全文获取类型
收费全文 | 32844篇 |
免费 | 1317篇 |
国内免费 | 43篇 |
专业分类
化学 | 22924篇 |
晶体学 | 243篇 |
力学 | 589篇 |
数学 | 4545篇 |
物理学 | 5903篇 |
出版年
2023年 | 262篇 |
2022年 | 234篇 |
2021年 | 436篇 |
2020年 | 563篇 |
2019年 | 528篇 |
2018年 | 696篇 |
2017年 | 640篇 |
2016年 | 1255篇 |
2015年 | 1015篇 |
2014年 | 1026篇 |
2013年 | 2107篇 |
2012年 | 2320篇 |
2011年 | 2487篇 |
2010年 | 1456篇 |
2009年 | 1234篇 |
2008年 | 2131篇 |
2007年 | 2098篇 |
2006年 | 1824篇 |
2005年 | 1684篇 |
2004年 | 1339篇 |
2003年 | 1042篇 |
2002年 | 937篇 |
2001年 | 715篇 |
2000年 | 612篇 |
1999年 | 445篇 |
1998年 | 334篇 |
1997年 | 255篇 |
1996年 | 383篇 |
1995年 | 253篇 |
1994年 | 246篇 |
1993年 | 287篇 |
1992年 | 258篇 |
1991年 | 181篇 |
1990年 | 158篇 |
1989年 | 141篇 |
1988年 | 133篇 |
1987年 | 133篇 |
1986年 | 130篇 |
1985年 | 190篇 |
1984年 | 155篇 |
1983年 | 127篇 |
1982年 | 116篇 |
1981年 | 106篇 |
1980年 | 90篇 |
1979年 | 105篇 |
1978年 | 87篇 |
1977年 | 80篇 |
1976年 | 86篇 |
1975年 | 76篇 |
1973年 | 86篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
921.
The solvothermal reaction of (N(C(4)H(9))(4))(2)[Re(2)Cl(8)] with trifluoroacetic acid and acetic anhydride leads to the new rhenium trifluoroacetate dimer N(C(4)H(9))(4)[Re(2)(OOCCF(3))Cl(6)] (1) and to the rhenium carbonyl dimer Re(2)(mu(2)-Cl)(2)(CO)(8) as the rhenium-reduced byproduct. The reaction of the precursor complex, N(C(4)H(9))(4)[Re(2)(OOCCF(3))Cl(6)] (1), with the organometallic carboxylic acid (CO)(6)Co(2)HCCCOOH leads to the cluster of clusters compound Re(2)(OOCCCHCo(2)(CO)(6))(4)Cl(2) (2), which has the dimer structure of Re(2)(OOCR)(4)Cl(2). Cyclic voltammetric measurements show that Re(2)(OOCCCHCo(2)(CO)(6))(4)Cl(2) (2) has one reduction centered on the dirhenium core and a reduction centered on the cobalt atoms. DFT calculations have been used to rationalize the observed displacements of the voltammetric signals in Re(2)(OOCCCHCo(2)(CO)(6))(4)Cl(2) (2) compared to the parent ligand (CO)(6)Co(2)HCCCOOH and rhenium pivalate. 相似文献
922.
