全文获取类型
收费全文 | 30392篇 |
免费 | 5286篇 |
国内免费 | 4610篇 |
专业分类
化学 | 22797篇 |
晶体学 | 428篇 |
力学 | 1696篇 |
综合类 | 261篇 |
数学 | 3838篇 |
物理学 | 11268篇 |
出版年
2024年 | 88篇 |
2023年 | 652篇 |
2022年 | 819篇 |
2021年 | 1109篇 |
2020年 | 1367篇 |
2019年 | 1367篇 |
2018年 | 1162篇 |
2017年 | 1129篇 |
2016年 | 1531篇 |
2015年 | 1502篇 |
2014年 | 1792篇 |
2013年 | 2326篇 |
2012年 | 2659篇 |
2011年 | 2744篇 |
2010年 | 2058篇 |
2009年 | 1860篇 |
2008年 | 2028篇 |
2007年 | 1732篇 |
2006年 | 1636篇 |
2005年 | 1500篇 |
2004年 | 1224篇 |
2003年 | 1048篇 |
2002年 | 1145篇 |
2001年 | 973篇 |
2000年 | 728篇 |
1999年 | 663篇 |
1998年 | 494篇 |
1997年 | 406篇 |
1996年 | 451篇 |
1995年 | 374篇 |
1994年 | 323篇 |
1993年 | 244篇 |
1992年 | 214篇 |
1991年 | 224篇 |
1990年 | 163篇 |
1989年 | 125篇 |
1988年 | 76篇 |
1987年 | 74篇 |
1986年 | 90篇 |
1985年 | 61篇 |
1984年 | 38篇 |
1983年 | 35篇 |
1982年 | 16篇 |
1981年 | 12篇 |
1980年 | 6篇 |
1979年 | 3篇 |
1975年 | 2篇 |
1959年 | 3篇 |
1957年 | 5篇 |
1936年 | 3篇 |
排序方式: 共有10000条查询结果,搜索用时 406 毫秒
991.
MALDI/FTMS中碰撞衰减机理对准确质量校正的影响 总被引:1,自引:0,他引:1
Collisional damping affects the relationship between ion mass and effective cyclotron frequency in Fourier transform mass spectrometry. The exact mass calibration equation(m/z=A/f+(mneutral/m^^+mneutral)k+B/f(f+(mneutral/m^^+mneutralk))was therefore derived from the characteristic equation of system model, force=m(dv/dt)=qE-qv×B0-ξv,a frictional damping force), in which k is amended by the shift of observed frequency of matrix ion or other known ion in external calibration. The mass obtained by the amended calibration equation is therefore immune to collisional damping and space-charge effects on mass accuracy. The relative errors of ion mass measured were all less than 2×10^-6. 相似文献
992.
The X-ray crystallographic structure was reported for a dinuclear copper(Ⅱ) complex with a tetraanionic ligand of p-tert-butylsulfonylcalix[4]arene [Cu2L(CH3OH)6]·4CH3OH (H4L=p-tert-butylsuffonylcalix[4]arene). The complex belongs to triclinic system, P1^-- space group, with a = 1.2303(3) nm, b = 1.2377(3) nm, c = 1.3110(3) nm, a =66.862(4)°, β= 67.206(4)°, γ=61.711(3)°, Z= 1, V= 1.5659(7) nm^3, Dc= 1.371 g/cm^3, F(000) = 682,μ(Mo Kα) = 0.883 mm^-1, R1 =0.0325, wR2=0.0870. In this complex, the calix[4]arene acts as a bis-tridentate chelating ligand with the 1,2-alternate conformation. 相似文献
993.
A series of poly(ether-amide) dendrimers with amino acids and peptides as the peripheral functional groups was synthesized,
and their structures were confirmed by nuclear magnetic resonance (NMR) and electrospray ionization-mass spectrometry (ESI-MS)
spectrometry. Molecular dynamics simulation of the peptide dendrimers in solution was performed, indicating that, the prior
conformations of the dendrimers were atom number dependent, i.e., with the increases of the atom number, the prior conformations
were more spherical. Also, the amino acid α-C atom radial distribution indicated that, with larger peripheral groups, more back-folding of the dendrimers occurred.
__________
Translated from Acta Chimica Sinica, 2007, 65(1): 21–26 [译自: 化学 通报] 相似文献
994.
Summary Dehydrogenation of propane to propylene in carbon dioxide was investigated over promoted Cr/SiO2. The results showed that the catalysts were effective for the reaction and CO2 in the feed promoted the catalytic activity. XRD, TPR and microcalorimetric adsorption techniques were used to study the structure and surface acidity of the catalysts. It was found that the surface acidity decreased with the increase of K in the Cr/SiO2 and led to the increase of selectivity toward propylene. A propane conversion of 31% with 91% selectivity to propylene over the 5%Cr-0.4%K/SiO2 catalyst was observed at 923 K with CO2 /C3H8 molar ratio of 3.6. 相似文献
995.
ZHANG Peng-Fei GU Yi-Xin GUO Jun-Li CHEN Min 《有机化学》2003,23(Z1):90-92
Both proteinogenic and non proteinogenic α-amino acids are of particular interest as constituents of peptide factors, peptidomimetics and antibiotics for the construction of modern selective drugs. [1] Furthemore, α-amino acid derivatives are interesting building units for chiral-pool syntheses of enantiomerically pure natural products. [2] Numerous efforts in modern organic synthesis are centered on the synthesis of enantiomerically pure α-amino acids. [3] During the past three decades efficient methods of asymmetric synthesis of α-amino acids have been developed; most of them are based on electrophilic transformations of organometallic intermediates. [4] Using the concept that the chirality of the carbohydrates can be exploited for diastereoselective reactions, Kunz and his cooperator had developed a Strecker synthesis with glycosyl amines as chiral auxiliaries. [5] 相似文献
996.
