全文获取类型
收费全文 | 52980篇 |
免费 | 6440篇 |
国内免费 | 5039篇 |
专业分类
化学 | 38555篇 |
晶体学 | 500篇 |
力学 | 2522篇 |
综合类 | 250篇 |
数学 | 6523篇 |
物理学 | 16109篇 |
出版年
2024年 | 76篇 |
2023年 | 852篇 |
2022年 | 998篇 |
2021年 | 1657篇 |
2020年 | 1709篇 |
2019年 | 1623篇 |
2018年 | 1382篇 |
2017年 | 1290篇 |
2016年 | 2182篇 |
2015年 | 2059篇 |
2014年 | 2505篇 |
2013年 | 3743篇 |
2012年 | 4533篇 |
2011年 | 4652篇 |
2010年 | 3006篇 |
2009年 | 3094篇 |
2008年 | 3235篇 |
2007年 | 2961篇 |
2006年 | 2699篇 |
2005年 | 2435篇 |
2004年 | 2467篇 |
2003年 | 1804篇 |
2002年 | 1647篇 |
2001年 | 1113篇 |
2000年 | 997篇 |
1999年 | 1057篇 |
1998年 | 898篇 |
1997年 | 819篇 |
1996年 | 896篇 |
1995年 | 762篇 |
1994年 | 666篇 |
1993年 | 610篇 |
1992年 | 567篇 |
1991年 | 443篇 |
1990年 | 404篇 |
1989年 | 302篇 |
1988年 | 283篇 |
1987年 | 255篇 |
1986年 | 206篇 |
1985年 | 246篇 |
1984年 | 226篇 |
1983年 | 183篇 |
1982年 | 138篇 |
1981年 | 118篇 |
1980年 | 101篇 |
1979年 | 64篇 |
1978年 | 54篇 |
1977年 | 55篇 |
1976年 | 53篇 |
1975年 | 55篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
红霉素A9-(1-异丙氧基环已基)肟的合成及其晶体结构 总被引:6,自引:1,他引:6
合成表征了红霉素A9-(1-异丙氧基环已基)肟的E和Z异构体,并在丙酮-水混 合溶液中培养出了前者的单晶,X射线衍射表明,其结构为正交晶系,P2_12_12_1 空间群,晶胞参数:a=2.3101(5) nm, b=2.3761(5) nm, c=0.97066(19)nm, V=5. 3279(8) nm~3,Z=4,μ=0.088 mm~(-1),F(000)=2064, D_c=1.176 g/cm~3。E-红 霉素A 9-(1-异丙氧基环已基)肟的晶体结构图明显表明1-异丙氧基环已基保护基 确实使十四元大环的构象发生了扭曲,使6-OH的周围空间不再拥挤,从而导致6- OH甲基化的选择性提高。 相似文献
992.
Paolesse R Nardis S Venanzi M Mastroianni M Russo M Fronczek FR Vicente MG 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(5):1192-1197
5,10,15-Triphenylcorrole (1) reacts with the Vilsmeier reagent (POCl(3)/DMF) to give the corresponding 3-formyl derivative 3 as the major product. The regioselectivity of the reaction was proven by X-ray crystallography and only traces of the 2-formyl isomer were observed. A more polar product is also observed and this compound becomes the major product when an excess of DMF is used for the preparation of the Vilsmeier reagent, while the formation of the 3-formyl isomer is almost completely suppressed. X-ray crystallography allowed us to identify this compound as the fully substituted N-ethane bridged derivative 4, formed from the attack of the Vilsmeier reagent at the inner core of the macrocycle. This compound is unique among porphyrinoid macrocycles, and further confirms the peculiarity of corrole chemistry. 相似文献
993.
Cp2TiCl2及(MeCp)2TiCl2在Et3N或NaNH2存在下与苄醇类化合物反应,高产率地合成了6个未见文献报道的二茂钛(Ⅳ)苄氧基衍生物,甲基二茂钛(Ⅳ)苄氧基化合物,经元素分析,HNMR和IR光谱确定了化合物的结构,并对其部分性质进行了讨论。 相似文献
994.
Simple and rapid determination of the drug naproxen in pharmaceutical preparations by heavy atom-induced room temperature phosphorescence 总被引:1,自引:0,他引:1
Segura Carretero A Cruces-Blanco C Ramírez García MI Cañabate Díaz B Fernández Gutiérrez A 《Talanta》1999,50(2):401-407
A simple, selective and sensitive heavy atom-induced room temperature phosphorimetric method (HAI-RTP) is described for the determination of naproxen (NAP) in pharmaceutical preparations. The phosphorescence signals are a consequence of intermolecular protection when analytes are, exclusively, in presence of a heavy atom salt and sodium sulfite as an oxygen scavenger to minimize RTP quenching. These variables selection constitute the basis of a HAI-RTP method for the determination of naproxen (detection limit 17.6 ng ml(-1); 1.71% relative standard deviation at 250 ng ml(-1)). The method has been applied satisfactorily to the analysis of pharmaceutical preparations. 相似文献
995.
María Pedrero Belén Casado F. Javier Manuel Villena Jose M. Pingarrón 《Fresenius' Journal of Analytical Chemistry》1994,349(7):546-551
An adsorptive stripping voltammetric method for the determination of the pesticide dinoseb (2-sec.-butyl-4,6-dinitrophenol) at the mercury film electrode is described. The deposition of the mercury film on a glassy carbon disk electrode was optimized. The temperature, at which the mercury film was deposited, was demonstrated to have a strong influence on the stripping peaks, the first one being much more intense than the second. A systematic study of the variables affecting the stripping response was carried out by differential pulse voltammetry. The results obtained have been compared with those at the HMDE; a significant improvement in the sensitivity of the method developed with the MFE was observed. Using a 300 s accumulation time, the limits of determination and detection were 3.6 × 10–10 and 1.1 × 10–10 mol L–1, respectively. The effect of the presence of several herbicides on the dinoseb response was also tested. The method has been applied to the determination of the pesticide in spiked apple juice at two concentration levels: 12.0 and 1.2 g L–1 of juice. 相似文献
996.
