全文获取类型
收费全文 | 57040篇 |
免费 | 18380篇 |
国内免费 | 198篇 |
专业分类
化学 | 63647篇 |
晶体学 | 96篇 |
力学 | 2352篇 |
综合类 | 1篇 |
数学 | 5564篇 |
物理学 | 3958篇 |
出版年
2024年 | 165篇 |
2023年 | 4140篇 |
2022年 | 1586篇 |
2021年 | 2752篇 |
2020年 | 4894篇 |
2019年 | 2718篇 |
2018年 | 2596篇 |
2017年 | 874篇 |
2016年 | 6032篇 |
2015年 | 5923篇 |
2014年 | 5380篇 |
2013年 | 5907篇 |
2012年 | 4170篇 |
2011年 | 2261篇 |
2010年 | 4002篇 |
2009年 | 3842篇 |
2008年 | 1903篇 |
2007年 | 1549篇 |
2006年 | 932篇 |
2005年 | 835篇 |
2004年 | 650篇 |
2003年 | 508篇 |
2002年 | 466篇 |
2001年 | 276篇 |
2000年 | 189篇 |
1999年 | 211篇 |
1998年 | 178篇 |
1997年 | 244篇 |
1996年 | 244篇 |
1995年 | 282篇 |
1994年 | 196篇 |
1993年 | 308篇 |
1992年 | 181篇 |
1985年 | 166篇 |
1984年 | 162篇 |
1982年 | 185篇 |
1981年 | 202篇 |
1980年 | 238篇 |
1979年 | 224篇 |
1978年 | 233篇 |
1977年 | 349篇 |
1976年 | 408篇 |
1975年 | 483篇 |
1974年 | 505篇 |
1973年 | 312篇 |
1972年 | 380篇 |
1971年 | 368篇 |
1970年 | 556篇 |
1969年 | 422篇 |
1968年 | 472篇 |
排序方式: 共有10000条查询结果,搜索用时 312 毫秒
961.
Vijay M. Krishnamurthy Dr. Brooks R. Bohall Chu‐Young Kim Dr. Demetri T. Moustakas Dr. David W. Christianson Prof. Dr. George M. Whitesides Prof. Dr. 《化学:亚洲杂志》2007,2(1):94-105
This paper describes a calorimetric study of the association of a series of seven fluorinated benzenesulfonamide ligands (C6HnF5?nSO2NH2) with bovine carbonic anhydrase II (BCA). Quantitative structure–activity relationships between the free energy, enthalpy, and entropy of binding and pKa and log P of the ligands allowed the evaluation of the thermodynamic parameters in terms of the two independent effects of fluorination on the ligand: its electrostatic potential and its hydrophobicity. The parameters were partitioned to the three different structural interactions between the ligand and BCA: the ZnII cofactor–sulfonamide bond (≈65 % of the free energy of binding), the hydrogen bonds between the ligand and BCA (≈10 %), and the contacts between the phenyl ring of the ligand and BCA (≈25 %). Calorimetry revealed that all of the ligands studied bind in a 1:1 stoichiometry with BCA; this result was confirmed by 19F NMR spectroscopy and X‐ray crystallography (for complexes with human carbonic anhydrase II). 相似文献
962.
Allison A. Calhoun Patrick D. Nicholson Alexander B. Barnes 《Polymer Degradation and Stability》2006,91(9):1964-1971
Thermo-oxidative effects on the surface energy of polypropylene were measured by inverse gas chromatography as a function of exposure time and temperature. Unaltered polypropylene had a surface energy of 33 mJ/m2. Oxidized polypropylene, after exposure to air at temperatures of 100 °C and 110 °C, had a range of maximum surface energies from 38 to 41 mJ/m2. Comparisons between FTIR carbonyl peak growth and the surface energy showed that both methods detect oxidation, though the increase in surface energy is detected before the carbonyl peak growth is noticeable. The work of adhesion predicted by the surface free energies obtained in this work between a coated calcium carbonate and polypropylene changes by 10% due to the oxidation of the polymer at 110 °C. 相似文献
963.
