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81.
Zois Syrgiannis 《Tetrahedron letters》2006,47(17):2961-2964
The thermodynamic parameters, ΔΔH# and ΔΔS#, were determined for the interception of an intermediate, with the structural characteristics of an aziridinium imide, by nucleophilic solvents during the reaction of 2-methyl-2-butene with N-phenyltriazolinedione. The experimentally measured parameters were found to be in favor of an SN2-‘like’ transition state and showed strong dependence on the bulkiness of the incoming molecule of the nucleophile-solvent. 相似文献
82.
Thermogravimetric analysis of hydroxyl terminated polybutadiene (HTPB) and its fractions of different molecular weights separated by preparative GPC shows two major stages of weight loss of different nature in a nitrogen atmosphere. The first stage is primarily depolymerisation, cyclisation and crosslinking of molecules and the second stage is mainly the decomposition of the residue from the first stage. The kinetic parameters, viz. activation energy E and pre-exponential factor A using four different non-isothermal integral equations show a systematic increase with increase in molecular weight for the first stage, whereas for the second stage, the effect of molecular weight on E and A values is not prominent. The increase in E and A values for the first stage is attributed to the formation of greater number of cyclised and crosslinked products from molecules of higher dimensions. Quantitative correlations between the kinetic constants and the molecular weight parameters were derived for the first stage as a quadratic curve following the equation: E or ln A = K1 − K2/M (where K1 and K2 are empirical constants whose values are different for the different molecular weight averages, viz. Mn, Mw and Mz and for the different equations). 相似文献
83.
Geometrical parameters associated with N-H ... N types of hydrogen bonds have been analysed using crystal structure data on
nucleic acids, amino acids and related compounds. Histograms depicting the frequency distribution of N-H ... N length (l) and H-N ... N angle (θ) have been drawn and conclusions on the favoured geometry of such bonds have been arrived at. The
distribution ofl shows a pronounced maximum in the range between 2.9? and 3.0? with an overall average of 2.98 ?. The θ distribution shows
a pronounced maximum for the hydrogen bond angle in the range 0°-10°, with a rapid fall-off in frequency for nonlinear hydrogen
bonds. The frequency shows a cos6θ dependence as compared to cos2θ dependence term used earlier to predict the angular dependence of hydrogen bond potential energy in proteins and polypeptides. 相似文献
84.
Time- and temperature-dependent SAXS-experiments were used to determine the effect of octene and butene co-units on the lamellar structure and the melting properties of polyethylene. As expected, melting points decrease with increasing co-unit content, but crystal thicknesses are not affected and depend on the crystallization temperature only. Results can be cast into some simple equations which describe the dependence:
相似文献
1. | Of the melting point Tf on the crystal thickness dc and the co-unit content xB |
2. | Of the equilibrium melting point on xB |
3. | Of dc on the crystallization temperature Tc |
4. | Of the long spacing L on Tc, xB and the molar mass |
5. | Of Tf on Tc. |
85.
对不同支化度和不同支链链长的20%(W/V)星形聚苯乙烯溶液测定了~(13)C NMR弛豫参数,用1g-x~2分布、Cole-Cole分布和构象跳跃模型对主链的分子运动进行了分析讨论,并对芳环侧基的内旋转运动也进行了分析,求出了活化能和跳跃速率。结果表明,轻度化学交联对相关时间分布有一定影响,对链段运动的势垒没有明显影响。支链链长对~(13)C NMR弛豫的影响和对线形聚合物的影响是类似的。 相似文献
86.
Baseline separation of ten new substituted [1-(imidazo-1-yl)-1-phenylmethyl)] benzothiazolinone and benzoxazolinone derivatives, with one chiral center, was achieved by CD-EKC using highly sulfated CDs (alpha, beta, gamma highly S-CDs) as chiral selectors. The influence of the type and concentration of the chiral selectors on the enantioseparations was investigated. The highly S-CDs exhibit a very high enantioselectivity power since they allow excellent enantiomeric resolutions compared to those obtained with the neutral CDs. The enantiomers were resolved with analysis times inferior to 2.5 min and resolution factors R(s) of 3.73, 3.90, 1.40, and 4.35 for compounds 1, 2, 3, and 5, respectively, using 25 mM phosphate buffer at pH 2.5 containing either highly S-alpha-CD, highly S-beta-CD, and highly S-gamma-CD (3 or 4% w/v) at 298 K, with an applied field of 0.30 kV/cm. The determination of the enantiomer migration order for the various analytes and the study of the analyte structure-enantioseparation relationships display the high contribution of the interactions between the analytes phenyl ring and the CDs to the enantiorecognition process. The thermodynamic study of the analyte-CD affinities permits us to improve our knowledge about the enantioseparation mechanism. 相似文献
87.
