全文获取类型
收费全文 | 7761篇 |
免费 | 292篇 |
国内免费 | 21篇 |
专业分类
化学 | 5834篇 |
晶体学 | 117篇 |
力学 | 143篇 |
数学 | 856篇 |
物理学 | 1124篇 |
出版年
2023年 | 51篇 |
2022年 | 156篇 |
2021年 | 144篇 |
2020年 | 127篇 |
2019年 | 136篇 |
2018年 | 107篇 |
2017年 | 91篇 |
2016年 | 231篇 |
2015年 | 220篇 |
2014年 | 265篇 |
2013年 | 420篇 |
2012年 | 502篇 |
2011年 | 593篇 |
2010年 | 326篇 |
2009年 | 317篇 |
2008年 | 513篇 |
2007年 | 469篇 |
2006年 | 435篇 |
2005年 | 428篇 |
2004年 | 357篇 |
2003年 | 285篇 |
2002年 | 281篇 |
2001年 | 115篇 |
2000年 | 84篇 |
1999年 | 102篇 |
1998年 | 73篇 |
1997年 | 76篇 |
1996年 | 99篇 |
1995年 | 59篇 |
1994年 | 78篇 |
1993年 | 63篇 |
1992年 | 67篇 |
1991年 | 56篇 |
1990年 | 49篇 |
1989年 | 35篇 |
1988年 | 36篇 |
1987年 | 30篇 |
1986年 | 38篇 |
1985年 | 43篇 |
1984年 | 40篇 |
1983年 | 40篇 |
1982年 | 55篇 |
1981年 | 36篇 |
1980年 | 34篇 |
1979年 | 40篇 |
1978年 | 27篇 |
1977年 | 32篇 |
1976年 | 28篇 |
1975年 | 23篇 |
1974年 | 23篇 |
排序方式: 共有8074条查询结果,搜索用时 31 毫秒
191.
J. Sanmartín M. R. Bermejo J. A. García-Vázquez J. Romero A. Sousa 《Transition Metal Chemistry》1993,18(5):528-530
Summary The electrochemical oxidation of anodic metals (iron and copper) in MeCN solutions of 2-pyridinone (HOPy), 1-hydroxy-2-pyridinethione (HPT), 2-pyridinemethanethiol-1-oxide (HPMTO) or its dimer 2,2-dithiodimethyldipyridine-1,1-dioxide (PMTO)2, gave the simple complexes Fe(OPy)2 · H2O, Cu(OPy)2 · 3H2O, Fe(PT)2 · 3H2O, Fe(PT)3, Cu(PT)2, Fe(PMTO)2·3H2O and Cu(PMTO)2·H2O, respectively. When 1,10-phenanthroline (phen) was added to the electrolytic phase, only two mixed complexes were obtained: Cu(OPy)2phen·3H2O and Fe(PT)2phen·2H2O. The possible molecular structures of the complexes were studied on the basis of their i.r. spectra and magnetic properties. 相似文献
192.
Jacqueline Ficini Jean dAngelo Arnaud Eman Anne Marie Touzin 《Tetrahedron letters》1976,17(9):683-686
193.
We describe the use of the polymeric surfactant poly(sodium undecylenic sulfate) (poly-SUS) as a stationary phase coating in open-tubular capillary electrochromatography (OT-CEC) coupled with electrospray ionization-mass spectrometry (ESI-MS) for the analysis of beta-blocker and benzodiazepine analytes. The production of a polymeric surfactant coating on the capillary inner wall involves (i) adsorption of the cationic polymer poly(diallyldimethylammonium chloride) (PDADMAC) to the inner surface of capillary, and (ii) adsorption of the negatively charged poly-SUS onto the cationic polymer layer via strong physical interaction of the two polymer layers. As compared with micellar electrokinetic chromatography (MEKC) coupled with ESI-MS, the main advantage of this proposed method is minimization of introduction of the monomeric or polymeric surfactant into the mass spectrometer, thus avoiding the interference of the nonvolatile micelle in ESI-MS. The effects of buffer pH and applied voltage on the separation of the analytes are also discussed. Under optimum conditions, four of the five beta-blockers and four benzodiazepines are separated. 相似文献
194.
The effect of vibrational structure on the frequency dependence of the first molecular hyperpolarizability of two thiophene-based charge-transfer chromophores is investigated. A time domain formulation is used to express the polarizability. The new expression includes the solvent-induced inhomogeneous distribution of electronic transition frequencies as well as the effect of the motion of solvent molecules that modulates the vibrational and electronic transition frequencies of the nonlinear optical molecule on which the first molecular hyperpolarizability depends. Resonance Raman scattering and one-photon absorption spectra of the chromophores are measured. By simultaneously fitting the experimental one-photon absorption spectrum and Raman cross sections of vibrational lines derived from resonance Raman scattering to a theoretical model, important parameters needed for the calculation of the first molecular hyperpolarizability are obtained. The first molecular hyperpolarizability is calculated as a function of frequency covering both nonresonance and two-photon resonance regions. The calculated result is compared with the measured hyperpolarizability as a function of frequency of the excitation laser. The resonance Raman-based analysis is shown to account reasonably well for the dispersion of the hyperpolarizability of the two charge transfer chromophores. 相似文献
195.
Rodrigues JA Abramovitch RA de Sousa JD Leiva GC 《The Journal of organic chemistry》2004,69(9):2920-2928
In preliminary communications, we reported the diastereoselective synthesis of cularine and sarcocapnine via the intramolecular ring closure of nitrenium and oxenium ions, a new highly diastereoselective reductive methylation with (+)-8-phenylmenthyl chloroacetate followed by reduction with sodium borohydride, and a facile entry to the isoquinoline precursors by aza-Wittig electrocyclic ring closure. We now report the full details of the syntheses of (+)-O-demethylcularine, (+)-cularine, (+)-sarcocapnidine, (+)-sarcocapnine, and (+)-crassifoline and describe different methods of synthesis of their precursors. 相似文献
196.