Zoya?Orekhova Yonit?SambiraEmail author Emanuel?Manzurola Alexander?Apelblat 《Journal of solution chemistry》2005,34(7):853-867
Conductivity measurements of DL-pyroglutamic acid and sodium pyroglutamate in dilute aqueous solutions were performed in the 288.15–323.15 K temperature range. The limiting molar conductances of pyroglutamate anion, λo(pGlu−, T) and the dissociation constants of pyroglutamic acid, K(T) were derived from the Onsager, and the Quint and Viallard conductivity equations. Densities of aqueous solutions with molalities lower than 0.5 mol-kg−1 were determined at 5 K intervals from T = 288.15 K to 333.15 K. Densities served to evaluate the apparent molar volumes, V2,φ(m, T), the cubic expansion coefficients, α (m,T) and the changes of the isobaric heat capacities with respect to pressure, (∂ CP/∂ P)T,m. They were correlated qualitatively with the changes in the structure of water when pyroglumatic acid is dissolved in it. 相似文献
964.
Wang Q Barclay JE Blake AJ Davies ES Evans DJ Marr AC McInnes EJ McMaster J Wilson C Schröder M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(14):3384-3396
A novel [NiS4Fe2(CO)6]cluster (1: 'S(4)'=(CH(3)C(6)H(3)S(2))(2)(CH(2))(3)) has been synthesised, structurally characterised and has been shown to undergo a chemically reversible reduction process at -1.31 V versus Fc(+)/Fc to generate the EPR-active monoanion 1(-). Multifrequency Q-, X- and S-band EPR spectra of (61)Ni-enriched 1(-) show a well-resolved quartet hyperfine splitting in the low-field region due to the interaction with a single (61)Ni (I=3/2) nucleus. Simulations of the EPR spectra require the introduction of a single angle of non-coincidence between g(1) and A(1), and g(3) and A(3) to reproduce all of the features in the S- and X-band spectra. This behaviour provides a rare example of the detection and measurement of non-coincidence effects from frozen-solution EPR spectra without the need for single-crystal measurements, and in which the S-band experiment is sensitive to the non-coincidence. An analysis of the EPR spectra of 1(-) reveals a 24 % Ni contribution to the SOMO in 1(-), supporting a delocalisation of the spin-density across the NiFe(2) cluster. This observation is supported by IR spectroscopic results which show that the CO stretching frequencies, nu(CO), shift to lower frequency by about 70 cm(-1) when 1 is reduced to 1(-). Density functional calculations provide a framework for the interpretation of the spectroscopic properties of 1(-) and suggest that the SOMO is delocalised over the whole cluster, but with little S-centre participation. This electronic structure contrasts with that of the Ni-A, -B, -C and -L forms of [NiFe] hydrogenase in which there is considerable S participation in the SOMO. 相似文献
965.
Two novel copper(I) complexes with Cu‐O bonds, [Cu2L2(PPh3)2](BF4)2 ( 1 ) and [Cu(L)(dppeo)](BF4) ( 2 ) ( L = 6‐(4‐diethylmethylphosphonatephenyl)‐2,2′‐bipyridine, dppeo = bis(diphenylphosphino)ethane monoxide), have been prepared and their structures characterized. In the binuclear complex 1 , the ligand L serves as tridentate donor with the N, N′ and O as coordination atoms, and the two CuI atoms are bridged through both P = O donor atoms in different ligand L with a triphenylphosphine molecule as auxiliary ligand. While in mononuclear complex 2 , both ligands L and dppeo behave as bidentate with N∧N from L and P∧O from dppeo chelating to CuI atom. 相似文献
966.