Micellar electrokinetic capillary chromatography for the determination of Viagra and its metabolite (UK-103,320) in human serum 总被引:1,自引:0,他引:1
Berzas Nevado JJ Rodríguez Flores J Castañeda Peñalvo G Rodríguez Fariñas N 《Electrophoresis》2001,22(10):2004-2009
Micellar electrokinetic capillary chromatography (MEKC) was investigated for the determination of Viagra (sildenafil citrate, SC) and its metabolite (UK-103,320) in human serum in a concentration range of clinical interest. For MEKC, human serum samples spiked with SC and UK were obtained directly after elution with methanol from a tC18 cartridge. The extract was evaporated and regenerated in a solution 1 mM of phosphate buffer (pH 12.3) which contained a methanol percentage of 20% that was analyzed using phosphate buffer (pH 12.3, 10 mM) containing 30 mM sodium dodecyl sulfate (SDS) as separation electrolyte and a fused-silica capillary. This method gave satisfactory interday precision with respect to migration times relative standard deviation (RSD < 1%) and linear responses for the concentration ranges investigated (0.50-3.50 mg L(-1) for the compound SC and 0.90-4.60 mg L(-1) for UK). An intraday RSD (n = 5 graphs) between the slopes of the calibration graphs was acceptable (6.40%) for SC and (3.37%) for UK. A satisfactory interday precision between slopes was also obtained (RSD 4.10% for SC and a RSD 2.72% for UK) which demonstrated the ruggedness of this method. Detection limits (S/N = 3) were about 200 ng/mL for both compounds in human serum. MEKC was shown as a good method with regards to simplicity, precision and sensitivity. 相似文献
923.
Érika Pinto Marinho A. G. Souza Danniely S. de Melo Iêda M. G. Santos Dulce M. A. Melo Walquíria J. da Silva 《Journal of Thermal Analysis and Calorimetry》2007,87(3):801-804
Because
of their electrical, magnetic and catalytic properties rare earth and transition
metal mixed oxides are important compounds. Lanthanum chromites have been
extensively used as solid oxide fuel cell (SOFC) interconnect materials. In
this work, lanthanum chromites partially substituted by alkaline earth metals
were synthesized by the urea combustion process. TG and DSC techniques were
used to evaluate the presence of the organic material in the powder after
reaction on the hot plate. The powders were calcinated at 900°C and characterized
by XRD and SEM. The results show that the particles have nanometric dimensions
and the perovskite structure was formed. 相似文献
924.
The thermodynamic functions Gibbs energy, enthalpy and entropy of solution, mixing and solvation of acetaminophen in propylene
glycol (PG) + ethanol (EtOH) cosolvent mixtures were evaluated from solubility data measured at several temperatures, using
the van't Hoff and Gibbs equations. The solubility was greater at 50% m/m of PG at 20.0^C, while it was greater at 80% of
PG at 40.0 ^C where m/m refers to mass percent. The solvation of this drug is appreciably greater in the mixtures than in
the pure solvents. By means of an enthalpy–entropy compensation analysis, complex behavior was found for the solution. From
0 up to 20% of PG and from 60 up to 100% of PG the solution process is enthalpy driven, whereas from 20 up to 60% of PG it
is entropy driven. These facts can be explained in terms of a decrease in the energy required for cavity formation in the
solvent for mixtures containing 20–60% of PG. 相似文献
925.
Badorrey R Cativiela C Díaz-de-Villegas MD Díez R Galbiati F Gálvez JA 《The Journal of organic chemistry》2005,70(24):10102-10105
[reaction: see text] Addition of trimethylsilyl cyanide to ketimines derived from (R)-2,2-dimethyl-1,3-dioxolan-4-yl methyl ketone to generate a quaternary stereocenter has been achieved with high yields and excellent diastereoselectivity. The stereoselectivity was found to be temperature and solvent dependent. The beta-hydroxy-alpha-amino nitrile of syn configuration was the major compound in kinetically controlled reactions, whereas the anti stereoisomer was obtained in excess in thermodynamically controlled reactions. Double stereodifferentiation under kinetic control conditions was successful, and the cyanation reaction occurred with complete syn diastereoselectivity using the matched pair. The versatility of the resulting amino nitrile as a synthetic intermediate was tested by performing the synthesis of orthogonally protected (R)-(2-aminomethyl)alanine. 相似文献
926.