M. E. M. Emam 《中国化学会会志》2002,49(3):319-323
The kinetic and thermodynamic parameters such as reaction order, activation energy, enthalpy, free energy and entropy change related to the thermal decomposition of Co(II), Ni(II) and Cu(II) hydrazone complexes of 4‐benzamido‐1‐(4‐actylpyridine)‐3‐thiosemicarbazone (BACPT) and 4‐benzamido‐1‐(pyridine‐3‐aldehye)‐3‐thiosemicarb‐azone (BAPT) were evaluated from differential thermal analysis (DTA) curves using Thomas‐Clarke's method. The thermal stability of these complexes are discussed in relation to the nature of the metalion and of the ligand present. A suitable mechanism for the thermal decomposition process of the complexes based on the data of the thermogravimetric analysis (TGA) was suggested. 相似文献
88.
Yunyu Yi Ronald Neufeld Selim Kermasha 《Journal of Sol-Gel Science and Technology》2006,38(3):251-259
Entrapment of membrane proteins is a challenging task compared to that involving soluble proteins. Chlorophyllase, a membrane
protein, was successfully entrapped in tetramethoxysilane-derived sol-gel. Pre-gel sol typically consists of an aqueous suspension
of chlorophyllase, precursors including tetramethoxysilane and/or methytrimethoxysilane, and sodium fluoride as catalyst.
To obtain a highly active entrapped enzyme preparation, the effects of various immobilization parameters, including the chemical
compositions of pre-gel sol (water/silane ratio, precursor type and proportions, enzyme loading, sodium fluoride concentration),
and sol-gel process parameters (aging and drying time and approach) have been investigated. Chlorophyllase demonstrated the
highest activity in gel derived from a pre-gel sol with water/silane ratio of 30 and enzyme loading of 0.257 mgprotein/ggel, and showed moderately lower activity in organically modified sol-gel than that in hydrophilic sol-gel. The effects of water/silane
ratio and precursor combinations on the activity of entrapped chlorophyllase were also studied by examining the pore morphology
of gel via nitrogen adsorption-desorption. Longer aging time leads to an entrapped chlorophyllase preparation with higher
activity. Chlorophyllase preparation demonstrated negligible activity after air-drying for 12 h while lyophilized chlorophyllase
preparation demonstrated 8, 4 and 4 times higher activity than air-dried, vacuum-dried and solvent-dried preparations. Chlorophyllase
demonstrated 30% higher activity in the improved sol-gel protocol than that from a non-optimized sol-gel protocol developed
in a previous study. 相似文献
89.
Summary A new equation is derived relating the retention index to the molecular polarizabilities, ionization potentials and permanent dipole moments of the stationary phase and the solute.Various implications of this equation to quantitative structure-retention relationships are discussed. 相似文献
90.
Matioli Graciette Zanin Gisella M. De Moraes Flávio F. 《Applied biochemistry and biotechnology》2002,98(1-9):947-961
The influence of substrate or product level on the initial velocity of cyclodextrin (CD) production by cyclodextringlycosyltransferase
from a Brazilian isolate of Bacillus firmus was studied. Our results indicate that the product γ-CD is a stronger inhibitor to the reaction than β-CD. Small saccharides
could also inhibit CD production, although to a lesser extent than the products, and maltose was the strongest inhibitor among
small saccharides. Increasing substrate concentration resulted in greater reduction on enzyme activity for the formation of
β-CD than for γ-CD. We modeled the kinetics of CD production with a set of four reversible reactions including the cyclization/coupling
reaction that forms/opens CDs, and three disproportionation reactions. Our model on the initial velocity data explained well
the substrate inhibition phenomenon. Kinetic parameters were determined by fitting the initial velocity data into our model. 相似文献