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121.
Bernard R Cornu D Baldeck PL Cáslavský J Létoffé JM Scharff JP Miele P 《Dalton transactions (Cambridge, England : 2003)》2005,(18):3065-3071
Non-centrosymmetric pi-conjugated systems incorporating closo-dodecaborate clusters, [NC-C6H4-C(H=N(H)-B12H11]-(2), [NC-C6H4-C(H)=C(H)-C(6)H(4)-C(H)=N(H)-B12H11]-(3), and [NC-C6H4-C(H)=C(H)-C6H4-C(H)=C(H)-C6H4-C(H)=N(H)-B12H11]-(4) have been synthesized by reaction of the monoamino derivative of B12, [B12H11NH3]-(1), with various arylaldehydes, R-C6H4-CHO. These Schiff base-like compounds were fully characterized by multinuclear NMR spectroscopy and mass spectrometry. In order to evaluate these boron rich pi-systems as potential materials for two-photon absorption (TPA) processes, UV linear absorption curves were recorded for 3 and 4, and comparatively studied with those of the boron-free pi-systems NC-C6H4-C(H)=N-CH3(5) and NC-C6H4-C(H)=C(H)-C6H4-C(H)=N-CH3(6). The donor effect of the boron cluster was evidenced by a shift to the lower energy of the absorption band in the spectra of systems incorporating B12. The two photon absorption (TPA) spectrum of compound , obtained by the up-conversion method, shows a resonance at 720 nm with a cross-section sigma(TPA) of 35 x 10(-50) cm(4) s photon(-1) molecule(-1). This value suggests the potential of B12 clusters to be used as new donor groups for the synthesis of non-linear materials. 相似文献
122.
Lindsey?Gillian?MackayEmail author C.?Peter?Taylor Richard?Bruce?Myors Ruth?Hearn Bernard?King 《Accreditation and quality assurance》2003,8(5):191-194
The selection of an appropriate isotope dilution mass spectrometry technique for the practical application of this potentially primary method of analysis is highly important. The NARL approach for the application of the exact matching double isotope dilution mass spectrometry technique developed by Henrion is presented. NARL's approach utilises exact matching to minimise the effect of measurement biases within the method but also includes the thorough examination of all other biasing factors. The approach has been successfully tested in international CCQM intercomparisons with other national metrology institutes. 相似文献
123.
Computations are performed on the interaction specificities of tetramethylammonium (TMA) for double-stranded oligonucleotides held in the B conformation. The effects of base sequence and chain length are investigated. In the short oligomers (helices formed from dinucleoside monophosphates and trinucleoside diphosphates), the interaction energies of TMA are larger in the major groove of (dG)n · (dC)n than in the minor groove of either (dA)n · (dT)n or (dA—dT)n. Upon lengthening the oligomers, and owing to the gradual shaping of the grooves of the helix and cumulative effect of the phosphates, TMA is shown to increasingly favor the minor groove of (dA)n · (dT)n with respect to the major groove of (dG)n · (dC)n, with a sizeable energy difference computed at the pentanucleoside hexaphosphate level. The binding of TMA in the minor groove of (dA)n · (dT)n involves stabilizing contacts with several sites, on the bases and on the deoxyriboses. Configurations locating the cation closer to the thymine strand are slightly preferred over configurations locating it closer to the adenine strand. 相似文献
124.
Manuel A. Fernandes Marcus Layh Bernard Omondi 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(7):o384-o385
The title compound, C10H11N, displays a crystallographic mirror plane that incorporates all the non‐H atoms, as well as the H atoms attached to the aromatic ring. The isocyano group is almost linear and shows an N[triple‐bond]C bond distance of 1.158 (3) Å. 相似文献
125.
The free energy barriers and a mechanism of the oxidation of the amino acid methionine in water and in granulocyte colony-stimulating factor (G-CSF) are analyzed via combined quantum mechanical and molecular mechanical (QM/MM) methods, constrained molecular dynamics, and committor probability calculations. The computed free energy barrier of free methionine amino acid is very close to the measured value (14.7 +/- 1.2 versus 15.5 +/- 0.02 kcal/mol). The reaction coordinate was found to be the difference between the O-O bond of H2O2 and the S-O bond, where the S is the sulfur atom of the methionine residue. It was confirmed by computing the committor probability distribution and the distribution of constrained forces that this coordinate is not coupled to the activation of other degrees of freedom. The computed free energies of the oxidation of methionine residues in G-CSF indicate that the protein environment has insignificant effects on the reaction barriers of oxidation. This result further validates our proposal that the access of solvent to methionine sites, as measured by the two-shell water coordination number, governs the kinetics of the oxidation reaction of methionine groups in a protein molecule. We also found that the number of hydrogen bonds between the distal oxygen of H2O2 and the water molecules near the methionine increases along the reaction coordinate as oxidation progresses, indicating that the charge separation developed during the oxidation by H2O2 is stabilized by specific interactions with water molecules, such as hydrogen bonding. 相似文献
126.
