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51.
J. Cable G. W. Adelstein J. Gore Carl Djerassi 《Journal of mass spectrometry : JMS》1970,3(4):439-453
The mass spectral fragmentation of a number of specially synthesized amino esters and ketones has been studied in which the distance between the two functionalities has been varied. The principal fragments formed following initial ionization are the even-electron immonium ions a and b. Further fragmentation of ion a in the amino esters occurs via non-specific processes. Therefore it is difficult to establish the degree of mobility of the positive charge in the fragment ions, notably whether the species with the charge present on the oxygen atom makes a significant contribution to the fragmentation. The β-(IIb) and γ-(IV) amino ketones show no McLafferty rearrangements after α-fission, thus demonstrating that uncoupling of the carbonyl π electrons is not a feasible trigger in lieu of charge localization. 相似文献
52.
Summary Gauss elimination applied to ann×n matrixA in floating point arithmetic produces (if successful) a factorization
which differs fromA by no more than
, for some of ordern times the unit roundoff. IfA is totally positive, then both computed factors
and
are nonnegative for sufficiently small unit roundoff and one obtains pleasantly small bounds for the perturbation inA which would account for the rounding errors committed in solvingAx=b forx by Gauss eliminationwithout pivoting. It follows that the banded linear system for the B-spline coefficients of an interpolating spline function can be solved safely by Gauss elimination without pivoting.Sponsored by the United States Army under Contract No. DAAG29-75-C-0024 and the National Science Foundation under Grant No. MPS72-00381 A01. 相似文献
53.
Light scattering measurements have been made on a number of commercially available optical grade glasses. By measuring the spectrum as well as intensity of the scattered light it was found possible both to obtain the total scattered intensity and to identify the origin of the scattering. The optical attenuation coefficient due to scattering was evaluated. It was found that in all glasses studied the total scattered intensity exceeds that in fused silica by at least a factor of two. 相似文献
54.
Francesco Carlà Giulio Campo Claudio Sangregorio Andrea Caneschi César de Julián Fernández Lourdes I. Cabrera 《Journal of nanoparticle research》2013,15(8):1-16
Quantum dots (QDs) have received considerable attention due to their unique optical and electrical properties. Although substantial research has focused on the potential applications and toxicological impacts of QDs, far less effort has been directed toward understanding their fate and transport in the environment. In this work, the effect of four coatings, polyethylene glycol functionalized polymer (PEGP), carboxyl derivatized polymer (COOHP), linoleic acid (LA), and polyacrylic acid-octylamine (PAA-OA), on the transport and retention of QDs in porous media were evaluated under environmentally relevant conditions. Aqueous QD suspensions (ca. 10 nM) were introduced into water-saturated columns packed with 40–50 mesh Ottawa sand at a pore-water velocity of 7.6 m/day. At an ionic strength (IS) of 3 mM and pH of 7, PEGP-coated QDs were completely retained within the column, while more than 60 % of COOHP-coated QDs were transported through a column run under identical conditions. When PAA-OA and LA were used as coatings, effluent QD recoveries increased to more than 65 and 89 % of the injected mass, respectively. Additionally, a decrease in pH from 9.5 to 5.0, or an increase of IS from 0 to 30 mM reduced the eluted mass of PAA-OA-coated QDs by more than 2 and 15 times, respectively. The relative mobility of coated QDs (LA > PAA-OA > COOHP > PEGP) was consistent with total interaction energy profiles between QDs and sand surfaces calculated based on Derjaguin–Landau–Verwey–Overbeek (DLVO) theory. At an IS of 3 mM (NaCl) and pH 7, a linear correlation was obtained between the fraction of eluted QDs and the magnitude of the primary interaction energy barrier. These findings demonstrate the strong dependence of QD transport on coating type and indicate that interaction energies based on DLVO theory can be used to predict the relative mobility of QDs in porous media. 相似文献
55.
