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81.
Synthesis of (−)‐Hebelophyllene E: An Entry to Geminal Dimethyl‐Cyclobutanes by [2+2] Cycloaddition of Alkenes and Allenoates 下载免费PDF全文
Dr. Johannes M. Wiest Dr. Michael L. Conner Prof. M. Kevin Brown 《Angewandte Chemie (International ed. in English)》2018,57(17):4647-4651
The first synthesis of hebelophyllene E is presented, along with assignment of its previously unknown relative configuration through synthesis of epi‐ent‐hebelophyllene E. Development of a catalytic enantioselective [2+2] cycloaddition of alkenes and allenoates provides access to the required chiral geminal dimethylcyclobutanes. Key to its success is the identification of a novel oxazaborolidine catalyst which promotes the cycloaddition in high enantioselectivities with good functional‐group tolerance (9 examples, up to 97:3 e.r.). Thus, a late‐stage cycloaddition using a fully functionalized alkene, followed by a diastereoselective reduction allows a concise entry to this class of natural products. 相似文献
82.
Aleksandra Minić Jovana P. Bugarinović Anka Pejović Danijela Ilić Komatina Goran A. Bogdanović Ivan Damljanović Dragana Stevanović 《Tetrahedron letters》2018,59(38):3499-3502
A simple one-pot synthesis of new ferrocene-containing 1,3-thiazinan-2-imines from 3-arylamino-1-ferrocenylpropan-1-ols and phenyl isothiocyanate has been developed. The key intermediate β-hydroxy thioureas were generated in situ using ultrasound irradiation and subsequent cyclization was achieved by the addition of acetic acid. The scope of the reaction towards various 3-arylamino-1-ferrocenylpropan-1-ols has been explored and the corresponding 3-aryl-6-ferrocenyl-N-phenyl-1,3-thiazinan-2-imines were obtained in moderate to high yields (52–90%). 相似文献
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The aep-PNA is a chiral and cyclic PNA analogue, which has a stronger and base dependent binding affinity with complementary DNA. To understand the base dependent properties at monomer level, the structural studies of aep-PNA-(T/C/A) monomers have been carried out focussing on the conformational analysis of pyrrolidine ring pucker in aep-PNA by 1H NMR and the coupling constant data fitted into PSEUROT software. The results indicate that the type of pyrrolidine pucker depends on the electronic nature of substituent, implying the effect of pyrimidine or purine substituents in determining the ring pucker in monomers. This may consequently influence the aep-PNA oligomer conformation. Since pyrrolidine nucleic acids have emerged as an important class of PNA analogues, present results may have importance for their future development. 相似文献
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In this work, we implemented and compared two different methods to impose the rigid‐body motion constraint on a solid particle moving inside a fluid. We consider a fictitious domain method to easily manage the particle motion. As the solid as well as the fluid inertia are neglected, the particle can be discretized through its boundary only. The rigid‐body motion is imposed via Lagrange multipliers on the boundary. In the first method, such constraints are imposed in discrete points on the boundary (collocation), whereas in the second the constraint is imposed in a weak way on elements dividing the particle surface. Two test problems, that is, a spherical and an ellipsoidal particle in a sheared Newtonian fluid, are chosen to compare the methods. In both cases, the analysis is carried out in 2D as well as in 3D. The results show that for the collocation method an optimal number of collocation points exist leading to the smallest error. However, small variations in the optimal value can generate large deviations. In the weak implementation, the error is only mildly affected by the number of elements used to discretize the particle boundary and by the Lagrange multiplier's interpolation space. A further analysis is carried out to study the effect of an approximated integration of weak constraints. A comparison between the two methods showed that the same accuracy can be achieved by using less constraints if the weak discretization is used. Finally, the rigid‐body motion imposed via weak constraints leads to better conditioned linear systems. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
88.
Zeynep Güven Lars Denker Hadi Dolati Daniela Wullschläger Dr. Bartosz Trzaskowski Dr. René Frank 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(32):e202200673
Donor-acceptor cyclopropanes or cyclobutanes are dipolar reagents, which are widely used in the synthesis of complex organic (hetero)cycles in ring expansion reactions. Applying this concept to boron containing heterocycles, the four-membered borete cyclo-iPr2N-BC10H6 reacted with the carbon donor ligands 2,6-xylylisonitrile and the carbene IMes :C(NMesCH)2 with ring expansion and ring fusion, respectively. In particular, the tetracyclic structure formed with IMes displays zwitterionic character and absorption in the visible region. In contrast to the carbene IMes, the heavier carbenoids :Si(NDippCH)2 and :Ga(AmIm) with a two-coordinate donor atom afford spiro-type bicyclic compounds, which display four-coordinate geometry at silicon or gallium. (TD-)DFT calculations provide deeper insight into the mechanism of formation and the absorption properties of these new compounds. 相似文献
89.
A detailed study of the geometry, aromatic character, electronic and magnetic properties for a series of positively charged N-doped polycyclic aromatic hydrocarbons (PAHs) was performed. Magnetic properties of the examined molecules were analyzed by means of the magnetically induced current density calculated using the diamagnetic-zero version of the continuous transformation of origin of current density (CTOCD-DZ) method. The comparative study of the local aromaticity of the studied molecules was performed using several different indices: energy effect (ef), harmonic oscillator model of aromaticity (HOMA) index, six centre delocalization index (SCI) and nucleus independent chemical shifts (NICS). The presence of N-atoms in the inner rings was found to cause a planarity distortion in the studied N-doped systems. The geometric changes and charged nature of the studied N-doped systems do not significantly influence the current density and the local aromaticity distribution in comparison with the corresponding parent benzenoid hydrocarbons. The present study demonstrates how quantum chemical calculations can be used for rational design of novel PAHs and for fine tuning of their properties. 相似文献
90.
The increasing application of positron emission tomography (PET) in nuclear medicine has stimulated the extensive development of a multitude of novel and versatile techniques to introduce fluorine-18, especially for the radiolabelling of biologically or pharmacologically active molecules. Taking into consideration that the introduction of fluorine-18 (t1/2=109.8 min) mostly proceeds under harsh conditions, radiolabelling of such molecules represents a challenge and is of enormous interest. Ideally, it should proceed in a regioselective manner under mild physiological conditions, in an acceptable time span, with high yields and high specific activities. Special attention has been drawn to 2-fluoroethyl and 3-fluoropropyl groups, which are often the active sites of radiofluorinated compounds. Precursors containing an ammonium leaving group – such as a strained azetidinium or aziridinium moiety – can help to overcome these obstacles leading to a convenient and mild introduction of [18F]fluoride with high radiochemical yields. 相似文献