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1.
    
The reaction of [{(η5-C5Me5)M(μ-Cl)Cl}2] {where M = Rh (1), Ir (2)} with functionalized phosphine viz., diphenyl-2-pyridylphosphine (PPh2Py) in dichloromethane solvent yield neutral ϰ1-P-coordinated rhodium and iridium complexes [(η5-C5Me5)RhCl21-P-PPh2Py)]3 and [(η5-C5Me5) IrCl21-P-PPh2Py)]4. Reaction of complexes 1 and 2 with the ligand PPh2Py in methanol under reflux give bis-substituted complexes such as [(η5-C5Me5)RhCl(ϰ1-P-PPh2Py)2]+ 5 and [(η5-C5Me5)IrCl(ϰ1-P-PPh2Py)2]+ 6, whereas stirring in methanol at room temperature gives P-, N-chelating complexes of the type [(η5-C5Me5)RhCl(ϰ2-P-N-PPh2Py)]+ 7 and [(η5-C5Me5)IrCl(ϰ2-P-N-PPh2Py)]+ 8. Neutral ϰ1-P-coordinated complexes [(η5-C5Me5)RhCl21-P-PPh2Py)]3 and [(η5-C5Me5)IrCl21-P-PPh2Py)]4 easily undergo conversion to the cationic P-, N-chelating complexes [(η5-C5Me5)RhCl(ϰ2-P-N-PPh2Py)]+ 7 and [(η5-C5Me5) IrCl(ϰ2-P, N-PPh2Py)]+ 8 on stirring in methanol at room temperature. These complexes are characterized by FT-IR and FT-NMR spectroscopy as well as analytical methods. The molecular structures of the representative complexes [(η5-C5Me5)RhCl21-P-PPh2Py)]3, [(η5-C5Me5)IrCl21-P-PPh2Py)]4 and hexafluorophosphate salt of complex [(η5-C5Me5)IrCl(ϰ2-P-PPh2Py)2]+ 6 are established by single-crystal X-ray diffraction methods  相似文献   
2.
The oxidation of symmetrical disulfides [D ,L ‐cystine ( 1 ) and 3,3′‐dithiobis(propionic acid) ( 2 )] with hydrogen peroxide in D2O–NaOH solution (pH 10–11) was studied by NMR spectroscopy. Assignments of the proton and carbon NMR signals of starting materials ( 1 and 2 ) and products of oxidation are based on conventional 1D NMR methods (DEPT, selective spin decoupling). Formation of C—S bond cleavage products or, in case of 2 , partially oxidized intermediates was not detected. The accelerating effect of Cu2+ cations, but not Fe3+ cations, on the oxidation rate of 1 in basic medium was demonstrated. Copyright © 2002 John Wiley & Sons, Ltd.  相似文献   
3.
4.
用中子活化法相对于54Fe(n,P)54Mn反应,在13.50—14.80MeV中子能区测量了Ba(n,x)134Cs,134Ba(n,2n)133Ba,140Ce(n,2n)139Ce,142Ce(n,2n)141Ce和23Na(n,2n)22Na的反应截面.并将所测的结果和其他作者的结果进行了比较,中子能量是用90Zr(n,2n)89m+gZr反应和93Nb(n,2n)92mNb反应截面比法测定的。  相似文献   
5.
Semi-empirical molecular orbital calculations were carried out for the compounds (C2H5)3As, (C2H5)3Ga and RAsH2 (R = C2H5, i-C3H7, i-C4H9, and t-C4H9) by using the CNDO/2-U program, and their capability of β-elimination reaction is compared on the basis of the torsion energy to the transition state, electrostatic interactions and orbital overlapping between the central atom and the β-hydrogen, and bond order of the metal-carbon, and carbon-hydrogen bond. In the comparison of (C2H5)3As with (C2H5)3Ga, we found that the β-elimination of (C2H5)3As could hardly be expected to take place in the thermal decomposition. The capability of β-elimination would be smaller in C2H5AsH2 than that in (C2H5)3As. Moreover when the ethyl group is replaced by a t-butyl group in RAsH2, the β-elimination reaction appears to become more difficult and a large possibility for a radical process is suggested.  相似文献   
6.