Xu X Zhao J Jiang D Kong J Liu B Deng J 《Analytical and bioanalytical chemistry》2002,374(7-8):1261-1266
A novel hydrogen peroxide biosensor was developed based on the immobilization of horseradish peroxidase (HRP) in a TiO(2) sol-gel matrix on an electropolymerized phenazine methosulfate (PMS) modified electrode surface. Such membranes are of interest due to their high surface area, biological compatibility, and ease of fabrication. HRP entrapped in the TiO(2) matix was stable and retained its activity to a large extent. Cyclic voltammetry and amperometric measurements were employed to demonstrate the feasibility of electron transfer between immobilized HRP and the glassy carbon electrode via electropolymerized PMS. The influence of various experimental parameters such as operating potential, pH, temperature, and stability was investigated for optimum analytical performance. The biosensor provided a wide linear calibration range from 4.0x10(-6) M to 1.0x10(-3) M, with a detection limit of 8.0x10(-7) M at a signal-to-noise ratio of 3. The sensor retained 80% of its original activity after two months of operation. 相似文献
997.
Results are reviewed from a study examining how structural modifications introduced by ozonization enhance the influence of kraft lignin on the crystallization of CaCO(3). Ozone treatment of kraft lignin in an aqueous environment is shown to increase its carboxylic acid and overall oxygen content and reduce its molecular weight. Calcium concentration and temperature were monitored in heated supersaturated solutions containing ozonized kraft lignins to gauge their influence on CaCO(3) crystallization processes. The presence of kraft lignin raises the temperature necessary to induce crystallization. This effect is shown to level off at relatively low lignin concentrations and be dependent on the extent of ozone treatment the kraft lignin has undergone. A linear correlation is found between crystallization temperatures and the carboxylic acid content of ozonized lignin samples indicating the introduction of these functional groups plays an important role in enhancing its inhibitory effect. Scanning electron microscopy images of crystals grown in the presence of kraft lignins show significant morphological modifications. These are consistent with specific or pseudo specific interactions between the lignin and crystal faces of calcite to inhibit growth parallel to its c axis. The influence over crystal morphology demonstrated by modified kraft lignin increases with increasing ozonization. Also presented here are crystallization temperature data for a range of kraft lignin ultrafiltration fractions, which indicate that the optimal (nominal) molecular weight of kraft lignin for inhibiting the crystallization of CaCO(3) lies between 5000 and 10000. 相似文献
998.
以紫外光谱法研究了青霉素G钾盐(Pen-K)在十六烷基三甲基溴化铵(CTAB)胶束体系中的水解反应, 并探讨了水解反应机理.结果表明, CTAB胶束对Pen-K的水解具有抑制作用; Pen-K在CTAB胶束体系水解时,体系pH值的变化与在水中相似, 表明H+浓度对这种抑制作用影响较小.红外光谱和微极性研究表明,部分Pen-K钾盐定位于CTAB胶束栅栏层中, 增加了其稳定性. 相似文献
999.
Zhai HJ Yang X Wang XB Wang LS Elliott B Boldyrev AI 《Journal of the American Chemical Society》2002,124(23):6742-6750
Although neutral and ionic O4(0/-/+) species have been observed experimentally and considered for energetic materials, O4(2-) and O5(2-) dianions have not yet been explored. O4(2-) is valent isoelectronic to the well-known ClO3- and SO3(2-) anions, and O5(2-) is valent isoelectronic to ClO4- and SO4(2-). All are stable, common anions in solutions and inorganic salts. In this article, we explore the possibility of making covalently bound O4(2-) and O5(2-) species stabilized in the forms of M+O4(2-) and M+O5(2-) (M = Li, Na, K, Cs) in the gas phase. Laser vaporization experiments using M-containing targets and an O2-seeded carrier gas yielded very intense mass peaks corresponding to MO4- and MO5-. To elucidate the structure and bonding of the newly observed MO4- and MO5- species, we measured their photoelectron spectra and then compared them with ab initio calculations and the spectra of ClO3-, Na+SO3(2-), ClO4-, and Na+SO4(2-). Careful analyses of the experimental and ab initio results showed, however, that the observed species are of the forms, O2-M+O2- and O2-M+O3-. The more interesting M+O4(2-) and M+O5(2-) species were found to be higher-energy isomers, but they are true minima on the potential energy surfaces, which suggests that it might be possible to synthesize bulk materials containing covalently bound tetra- and pentatomic oxygen building blocks. 相似文献
1000.
J. S. Guo E. D. Sudol J. W. Vanderhoff M. S. El-Aasser 《Journal of polymer science. Part A, Polymer chemistry》1992,30(5):691-702
Particle nucleation in the polymerization of styrene microemulsions was found to take place throughout the polymerization as indicated by measurements of the particle number as a function of conversion. A mechanism based on the nucleation in the microemulsion droplets was proposed to explain the experimental findings although homogeneous nucleation and coagulation during polymerization were not completely ruled out. A thermodynamic model was developed to simulate the partitioning of monomer in the different phases during polymerization. The model predicts that the oil cores of the microemulsion droplets were depleted early in the polymerization (4% conversion). Due to the high monomer/polymer swelling ratio of the polymer particles, most of the monomer resides in the polymer particles during polymerization. The termination of chain growth inside the polymer particles was attributed to the chain transfer reaction to monomer. The low n? (less than 0.5) of the microemulsion system was attributed to the fast exit of monomeric radicals. 相似文献