Application of matrix solid-phase dispersion to the determination of a new generation of fungicides in fruits and vegetables 总被引:8,自引:0,他引:8
A method based on matrix solid-phase dispersion (MSPD) and gas chromatography to determine eight fungicides in fruits and vegetables is described. Fungicide residues were identified and quantified using nitrogen-phosphorus detection and electron-capture detection connected in parallel and confirmed by mass spectrometric detection. The method required 0.5 g of sample, C18 bonded silica as dispersant sorbent, silica as clean-up sorbent and ethyl acetate as eluting solvent. Recoveries from spiked orange, apple, tomato, artichoke, carrot and courgette samples ranged from 62 to 102% and relative standard deviations were less than 15% in the concentration range 0.05-10 mg kg(-1). Detection and quantitation limits ranged 3-30 microg kg(-1) and 10-100 microg kg(-1), respectively, with linear calibration curves up to 10 mg kg(-1). The analytical characteristics of MSPD compared very favourably with the results of a classical multiresidue method, which uses ethyl acetate and anhydrous sodium sulphate for the extraction. 相似文献
927.
Palacios F Aparicio D Ochoa De Retana AM de los Santos JM Gil JI Alonso JM 《The Journal of organic chemistry》2002,67(21):7283-7288
A simple and efficient asymmetric synthesis of 2H-azirine-2-phosphine oxides 3 is described. The key step is a solid-phase bound achiral or chiral amine-mediated Neber reaction of beta-ketoxime tosylates derived from phosphine oxides 1. Reaction of 2H-azirines 3 and 11 with carboxylic acids 4 gives phosphorylated ketamides 5 and 12. Ring closure of ketamides 5 and 12 with triphenylphosphine and hexachloroethane in the presence of triethylamine leads to the formation of phosphorylated oxazoles 8 and 13. 相似文献
928.
[reaction: see text] Tetrasubstituted pyrazines containing two phosphonate groups 2 in positions 2 and 5 and trisubstituted pyrazines containing a phosphonate 5 or a phosphine oxide group 7 in position 2 are obtained by thermal treatment of 2H-azirine-2-phosphonates 1 and -phosphine oxides 6. These pyrazines can also be prepared from beta-ketoxime tosylates 9 and 10 or from oxime derived from phosphine oxide 11. 相似文献
929.
Density-functional theory studies on the [2 + 2] reaction between N-silylimines and ketenes to form the corresponding 2-azetidinones (beta-lactams) help to clarify several aspects on the mechanism of the Staudinger reaction. This reaction has been studied experimentally by Panunzio et al. It is shown that the formation of the 2-azetidinone ring takes place via two consecutive reactions. The first reaction consists of the nucleophilic addition of the iminic nitrogen to the sp-hybridized carbon atom of the ketene, with simultaneous migration of the silyl group from the imine to the oxygen atom of the ketene. This leads to silyl enol intermediates, in good agreement with the experimental results. Formation of the N-silylated beta-lactam takes place via a domino reaction consisting of a conrotatory thermal electrocyclization followed by a new silatropic rearrangement. It is also found that isomerization of the starting N-silylimine has a lower activation barrier than that associated with the formation of the C-N bond, which explains the stereochemical outcome experimentally observed. Further considerations on the asymmetric torquoelectronic effects involved in this reaction are also reported. 相似文献
930.
Sáenz-Carbonell Luis Loyola-Vargas Víctor M. 《Applied biochemistry and biotechnology》1997,61(3):321-337
Hairy roots are less susceptible to manipulation by changes in medium composition than callus and cell suspension cultures.
However, when the individual components of the Gamborg’s B5 medium were modified one by one, several of them modified the yield of root cultures. Nitrogen (N) source changes, the absence
of phosphorus (P), calcium (Ca), and cobalt (Co), and the increase in the sucrose content of the medium increased the level
of alkaloids inDatura stramonium hairy root cultures. The use of ammoniun as N source provoked the alkaloid excretion into the medium. The addition of different
auxins inhibited the alkaloid accumulation, but the addition of abscisic acid (ABA) did not change the alkaloid content of
the cultures. The use of MeJa increased the content of hyoscyamine to 100%. 相似文献