Silica particle-stabilized emulsions of silicone oil and water: aspects of emulsification 总被引:1,自引:0,他引:1
A study of the emulsification of silicone oil and water in the presence of partially hydrophobic, monodisperse silica nanoparticles is described. Emulsification involves the fragmentation of bulk liquids and the resulting large drops and the coalescence of some of those drops. The influence of particle concentration, oil/water ratio, and emulsification time on the relative extents of fragmentation and coalescence during the formation of emulsions, prepared using either batch or continuous methods, has been investigated. For batch emulsions, the average drop diameter decreases with increasing particle concentration as the extent of limited coalescence is reduced. Increasing the oil volume fraction in the emulsion at fixed aqueous particle concentration results in an increase in the average drop diameter together with a dramatic lowering of the uniformity of the drop size distribution as coalescence becomes increasingly significant until catastrophic phase inversion occurs. For low oil volume fractions (phi(o)), fragmentation dominates during emulsification since the mean drop size decreases with emulsification time. For higher phi(o) close to conditions of phase inversion, coalescence becomes more prevalent and the drop size increases with time with stable multiple emulsions forming as a result. 相似文献
127.
Engel CK Pirard B Schimanski S Kirsch R Habermann J Klingler O Schlotte V Weithmann KU Wendt KU 《Chemistry & biology》2005,12(2):181-189
Inhibitors for matrix metalloproteinases (MMPs) are under investigation for the treatment of cancer, arthritis, and cardiovascular disease. Here, we report a class of highly selective MMP-13 inhibitors (pyrimidine dicarboxamides) that exhibit no detectable activity against other MMPs. The high-resolution X-ray structures of three molecules of this series bound to MMP-13 reveal a novel binding mode characterized by the absence of interactions between the inhibitors and the catalytic zinc. The inhibitors bind in the S1' pocket and extend into an additional S1' side pocket, which is unique to MMP-13. We analyze the determinants for selectivity and describe the rational design of improved compounds with low nanomolar affinity. 相似文献
128.
The NaF-AlF(3) system with additions of CaF(2) and MgF(2) has been studied with Raman and vapor pressure measurements for 3 >/= CR (NaF/AlF(3) molar ratio) >/= 1 and up to 50 mol % additive. The results show that the binary melt can be described using the two equilibria AlF(6)(3)(-) = AlF(6)(2)(-) + F(-) and AlF(5)(2)(-) = AlF(4)(-) + F(-) with equilibrium constants 0.25 and 0.05, respectively, at 1293 K. Both reactions have positive reaction enthalpies. The first equilibrium is strongly shifted to the right resulting in a melt mixture with very low AlF(6)(3)(-) concentrations even at the Na(3)AlF(6) composition. Evidence for nonideal mixing of anions was found. For the ternaries, models based on Raman data are presented and compared with vapor pressure measurements. Good agreement is observed when association between the additives, CaF(2) or MgF(2), with the AlF(5)(2)(-) ions in the melt was considered. This association could be experimentally observed through a band broadening and a slight shift in the AlF(5)(2)(-) band frequency. Our vapor pressures and Raman data both indicate that MgF(2) clearly acts as an acid when added to NaF-AlF(3) melts of any composition. When CaF(2) is added, a slight decrease of vapor pressure occurs. Raman data indicate a decrease of AlF(4)(-) concentration, corresponding to a dissociation of CaF(2) with liberation of F(-) ions. All these results are, however, very much dependent on the initial melt composition. These data are explained in terms of acid-base, dilution, and association reactions of the solute with the solvent. 相似文献
129.
Bernard W. TaylorIII Arthur J. Keown Allen G. Greenwood 《The Journal of the Operational Research Society》1983,34(5):379-390
The decision-making process involved in the procurement of military weapon systems, although quite critical and complex, still encompasses the basic characteristics of a capital budgeting problem. Given a number of expenditure items and a limited budget, it is desired to procure those weapon systems that will achieve the goals and objectives of the government and/or military in the most efficient manner. Since these objectives are typically numerous and diverse, traditional decision-making techniques are not applicable. As such, integer goal programming is suggested as a technique to be employed to determine the number of military aircraft to be procured, given conflicting expenditure, budget and effectiveness goals. This method is demonstrated via a case example in which the solution results are presented. 相似文献
130.
The nonintercalative binding of an aliphatic and an aromatic bisguanylhydrazone (BGH) to the minor groove of double-stranded (dA-dT)
n
oligomers is investigated by means of theoretical computations. The preferred binding arrangements of both BGHs are stabilized by a number of H-bonding interactions with sites O2(T), N3(A) and o1 on the two strands, and require limited conformational rearrangements of the BGHs around their C-C single bonds. The intermolecular interaction energy is larger with the aliphatic BGH than with the aromatic one. The energy difference is, however, considerably reduced when the oligomer is lengthened: it passes from 16.1 kcal/mole at the heptamer level, to 7.9 kcal/mole at the undecamer level and to 4.6 kcal/mole when each strand of the undecamer is flanked with a complementary complete helical turn of phosphates, on both the 3 and 5 termini.The interaction energies of the BGHs with water molecules in the first hydration shell are, however, also larger with the aliphatic BGH, than with the aromatic BGH. This energy difference is further enhanced when one considers also the water molecules in the second shell. It becomes greater than the difference in the interaction energy of the two BGHs with (dA-dT)
n
for large values of n. When the dehydration energy of BGHs is taken into account the overall energy balance is then more favorable for the interaction of the aromatic than of the aliphatic BGH with the polynucleotide. This last conclusion is in agreement with experimental results. 相似文献