Pentacyclic isoxazolines were obtained by the cycloaddition of benzonitrile oxide to norbornene-azetidinone-fused 3,1-oxazines. The constitutions of two of the isomers obtained, and the configurations and conformations of all products, were determined by means of 1H and 13C NMR spectroscopy and DNOE experiments.  相似文献   
7.
An NMR study of one new and several known abietane diterpenes isolated from the roots of Aegiphila lhotzkyana is described. In addition to 1D NMR, several 2D shift‐correlated NMR pulse sequences (1H–1H‐COSY, NOESY, HMQC and HMBC) were used to establish all the structures, and unambiguously perform the 1H and 13C chemical shift assignments of the new natural diterpene and three derivatives, the NMR data for which have not been reported previously. Revision of current data assignment for teuvincenone H is also suggested. Copyright © 2003 John Wiley & Sons, Ltd.  相似文献   
8.
Disordered Sr2FeMoO6 shows a drastic reduction in saturation magnetization compared to highly ordered samples, moreover magnetization as a function of the temperature for different disordered samples shows qualitatively different behaviours. We investigate the origin of such diversity by performing spatially resolved photoemission spectroscopy on various disordered samples. Our results establish that extensive electronic inhomogeneity, arising most probably from an underlying chemical inhomogeneity in disordered samples, is responsible for the observed magnetic inhomogeneity. It is further pointed out that these inhomogeneities are connected with composition fluctuations of the type Sr2Fe1+x Mo1-x O6 with Fe-rich (x > 0) and Mo-rich (x < 0) regions. Dedicated to Prof J Gopalakrishnan on his 62nd birthday.  相似文献   
9.
Reduced forms of iso‐α‐acids (isohumulones), used in modern beer brewing were separated and characterized by 1H and 13C NMR spectroscopy. Components from mixtures of rho‐iso‐α‐acids, tetrahydro‐iso‐α‐acids, and hexahydro‐iso‐α‐acids were isolated using high‐performance liquid chromatography (HPLC) and analyzed by use of one‐ and two‐dimensional NMR experiments. The data presented assign the identities of the main peaks in the HPLC traces for the reduced iso‐α‐acids. Previous tentative assignments regarding the cis and trans configurations and the structures of the acyl residues of the reduced iso‐α‐acids were confirmed and extensive NMR assignments were made. Furthermore, the previously unknown stereochemistry in the C‐4 side‐chain of the rho‐ and hexahydro‐iso‐α‐acids was assigned. Copyright © 2003 John Wiley & Sons, Ltd.  相似文献   
10.
Interfacial rheological properties and their suitability for foam production and stability of two vegetable proteins were studied and compared to β-casein. Proteins used ranged from flexible to rigid/globular in the order of β-casein, gliadin and soy glycinin. Experiments were performed at pH 6.7. Network forming properties were characterised by the surface dilational modulus (determined with the ring trough) and the critical falling film length (Lstill) at which a stagnant protein film will break. Gliadin had the highest dilational modulus, followed by glycinin and β-casein, whereas glycinin formed the strongest film against fracture in the overflowing cylinder. The rate of decrease in the surface tension was studied at the air–water (Wilhelmy plate method) and the oil–water interface (bursting membrane) and the dynamic surface tension during compression and expansion in the caterpillar. Gliadin had the lowest equilibrium interfacial tensions and β-casein the lowest dynamic surface tension during expansion. Hardly any foam could be formed at a concentration of 0.1 g/l by shaking. At a concentration of 1.4 g/l most foam was formed by β-casein, followed by gliadin and glycinin. It seems that in the first place the rate of adsorption is important for foam formation. For the vegetable proteins, adsorption was slow. This resulted in lower foamability, especially for glycinin.  相似文献   
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