全文获取类型
收费全文 | 1817篇 |
免费 | 49篇 |
国内免费 | 9篇 |
专业分类
化学 | 1045篇 |
晶体学 | 24篇 |
力学 | 78篇 |
数学 | 369篇 |
物理学 | 359篇 |
出版年
2023年 | 20篇 |
2022年 | 60篇 |
2021年 | 75篇 |
2020年 | 70篇 |
2019年 | 82篇 |
2018年 | 41篇 |
2017年 | 50篇 |
2016年 | 83篇 |
2015年 | 59篇 |
2014年 | 80篇 |
2013年 | 126篇 |
2012年 | 131篇 |
2011年 | 129篇 |
2010年 | 60篇 |
2009年 | 58篇 |
2008年 | 75篇 |
2007年 | 66篇 |
2006年 | 50篇 |
2005年 | 55篇 |
2004年 | 48篇 |
2003年 | 31篇 |
2002年 | 41篇 |
2001年 | 24篇 |
2000年 | 27篇 |
1999年 | 14篇 |
1998年 | 17篇 |
1997年 | 8篇 |
1996年 | 25篇 |
1995年 | 6篇 |
1994年 | 11篇 |
1993年 | 14篇 |
1992年 | 13篇 |
1991年 | 9篇 |
1990年 | 13篇 |
1989年 | 10篇 |
1988年 | 11篇 |
1987年 | 16篇 |
1986年 | 12篇 |
1985年 | 12篇 |
1984年 | 19篇 |
1982年 | 22篇 |
1981年 | 16篇 |
1980年 | 17篇 |
1979年 | 20篇 |
1978年 | 5篇 |
1977年 | 9篇 |
1976年 | 10篇 |
1975年 | 7篇 |
1974年 | 4篇 |
1968年 | 3篇 |
排序方式: 共有1875条查询结果,搜索用时 0 毫秒
41.
Nguyen HP Ortiz IP Temiyasathit C Kim SB Schug KA 《Rapid communications in mass spectrometry : RCM》2008,22(14):2220-2226
Crude oil fingerprints were obtained from four crude oils by laser desorption/ionization mass spectrometry (LDI-MS) using a silver nitrate cationization reagent. Replicate analyses produced spectral data with a large number of features for each sample (>11,000 m/z values) which were statistically analyzed to extract useful information for their differentiation. Individual characteristic features from the data set were identified by a false discovery rate based feature selection procedure based on the analysis of variance models. The selected features were, in turn, evaluated using classification models. A substantially reduced set of 23 features was obtained through this procedure. One oil sample containing a high ratio of saturated/aromatic hydrocarbon content was easily distinguished from the others using this reduced set. The other three samples were more difficult to distinguish by LDI-MS using a silver cationization reagent; however, a minimal number of significant features were still identified for this purpose. Focus is placed on presenting this multivariate statistical method as a rapid and simple analytical procedure for classifying and distinguishing complex mixtures. 相似文献
42.
The development of a new method for stereoselective glycosylation with glycosyl trichloroacetimidate donors employing cationic palladium(II), Pd(CH(3)CN)(4)(BF(4))(2), is described. This process employs Pd(CH(3)CN)(4)(BF(4))(2) as an efficient activator, providing access to a variety of disaccharides and glycopeptides. This reaction is highly stereoselective and proceeds under mild conditions with low catalyst loading. Interestingly, this palladium catalysis directs beta-glucosylations in the absence of classical neighboring group participation. 相似文献
43.
We report on the observation of the excitation/emission spectrum of a dendrimer-encapsulated gold nanocluster; the synthesis of Au-PAMAM was based on reduction of HAuCl4 x 3 H2O co-dissolved in methanol together with fourth-generation OH-terminated PAMAM. 相似文献
44.
Li YS Tran T Xu Y Vecchio NE 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2006,65(3-4):779-786
Trimethoxypropylsilane (TMPS) and bis(trimethoxysilyl)ethane (BTMSE) were used as surface modifiers of metal vie the sol-gel process and dip coating. In addition to the single coating of Al, Cu and Sn, double treatments of Al were also conducted by combining coatings with these sol-gels in different sequences. Reflection and absorption infrared spectroscopy (RAIR) was employed to characterize and to trace the proceeding of the sol-gel process of the films. It was found that the silanol condensation occurs in the coating films on Al and the covalent linkage exists between the TMPS film and copper surface. From the assigned vibration modes, two conformers were identified in pure TMPS, TMPS sol-gel and coated film. A series of dip coating experiments with different concentrations of TMPS sol-gel was conducted, and the results from the collected RAIR spectra of the coated samples suggested that the coated Cu consistently has a better RAIR spectrum than that of the coated Al. The TMPS sol-gel appeared to have a better affinity to Cu than to Al. The temperature effect and the aging effect in the coating films were studied. X-ray photoelectronic spectroscopy (XPS) was employed to characterize the coated film, and the XPS data confirm the formation of the siloxane film from the silane coupling agents (SCA). Electrochemical impedance spectra (EIS) have been collected for bare Al and Cu, BTMSE sol-gel coated Al, and TMPS sol-gel coated Cu in 0.15M NaCl solution. The corresponding electronic circuit parameters have been determined to match the experimental EIS data. 相似文献
45.
