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61.
The morphology of WC grains is examined by ab initio calculations, and by transmission electron microscopy in a WC-Co cemented carbide. Two compositions are studied to determine the effect of carbon chemical potential on the shape development. The WC grains are found to be truncated triangles, and the grain morphology is adequately reproduced by the ab initio calculations. The energy difference between the two types of grain facets is shown to be due to the formation of stronger bonds with more covalent character between low coordinated W and Co atoms at one type of facet. 相似文献
62.
Phipps RK Petersen BO Christensen KB Duus JØ Frisvad JC Larsen TO 《Organic letters》2004,6(20):3441-3443
[structure: see text] Hesseltin A 1, a novel compound of mixed polyketide-terpenoid origins was isolated from the filamentous fungus Penicillium hesseltinei. The structure and stereochemistry were determined from extensive one- and two-dimensional NMR and mass spectral data. 相似文献
63.
Abrahamian E Fox PC Naerum L Christensen IT Thøgersen H Clark RD 《Journal of chemical information and computer sciences》2003,43(2):458-468
Pharmacophore triplets and quartets have been used by many groups in recent years, primarily as a tool for molecular diversity analysis. In most cases, slow processing speeds and the very large size of the bitsets generated have forced researchers to compromise in terms of how such multiplets were stored, manipulated, and compared, e.g., by using simple unions to represent multiplets for sets of molecules. Here we report using bitmaps in place of bitsets to reduce storage demands and to improve processing speed. Here, a bitset is taken to mean a fully enumerated string of zeros and ones, from which a compressed bitmap is obtained by replacing uniform blocks ("runs") of digits in the bitset with a pair of values identifying the content and length of the block (run-length encoding compression). High-resolution multiplets involving four features are enabled by using 64 bit executables to create and manipulate bitmaps, which "connect" to the 32 bit executables used for database access and feature identification via an extensible mark-up language (XML) data stream. The encoding system used supports simple pairs, triplets, and quartets; multiplets in which a privileged substructure is used as an anchor point; and augmented multiplets in which an additional vertex is added to represent a contingent feature such as a hydrogen bond extension point linked to a complementary feature (e.g., a donor or an acceptor atom) in a base pair or triplet. It can readily be extended to larger, more complex multiplets as well. Database searching is one particular potential application for this technology. Consensus bitmaps built up from active ligands identified in preliminary screening can be used to generate hypothesis bitmaps, a process which includes allowance for differential weighting to allow greater emphasis to be placed on bits arising from multiplets expected to be particularly discriminating. Such hypothesis bitmaps are shown to be useful queries for database searching, successfully retrieving active compounds across a range of structural classes from a corporate database. The current implementation allows multiconformer bitmaps to be obtained from pregenerated conformations or by random perturbation on-the-fly. The latter application involves random sampling of the full range of conformations not precluded by steric clashes, which limits the usefulness of classical fingerprint similarity measures. A new measure of similarity, The Stochastic Cosine, is introduced here to address this need. This new similarity measure uses the average number of bits common to independently drawn conformer sets to normalize the cosine coefficient. Its use frees the user from having to ensure strict comparability of starting conformations and having to use fixed torsional increments, thereby allowing fully flexible characterization of pharmacophoric patterns. 相似文献
64.
Ball G Vant K Christensen N 《Physical review. E, Statistical physics, plasmas, fluids, and related interdisciplinary topics》2000,61(2):1299-1311
We present a detailed numerical study of a chaotic classical system and its quantum counterpart. The system is a special case of a kicked rotor and for certain parameter values possesses cantori dividing chaotic regions of the classical phase space. We investigate the diffusion of particles through a cantorus. A quantum analysis confirms that the cantori act as barriers. We numerically estimate the classical phase space flux through the cantorus per kick and relate this quantity to the behavior of the quantum system. We introduce decoherence via environmental interactions with the quantum system and observe the subsequent increase in the transport of quantum particles through the boundary. 相似文献
65.
Peter G. Casazza Ole Christensen 《Proceedings of the American Mathematical Society》2001,129(1):145-154
A Weyl-Heisenberg frame
for allows every function to be written as an infinite linear combination of translated and modulated versions of the fixed function . In the present paper we find sufficient conditions for to be a frame for , which, in general, might just be a subspace of . Even our condition for to be a frame for is significantly weaker than the previous known conditions. The results also shed new light on the classical results concerning frames for , showing for instance that the condition A>0$">is not necessary for to be a frame for . Our work is inspired by a recent paper by Benedetto and Li, where the relationship between the zero-set of the function and frame properties of the set of functions is analyzed.
for allows every function to be written as an infinite linear combination of translated and modulated versions of the fixed function . In the present paper we find sufficient conditions for to be a frame for , which, in general, might just be a subspace of . Even our condition for to be a frame for is significantly weaker than the previous known conditions. The results also shed new light on the classical results concerning frames for , showing for instance that the condition A>0$">is not necessary for to be a frame for . Our work is inspired by a recent paper by Benedetto and Li, where the relationship between the zero-set of the function and frame properties of the set of functions is analyzed.
66.