Rubbers containing a low level of unsaturation such as EPT may be metalated with a chelate made from s-butyllithium and N,N,N′- N′ -tetramethylethylethylenediamine. The lithiated polymers, reacted with styrene, result in polystyrene graft copolymers. The physical properties are affected by graft level and polystyrene content. 相似文献
56.
The influence of an asymmetric periodic grooved cell surface on the 2D static director configuration of a nematic liquid crystal has been investigated. The minimum in the Frank-Oseen free energy was solved numerically with the Rapini-Papoular form of the surface anchoring energy at the nematic-grating interface. Results are presented for the variation of pretilt angle in the tilted bulk director field as a function of the surface groove depth, pitch and asymmetry and the bulk parameters. The simulations demonstrate the existence of two energetically degenerate high and low pretilted bulk alignment configurations. The pretilt values in these two regimes and also for the low tilt regime with finite surface anchoring are consistent with experimental results. An effective increase in the resolution of the model is obtained by using an irregular grid to describe the surface profile. 相似文献
57.
Qin Dai Carl Walkey Warren C. W. Chan 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(20):5193-5196
In protein‐rich environments such as the blood, the formation of a protein corona on receptor‐targeting nanoparticles prevents target recognition. As a result, the ability of targeted nanoparticles to selectively bind to diseased cells is drastically inhibited. Backfilling the surface of a targeted nanoparticle with polyethylene glycol (PEG) molecules is demonstrated to reduce the formation of the protein corona and re‐establishes specific binding. The length of the backfilled PEG molecules must be less than the length of the ligand linker; otherwise, PEG interferes with the binding of the targeting ligand to its corresponding cellular receptor. 相似文献
58.
Jens Mohr Prof. Dr. Martin Oestreich 《Angewandte Chemie (International ed. in English)》2014,53(48):13278-13281
The hydrogenation of oximes and oxime ethers is usually hampered by N? O bond cleavage, hence affording amines rather than hydroxylamines. The boron Lewis acid B(C6F5)3 is found to catalyze the chemoselective hydrogenation of oxime ethers at elevated or even room temperature under 100 bar dihydrogen pressure. The use of the triisopropylsilyl group as a protecting group allows for facile liberation of the free hydroxylamines. 相似文献
59.
Xing Zhang Shao-Yuan Su Xuan-Ting Chen Ling-Yi Shen Qi-Long Zhang Xin-Long Ni Hong Xu Zhi-Yong Wang Carl Redshaw 《Molecules (Basel, Switzerland)》2022,27(8)
In comparison with the numerous studies that have centered on developing molecular frameworks for the functionalization of fluorescent materials, less research has addressed the influence of the side chains, despite such appendages contributing significantly to the properties and applications of fluorescent materials. In this work, a new series of cationic fluorescent probes with AIE characteristics have been developed, which exhibit unique sensitivity for charge-diffusion anions, namely HSO3−, via the interactions of ions and the cooperation of the controllable hydrophobicity. The impact of the alkyl chain length attached at the cationic probes suggested that the fluorescent intensity and sensitivity of the probes could be partially enhanced by adjusting their aggregation tendency through the action of the hydrophobic effect under aqueous conditions. DLS and SEM images indicated that different particle sizes and new morphologies of the probes were formed in the anion-recognition-triggered self-assembly process, which could be attributed to the composite effect of electrostatic actions, Van der Waals forces and π-π stacking. 相似文献
60.
I. Fabrici J. Harant T. Madaras S. Mohr R. Soták C. T. Zamfirescu 《Journal of Graph Theory》2020,95(1):125-137
A graph is 1-planar if it has a drawing in the plane such that each edge is crossed at most once by another edge. Moreover, if this drawing has the additional property that for each crossing of two edges the end vertices of these edges induce a complete subgraph, then the graph is locally maximal 1-planar. For a 3-connected locally maximal 1-planar graph G, we show the existence of a spanning 3-connected planar subgraph and prove that G is Hamiltonian if G has at most three 3-vertex-cuts, and that G is traceable if G has at most four 3-vertex-cuts. Moreover, infinitely many nontraceable 5-connected 1-planar graphs are presented. 相似文献