Abstract— Pulmonary macrophages obtained from neonatal rats contain approximately four times the activity of cyanide resistant superoxide dismutase and catalase compared with the cells from adult animals. The activity is highest immediately after birth and diminishes with age until the minimum level is reached at approximately 3 weeks of age. Superimposed upon this change in basal activity is the capability of neonatal cells to synthesize additional cyanide resistant superoxide dismutase and catalase when either the animals or isolated pulmonary macrophages are exposed to 95–100% oxygen. The inductive effect begins at 2–3 days after birth, peaks at 10 days, and disappears at approximately 15 days after birth. In contrast to adult rats, neonatal rats are extremely resistant to the toxic effects of oxygen. If, however, the oxygen mediated increase in both enzymes is prevented or the maximum effective pulmonary macrophage number is diminished in test animals, these animals become vulnerable to toxic effects of oxygen exposure, observed by gross and histologic examination of lung tissue, in a manner similar to adult animals. These data indicate that both cyanide-resistant superoxide dismutase and catalase may be part of the endogenous defense mechanisms which provide neonatal rats with an exceptional resistance to oxygen toxicity. 相似文献
197.
Anne Vessieres Daniel Touchard Pierre Dixneuf 《Journal of organometallic chemistry》1976,118(1):93-100
Heterodienetricarbonyliron complexes react with ligands ( L = PMe2Ph, P(OMe)3 or P(OPh)3) to give the adducts (enone)Fe(CO)3L with the ethylenic double bond coordinated only to the iron(0). Electron-releasing and low-steric effects of L make the reaction which is specific for enones easier compared to that for dienes. PMe2Ph allows enone exchange and P(OPh)3 promotes carbonyl elimination. Ligand influence is shown by infrared spectroscopy and by the shielding of ethylenic protons in NMR spectroscopy. 相似文献
198.
Pedro de Lima Neto Mohamed Atik Luis A. Avaca Michel A. Aegerter 《Journal of Sol-Gel Science and Technology》1994,1(2):177-184
ZrO2 coatings deposited on 316 L stainless steel sheets were synthesized by sol-gel method using Zr(OC3H7)4 as precursor and isopropanol, glacial acetic acid, and water as solvents for application with ultrasounds. Different solutions for dip-coating were prepared with compositions varying between 0.025 and 0.9 mol/dm3 of ZrO2. X-ray diffraction shows that the films densified at 800°C are crystalline with a tetragonal structure. The thickness of the coatings varied from 0.35–0.75 m. The influence of the ZrO2 coatings on the corrosion behavior of stainless steel substrates in aqueous NaCl was studied through potentiodynamic polarization curves at 1 mV/s. The values of the electrochemical parameters allow for an explanation of the role of the films in the increased resistance of steel against corrosion in moderately aggressive environments. 相似文献
199.
A tungsten-rhodium treatment on the integrated platform of a transversely heated graphite atomiser was used as a permanent chemical modifier for the determination of copper in biological materials by using digested samples as well as slurry sampling in electrothermal atomic absorption spectrometry. The W-Rh permanent modifier was as efficient as Pd+Mg(NO(3))(2) conventional modifier for obtaining good Cu thermal stabilisation in the digested and slurry samples. The permanent W-Rh modifier remained stable by approximately 300 and 250 firings when 20 mul of digested sample and 20 mul of slurry were delivered into the atomiser, respectively. In addition, the permanent modifier increased the tube lifetime up to 1370 and 744 analytical measurements in the digested and slurry samples, respectively. Also, when the W-Rh permanent modifier was employed, there was less variation of the slope of the analytical curves during the total atomiser lifetime, resulting in a decreased need of re-calibration during routine analysis, increasing the sample throughput, and consequently diminishing the variable analytical costs. Detection limits obtained with W-Rh permanent modifier were 0.64 and 0.33 mug g(-1) Cu for digested (dilution factor 100 ml g(-1)) and 1.0% m/v slurries of biological materials, respectively. Results for the determination of copper in the samples were in agreement with those obtained with decomposed sample solutions by using Pd+Mg(NO(3)), since no statistical differences were found after applying the paired t-test at the 95% level. 相似文献
200.
Stanciu C Hino SS Stender M Richards AF Olmstead MM Power PP 《Inorganic chemistry》2005,44(8):2774-2780
The synthesis and characterization of the first divalent germanium, tin, and lead monoamide derivatives of the parent amide group -NH(2) are presented. They have the general formula (ArMNH(2))(2) (M = Ge, Ar = Ar'(C(6)H(3)-2,6-Pr(i)(2)) or Ar* (C(6)H(3)-2,6(C(6)H(2)-2,4,6-Pr(i)(3))); M = Sn, Ar = Ar*; M = Pb, Ar = Ar*). For germanium and tin, they were obtained by reacting the corresponding terphenyl halides of the group 14 elements with liquid ammonia in diethyl ether. The lead amide derivative (Ar*PbNH(2))(2) was synthesized by reaction of LiNH(2) with Ar*PbBr in diethyl ether. The compounds were characterized by IR and multinuclear NMR spectroscopies and by X-ray crystallography in the case of the (Ar'GeNH(2))(2) or (Ar*SnNH(2))(2) derivatives. They possess dimeric structures with two -NH(2) groups bridging the germanium and tin centers. For lead, the reaction with ammonia led to isolation of a stable ammine complex of formula Ar*PbBr(NH(3)) which was characterized by IR and NMR spectroscopies and by X-ray crystallography. It is the first structural characterization of a divalent lead ammine complex. 相似文献