Tomohiro Ohta Takeru Ito Masahiro Shimizu Lisa Tauchi Huy‐Danh Nguyen‐Tran Jong‐Chul Park Byoung‐Suhk Kim Ick‐Soo Kim Kazuchika Ohta 《先进技术聚合物》2011,22(12):2653-2658
We have developed a novel synthetic method that enables us to easily synthesize metal‐capsulated carbon nanotubes (CNTs) in a laboratory by using a combined technology of electrospinning‐metallization and microwave heating. These techniques greatly shorten the time for the synthesis of the CNTs in comparison with the conventional methods. TEM analysis confirmed a successful formation of the CNTs, and the resulting CNTs were multi‐walled and found to be about 25–100 nm in diameters. The products prepared by heating at 600 and 900°C exhibited less‐developed and strongly curved CNTs, whereas the products prepared by heating at 700 and 800°C relatively well‐developed long CNTs. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
46.
Density functional theory and multiconfigurational CASPT2 and density matrix renormalization group DMRG-CASPT2 have been employed to study the low-lying states of NbGen−/0/+ (n = 1–3) clusters. With the DMRG-CASPT2 method, the active spaces are extended to a size of 20 orbitals. For most of the states, the CASPT2 relative energies are comparable with the DMRG-CASPT2 results. The leading configuration, bond distances, vibrational frequencies, and relative energies of the low-lying states of these clusters were calculated. The ground states of these clusters were computed to be 3Δ, 4Φ, and 5Φ of NbGe−/0/+; 3A2, 4B1, and 3B1 of cyclic-NbGe2−/0/+; and 1A′, 12A″ and 12A′′ (2E), and 3A″ of tetrahedral-NbGe3−/0/+ isomers. For NbGe cluster, our calculations proposed that the 6∑ is almost degenerate with the 4Φ with the CASPT2 and DMRG-CASPT2 relative energies of 0.05 and 0.06 eV. The adiabatic detachment energies of NbGen− (n = 1–3) clusters were estimated to be 1.46, 1.55, and 2.18 eV by the CASPT2 method. The relevant detachment energies of the anionic ground state and the ionization energies of the neutral ground states are evaluated at the CASPT2 level. 相似文献
47.
The rhodium-catalyzed regioselective amination of tertiary allylic trichloroacetimidates with unactivated aromatic amines is a direct and efficient approach to the preparation of α,α-disubstituted allylic aryl amines in good yield and with excellent regioselectivity. This method is applicable to a variety of unactivated primary and secondary amines and allows for the preparation of reverse prenylated indoles in two steps. 相似文献
48.
The gas-surface reaction dynamics of NO impinging on an iron(II) phthalocyanine (FePc) monolayer were investigated using King and Wells sticking measurements. The initial sticking probability was measured as a function of both incident molecular beam energy (0.09-0.4 eV) and surface temperature (100-300 K). NO adsorption onto FePc saturates at 3% of a monolayer for all incident beam energies and surface temperatures, suggesting that the final chemisorption site is confined to the Fe metal centers. At low surface temperature and low incident beam energy, the initial sticking probability is 40% and decreases linearly with increasing beam energy and surface temperature. The results are consistent with the NO molecule sticking onto the FePc molecules via physisorption to the aromatics followed by diffusion to the Fe metal center, or precursor-mediated chemisorption. The adsorption mechanism of NO onto FePc was confirmed by control studies of NO sticking onto metal-free H2Pc, inert Au111, and reactive Al111. 相似文献
49.
Pham TN Hinchley SL Rankin DW Liptaj T Uhrín D 《Journal of the American Chemical Society》2004,126(40):13100-13110
We have developed methodology for the determination of solution structures of small molecules from residual dipolar coupling constants measured in dilute liquid crystals. The power of the new technique is demonstrated by the determination of the structure of methyl beta-d-xylopyranoside (I) in solution. An oriented sample of I was prepared using a mixture of C(12)E(5) and hexanol in D(2)O. Thirty residual dipolar coupling constants, ranging from -6.44 to 4.99 Hz, were measured using intensity-based J-modulated NMR techniques. These include 15 D(HH), 4 (1)D(CH), and 11 (n)D(CH) coupling constants. The accuracy of the dipolar coupling constants is estimated to be < +/- 0.02 Hz. New constant-time HMBC NMR experiments were developed for the measurement of (n)D(CH) coupling constants, the use of which was crucial for the successful structure determination of I, as they allowed us to increase the number of fitted parameters. The structure of I was refined using a model in which the directly bonded interatom distances were fixed at their ab initio values, while 16 geometrical and 5 order parameters were optimized. These included 2 CCC and 6 CCH angles, and 2 CCCC and 6 CCCH dihedral angles. Vibrationally averaged dipolar coupling constants were used during the refinement. The refined solution structure of I is very similar to that obtained by ab initio calculations, with 11 bond and dihedral angles differing by 0.8 degrees or less and the remaining 5 parameters differing by up to 3.3 degrees . Comparison with the neutron diffraction structure showed larger differences attributable to crystal packing effects. Reducing the degree of order by using dilute liquid crystalline media in combination with precise measurement of small residual dipolar coupling constants, as shown here, is a way of overcoming the limitation of strongly orienting liquid crystals associated with the complexity of (1)H NMR spectra for molecules with more than 12 protons. 相似文献
50.
Summary An ,-appended eighteen carbon chains hypercin derivative (2) was synthesized starting from emodin. The overall yield of the seven step synthesis was 12%. The1H and13C NMR, absorption, and emission spectroscopic properties were measured;2 can be dissolved even in apolar solvents and polyethylene.
Synthese und Eigenschaften eines mit C18-Ketten ,-substituierten Hypericinderivats
Zusammenfassung Ein in den Positionen , mit zwei C18-Ketten substituiertes Derivat des Hypericins (2) wurde ausgehend von Emodin synthetisiert. Die Gesamtausbeute der siebenstufigen Synthese betrug 12%. Die1H- und13C-NMR, absorptions- und emissionsspektroskopischen Eigenschaften wurden gemessen;2 kann sogar in apolaren Lösungsmitteln und Polyethylen gelöst werden.相似文献