Dr. Marcella Chiari Francesco Damin Alessandra Melis Roberto Consonni 《Electrophoresis》1998,19(18):3154-3159
New copolymers of acrylamide and β-D -glucopyranoside were synthesized and characterized. The different reactivity of the two monomers towards radical polymerization meant we could control the growth of the polymer chains whose length was inversely related to the number of glucose residues incorporated in the copolymers. The properties of these polymers were investigated in the separation of oligonucleotides and double-stranded DNA by capillary electrophoresis (CE) in coated and uncoated capillaries. The new copolymers were a suitable matrix for CE due to their high-resolving capacity and low viscosity. We also looked into the advantages of a new method of dynamic suppression of electroosmotic flow based on the addition of small amounts (0.03–0.05%) of dimethylacrylamide to the sieving and to the running buffer. A complete test was run on the reproducibility and efficiency of separations carried out in a permanently and dynamically coated capillary, and the advantages and disadvantages of the two methods were compared. 相似文献
967.
Using variational Monte Carlo and a simple explicitly correlated wave function we have computed the Born-Oppenheimer energy of the H2 ground state (X 1Sigmag+) at 24 internuclear distances. We have also calculated the diagonal correction to the Born-Oppenheimer approximation and the lowest-order relativistic corrections at each distance using variational Monte Carlo techniques. The nonadiabatic values are evaluated from numerical derivatives of the wave function with respect to the nuclear coordinates. With this potential energy surface we have computed several of the lowest vibrational-rotational energies for this system. Our results are in good agreement with the best values found in the literature. 相似文献
968.
The stereochemistry of the cyclobutanones 1-7, resulted from the reaction of t-butylcyanoketene with bicyclo[2.2.1]heptene, bicyclo[2.2.1]heptadiene, 1,4 - dihydro - 1,4 - methanonaphthalene, 1,4 - dihydro - 9 - (1 - methylethylidene) - 1,4 - methanonaphthalene, 1,4 - dihydro - 1,4 - epoxynaphthalene, l,4,4a,8b - tetrahydro - 1,4 - methanobiphenylene (l,4,4a,8b) and 1,4,4a,8b - tetrahydro - 1,4 - methanobiphenylene(1,4,4aβ,8bβ) was established as having the cyclobutanone ring exo and the t-Bu group in the configuration. These findings represent a stereochemical argument in favour of a π2s + π2a reaction mode of t-butylcyanoketene to the above mentioned bicyclo[2.2.1]heptene derivatives. Observations regarding preservation of the original configurations of alkenes as well as the geometrical distorsion of the cyclobutanones are shortly discussed. 相似文献
969.
Jürgen Pebler Klaus Schmidt Kurt Dehnicke Prof. Dr. Johann Weidlein 《无机化学与普通化学杂志》1978,440(1):269-277
121Sb Mössbauer Spectra of Antimony (V) Compounds. II The Mössbauer resonance effect of 121Sb has been studied at 4.2 K in a series of 11 antimony(V) compounds which are in most cases bridged. Isomer shift and quadrupole splitting variations are considered in the light of results of X-ray and vibrational spectroscopy. Preparation and the vibrational spectra of [NMe4][SbCl4(n3)2] are described. Within the limitations of available structural data related tin compounds are compared with those of corresponding 119Sn Mössbauer spectra. 相似文献
970.
Prof. Dr. W. Kratz 《Monatshefte für Mathematik》1981,91(4):275-289
Given semi-normsf andg on
n
and a real number >0. Then the successive minima off under the constraintg are defined by
j
: = inf {: there existj linear independent vectors inZ
n
withf andg}. The main theorem of this paper (Lagrange multiplier theorem) states that the successive minima of a certainnorm h on
n
(without constraints) coincide with the
j
's up to bounded factors. Moreover, this norm is constructed explicitly. Using Minkowski's wellknown theorem on successive minima and our result certain inequalities on simultaneous Diophantine approximations are derived. 相似文献