This paper presents a new algorithm for optimal parameter estimation problems with linear constraints. The algorithm developed is based on least absolute-value approximations. The problem is solved first using a least-error-square technique, where we add to the cost function the equality constraints via Lagrange multipliers, to obtain a good estimate for the residuals of the measurements, having gained this information, we choose a number of measurements with the smallest residuals. This number equals the number of parameters to be estimated minus the number of constraints. Using these measurements together with the constraints, we obtain a number of observations equal to the number of parameters to be estimated. By using this technique, we show that there is no need to either iterate or use linear programming to obtain the estimation.This work was supported by the Natural Sciences and Engineering Research Council of Canada, Grant A4146. 相似文献
67.
Reed M. Izatt Gypzy C. Lindh Ronald L. Bruening Peter Huszthy John D. Lamb Jerald S. Bradshaw James J. Christensen 《Journal of inclusion phenomena and macrocyclic chemistry》1987,5(6):739-745
The macrocycle-mediated fluxes of several alkali metal cations have been determined in a H2O-CH2Cl2-H2O liquid membrane system. Water-insoluble proton-ionizable macrocycles of the pyridono type were used. The proton-ionizable feature allows the coupling of cation transport to reverse H+ transport. This feature offers promise for the effective separation and/or concentration of alkali metal ions with the metal transport being driven by a pH gradient. A counter anion in the source phase is not co-transported. The desired separation of a particular metal ion involves its selective complexation with the macrocycle, subsequent extraction from the aqueous phase to the organic phase, and exchange for H+ at the organic phase-receiving phase interface. Factors affecting transport which were studied include ring size, source phase pH, and receiving phase pH. Lithium was transported at a rate higher than that of the other alkali metals in both single and competitive systems using a 15-crown-5 pyridono carrier. 相似文献
68.
Jan F. Biernat Maria Bochenska Jerald S. Bradshaw Hiroyuki Koyama Gypzy Lindh John D. Lamb James J. Christensen Reed M. Izatt 《Journal of inclusion phenomena and macrocyclic chemistry》1987,5(6):729-738
Five new macrocyclic ligands each containing two sulfonamide groups have been prepared. Three of these compounds contain one or two chloro substituents and the other two have one or two pyridine subcyclic units. A seventeen-membered ring ligand (4) was found to be an excellent transport agent for all alkali metal cations in a water-methylene chloride-water bulk liquid membrane system when the pH of the source phase was 13 or higher. The chlorine-substituted analog (5) was a poor transport agent for the alkali metal cations possibly because the chlorine atom blocked entry to the macrocycle cavity. An open-chain analog containing two sulfonamide groups was particularly effective in transporting cesium ions. 相似文献
69.
A high performance liquid chromatography (HPLC) method with fluorescence detection including an on-line purification was established for determination of catecholamines in human urine. The method was evaluated using samples of pooled urine spiked with catecholamines and validated for measurements of catecholamines in urine of healthy individuals in a field study. The laboratory method evaluation study showed that the recovery of the method was 0.82 (confidence interval (CI): 0.79-0.86) and 0.92 (CI: 0.89-0.95) for noradrenaline and adrenaline, respectively. Thus, correction factors of 0.82(-1) and 0.92(-1) were applied to correct the measurement results for this systematic effect. Furthermore, an uncertainty budget was generated for the analytical method using the BIPM-approach recommended by the International Organization for Standardization. The relative uncertainty of the method was estimated to be 10-12%, which was consistent with the observed relative variability found in the method evaluation. The method was evaluated in accordance with EURACHEM Guidance Document No 1 concerning accreditation for chemical laboratories with respect to accuracy and precision. The field study showed that the standard deviation of the method was sufficiently low to distinguish between persons working with two different processes of garbage collection, i.e. collection using four wheeled containers versus collection using bins. 相似文献
70.
M. D. Thompson J. S. Bradshaw S. F. Nielsen C. T. Bishop F. T. Cox P. E. Fore G. E. Maas R. M. Izatt J. J. Christensen 《Tetrahedron》1977,33(24):3313-3316
A series of macrocyclic ether-esters has been prepared by treating various glycols with adipoyl chloride and various substituted malonyl, succinyl and glutaryl chlorides. The prepared compounds include: 15-ethyl- and 15-phenyl-1,4,7,10,13-pentaoxacyclohexadecane-14,16-dione (5 and 6); 15-methyl-, 15-phenyl-, cis-cyclohexo-[o]-and benzo-[o]-1,4,7,10,13-pentaoxacycloheptadecane-14,17-dione (7–10); trans,trans-1,4,7,10,13,18,21,24,27,30-de-caoxacyclotetratriacontane-15, 32-diene-14,17,31,34-tetraone (11); 1,4,7,10,13-pentaoxacyclooctadecane-14,18-dione (12); 15,15,16,16,17,17-hexafluoro- and 16-methyl-1,4,7,10,13-pentaoxacyclooctadecane-14,18-dione (13 and 14); 1,4,7,10-tetraoxacyclohexadecane-11,16-dione (15); and 1,4,7,10,13-pentaoxacyclononadecane-14,19-dione (16). 相似文献