Alvarez S Aullón G Fandos R García Fierro JL Ocón P Otero A Rojas S Terreros P 《Dalton transactions (Cambridge, England : 2003)》2005,(5):938-944
The reaction of [Rh(micro-Cl)(COD)]2 with 4,6-dimethyl-pyrimidinethiolate (Me2-pymt) and subsequent substitution of COD by CO yields [Rh(Me2-pymt)(CO)2]. The stacking pattern found in this compound is in contradiction with previously studied comparable square-planar complexes of type d8-[M(chelate)(monodentate)2] in which each ligand has different pi-acidic character. A theoretical study of the intermolecular interactions and conformation of the title compound has been carried out, combining semi-empirical band calculations on the real chains and ab initio(MP2 level) calculations on a model dimer. The combination of electronic and steric effects determines the rotation of the successive monomers and the deviation from linearity of the one-dimensional stacks. Its behaviour in solution is also special, developing a blue colour and forming micelles, when adding water to acetone solutions. 相似文献
997.
Ignés-Mullol J Claret J Albalat R Crusats J Reigada R Romero MT Sagués F 《Langmuir : the ACS journal of surfaces and colloids》2005,21(7):2948-2955
Preparation of Langmuir monolayers of a mixture of trans- and cis-isomers of an azobenzene derivative, 4-[4-[(4-octylphenyl)azo]phenoxy]butanoic acid, results in the segregation of birefringent trans-isomer domains embedded in an isotropic medium of cis-isomers. Brewster angle microscopy observations allow us to identify different textures inside the domains depending on surface pressure, temperature, and domain size. The evolution of the monolayer in the dark, from initial droplets formed after spreading to a stable stripe texture, is described. The dynamics of domain coalescence and some morphological transitions induced by temperature and surface pressure changes are also discussed. A simple theoretical model is included to supplement some of these experimental observations. 相似文献
998.
Biosorption of copper(II) and zinc(II) from aqueous solution by Pseudomonas putida CZ1 总被引:1,自引:0,他引:1
Chen XC Wang YP Lin Q Shi JY Wu WX Chen YX 《Colloids and surfaces. B, Biointerfaces》2005,46(2):101-107
To study Pseudomonas putida CZ1, having high tolerance to copper and zinc on the removal of toxic metals from aqueous solutions, the biosorption of Cu(II) and Zn(II) by living and nonliving P. putida CZ1 were studied as functions of reaction time, initial pH of the solution and metal concentration. It was found that the optimum pH for Zn(II) removal by living and nonliving cells was 5.0, while it was 5.0 and 4.5, respectively, for Cu(II) removal. At the optimal conditions, metal ion biosorption was increased as the initial metal concentration increased. The adsorption data with respect to both metals provide an excellent fit to the Langmuir isotherm. The binding capacity of living cells is significantly higher than that of nonliving cells at tested conditions. It demonstrated that about 40-50% of the metals were actively taken up by P. putida CZ1, with the remainder being passively bound to the bacterium. Moreover, desorption efficiency of Cu(II) and Zn(II) by living cells was 72.5 and 45.6% under 0.1M HCl and it was 95.3 and 83.8% by nonliving cells, respectively. It may be due to Cu(II) and Zn(II) uptake by the living cells enhanced by intracellular accumulation. 相似文献
999.
Density functional theory has been applied at the B3LYP/6-311+G(d,p)//B3LYP/6-31G(d) level to examine the energetics of alpha,beta- versus beta,gamma-unsaturation for some common organic functional groups. Specifically, the relative stabilities of allyl-X (H2C=CHCH2X) and 1-propenyl-X (H3CCH=CHX) isomers have been computed for X = methyl, vinyl, phenyl, formyl, acetyl, methoxy, methylthio, methylsulfinyl, methylsulfonyl, sulfamoyl, and methoxysulfonyl, and the results are compared to available experimental data. The intrinsic preference of 3 kcal/mol for the 1-propenyl isomer when X = CH3 is exceeded by 2-4 kcal/mol for first-row conjugating groups, but it is not met for the sulfur-containing groups. In particular, alpha,beta-unsaturation is favored by less than 1 kcal/mol for the sulfone and sulfonamide analogues, while it is preferred by 8 kcal/mol for the vinyl-substituted case. Detailed structural results and torsional energy profiles are also reported. 相似文献
1000.
Luque Ruiz I García GC Gómez-Nieto MA 《Journal of chemical information and computer sciences》2004,44(6):1903-1911
The increase in the size and complexity of chemical databases necessitates the proposal and development of efficient methods of classification and recovery of information, which supposes proposal of a model of classification of database records and the use of a compatible model of screening for inspection of clusters and recovery of the molecules that satisfy the search criterion. The cycle graphs model based on consideration of all the cycles and chains (and equivalent cycles and chains) present in the molecular structure has been proven appropriate for classification of chemical databases, giving rise to a generation of different classification levels depending on the structural elements (cycles and chains) that are considered. In this paper we propose a screening model, compatible with the cycle graphs model, based on a hierarchy of levels of abstraction. The set of molecules that satisfies a screening model (or selection criterion) diminishes as we advance in the hierarchy of levels of the model, which allows filtering of records and, therefore, an increase in the efficiency of the screening process. In the following work of this series we describe and validate the screening tool developed. 相似文献