P Day R Salzet M Fournier I 《Analytical and bioanalytical chemistry》2011,401(1):149-165
The large amount of data generated using matrix-assisted laser desorption/ionization mass spectrometric imaging (MALDI-MSI)
poses a challenge for data analysis. In fact, generally about 1.108–1.109 values (m/z, I) are stored after a single MALDI-MSI experiment. This imposes processing techniques using dedicated informatics tools
to be used since manual data interpretation is excluded. This work proposes and summarizes an approach that utilizes a multivariable
analysis of MSI data. The multivariate analysis, such as principal component analysis–symbolic discriminant analysis, can
remove and highlight specific m/z from the spectra in a specific region of interest. This approach facilitates data processing and provides better reproducibility,
and thus, broadband acquisition for MALDI-MSI should be considered an effective tool to highlight biomarkers of interest.
Additionally, we demonstrate the importance of the hierarchical classification of biomarkers by analyzing studies of clusters
obtained either from digested or undigested tissues and using bottom-up and in-source decay strategies for in-tissue protein
identification. This provides the possibility for the rapid identification of specific markers from different histological
samples and their direct localization in tissues. We present an example from a prostate cancer study using formalin-fixed
paraffin-embedded tissue. 相似文献
104.
Wan S Wu F Rech JC Green ME Balachandran R Horne WS Day BW Floreancig PE 《Journal of the American Chemical Society》2011,133(41):16668-16679
The potent cytotoxins pederin and psymberin have been prepared through concise synthetic routes (10 and 14 steps in the longest linear sequences, respectively) that proceed via a late-stage multicomponent approach to construct the N-acyl aminal linkages. This route allowed for the facile preparation of a number of analogs that were designed to explore the importance of the alkoxy group in the N-acyl aminal and functional groups in the two major subunits on biological activity. These analogs, including a pederin/psymberin chimera, were analyzed for their growth inhibitory effects, revealing several new potent cytotoxins and leading to postulates regarding the molecular conformational and hydrogen bonding patterns that are required for biological activity. Second generation analogs have been prepared based on the results of the initial assays and a structure-based model for the binding of these compounds to the ribosome. The growth inhibitory properties of these compounds are reported. These studies show the profound role that organic chemistry in general and specifically late-stage multicomponent reactions can play in the development of unique and potent effectors for biological responses. 相似文献
105.
Nickel hydrides supported by a terphenyl diphosphine were synthesized and found to undergo nickel-to-arene H-transfers. Some of the resulting complexes also undergo the reverse (C-to-Ni) H-migration, indicating the potential for storing H-equivalents in this type of pincer ligand. NMR spectroscopy, single crystal X-ray diffraction, and isotopic labeling studies investigating the mechanism of these processes are discussed. 相似文献
106.
Páez-Hernández D Murillo-López JA Arratia-Pérez R 《The journal of physical chemistry. A》2011,115(32):8997-9003
A systematic study of a series of An(COT)(2) compounds, where An = Th, Pa, U, and COT represents cyclooctatetraene, has been performed using relativistic density functional theory. The ZORA Hamiltonian was applied for the inclusion of relativistic effects, taking into account all of the electrons for the optimization and explicitly including spin-orbit coupling effects. Time-dependent density functional theory (TDDFT) was used to calculate the excitation energies with the GGA SAOP functional, and the electronic transitions were analyzed using double group irreducible representations. The calculated excitation energies are in perfect correlation with the increment of the ring delocalization as it increases along the actinide series. These results are sufficient to ensure that, for these complexes, the increment in delocalization, as indicated by ELF bifurcation and NICS analysis, leads to a shift in the maximum wavelength of absorption in the visible region. Also, delocalization in the COT ring increases along the actinide series, so the systems become more aromatic because of a modulation induced by the actinides. 相似文献
107.
We have applied crystal structure prediction methods to understand and predict the formation of a DMSO solvate of the anti-convulsant drug carbamazepine (CBZ), in which the DMSO molecules are disordered. Crystal structure prediction calculations on the 1:1 CBZ:DMSO solvate revealed the generation of two similar low energy structures which differ only in the orientation of the DMSO molecules. Analysis of crystal energy landscapes generated at 0 K suggests the possibility of solvent disorder. A combined computational and experimental study of the changes in the orientation of the DMSO within the crystal structure revealed that the nature of the disorder changes with temperature. At low temperature, the DMSO disorder is static whilst at high temperature the DMSO configurations can interconvert by a 180° rotation of the DMSO molecules within the lattice. This 180° rotation of the DMSO molecules drives a phase change from a high temperature dynamically disordered phase to a low temperature phase with static disorder. Crystallisation of a DMSO solvate of the related molecule epoxycarbamazepine resulted in a different degree of DMSO disorder in the crystal structure, despite the similarity of the carbamazepine and epoxycarbamazepine molecules. We believe consideration of disorder and its contribution to entropy and crystal free energies at temperature other than 0 K is fundamental for the accuracy of future energy rankings in crystal structure prediction calculations of similar solvated structures. 相似文献
108.
109.
A range of nematogenic materials which incorporate a 2,6-disubstituted naphthyl moiety and a terminal cyano-substituent have been synthesized by using palladium-catalysed cross-coupling procedures involving arylboronic acids and alkynylzinc reagents with aryl iodides, bromides and trifluoromethanesulphonates (triflates). The compounds have very high nematic phase stability, but their melting points are also quite high. The birefringences were measured using an extrapolation technique and the values were found to be between 0·26 and 0·42. 相似文献
110.
A multi-level recording method is implemented in a photobleaching polymer using two-photon excitation under continuous wave illumination. It is experimentally shown that information encoded with ten levels of darkness can be successfully stored. This multi-level bit optical data storage method is of importance in increasing the storage density of a recording material and the speed of data access. 相似文献