全文获取类型
收费全文 | 2410篇 |
免费 | 37篇 |
国内免费 | 12篇 |
专业分类
化学 | 1530篇 |
晶体学 | 16篇 |
力学 | 44篇 |
数学 | 374篇 |
物理学 | 495篇 |
出版年
2022年 | 11篇 |
2021年 | 12篇 |
2020年 | 16篇 |
2019年 | 25篇 |
2017年 | 17篇 |
2016年 | 37篇 |
2015年 | 35篇 |
2014年 | 33篇 |
2013年 | 93篇 |
2012年 | 100篇 |
2011年 | 124篇 |
2010年 | 69篇 |
2009年 | 66篇 |
2008年 | 128篇 |
2007年 | 110篇 |
2006年 | 142篇 |
2005年 | 123篇 |
2004年 | 120篇 |
2003年 | 77篇 |
2002年 | 96篇 |
2001年 | 45篇 |
2000年 | 45篇 |
1999年 | 31篇 |
1998年 | 27篇 |
1997年 | 25篇 |
1996年 | 34篇 |
1995年 | 32篇 |
1994年 | 37篇 |
1993年 | 28篇 |
1992年 | 35篇 |
1991年 | 20篇 |
1990年 | 19篇 |
1989年 | 40篇 |
1988年 | 27篇 |
1987年 | 19篇 |
1986年 | 22篇 |
1985年 | 24篇 |
1984年 | 28篇 |
1983年 | 28篇 |
1982年 | 38篇 |
1981年 | 37篇 |
1980年 | 33篇 |
1979年 | 30篇 |
1978年 | 31篇 |
1977年 | 42篇 |
1976年 | 32篇 |
1975年 | 25篇 |
1974年 | 33篇 |
1973年 | 38篇 |
1972年 | 11篇 |
排序方式: 共有2459条查询结果,搜索用时 15 毫秒
121.
Michael V. Gorshkov Christophe D. Masselon Gordon A. Anderson Harold R. Udseth Richard Harkewicz Richard D. Smith 《Journal of the American Society for Mass Spectrometry》2001,12(11):1169-1173
A fast dynamic ion cooling technique based upon the adiabatic invariant phenomenon for Fourier transform ion cyclotron resonance mass spectrometry (FTICR) is presented. The method cools ions in the FTICR trap more efficiently, within a few hundred milliseconds without the use of a buffer gas, and results in a substantial signal enhancement. All performance aspects of the FTICR spectrum, e.g., peak intensities, mass resolution, and mass accuracy, improve significantly compared with cooling based on ion-ion interactions. The method may be useful in biological applications of FTICR, such as in proteomic studies involving extended on-line liquid chromatography (LC) separations, in which both the duty cycle and mass accuracy are crucially important. 相似文献
122.
Saeed KA Ayorinde FO Eribo BE Gordon M Collier L 《Journal of AOAC International》2001,84(4):1109-1115
Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) was used for the characterization of a partially transesterified poly(beta-hydroxyalkanoate) (PHA), a polymer produced by the bacterial strain Alcaligenes eutrophus with saponified vegetable oils as the sole carbon sources. The transesterification was carried out separately under acidic and basic conditions to obtain PHA oligomers weighing <10 kDa. The intact oligomers were detected in their cationized forms, [M + Na]+ and [M + K]+, by MALDI-TOFMS. A composition analysis, using the MALDI-TOF spectra, indicated that the oligomers obtained via acid catalysis contained a methyl 3-hydroxybutyrate end group, and those obtained by base catalysis had a methyl crotonate (olefinic) end group. In addition to hydroxybutyrate (HB), the oligomers were found to contain a small percentage of hydroxyvalerate, which was independently confirmed by gas chromatography/mass spectrometry. In comparison, analysis of a commercial PHA polymer, transesterified under identical conditions, showed only the presence of HB, i.e., a pure poly(HB) homopolymer. 相似文献
123.
Louis D. Quin Michael D. Gordon Joan E. Macdiarmid 《Journal of heterocyclic chemistry》1982,19(5):1041-1044
Replacement of C-4 with a hetero substituent (NR,O,S) in the 1-vinyl-3,4-dihydronaphthalene system has provided a new type of diene for participation in the McCormack cycloaddition reaction with P(III) halides. The tricyclic phospholene oxides so obtained are the first to bear an additional heteroatom in the ring system. 1,2-Dihydro-7-methoxy-1-(p-toluenesulfonyl)-4-vinylquinoline is a stable solid that reacts with methylphosphonous dichloride to give, after hydrolysis of the cycloadduct, the 1,2,4,5-tetrahydro-1H-phospholo-[2,3-c]quinoline ring system. The dihydroquinoline moiety was aromatized by detosylation with potassium t-butoxide. The tendency of 4-vinyl-2H-benzopyran to dimerize was a serious complication in its use, and the cycloaddition with methylphosphonous dichloride proceeded only in low yield. The product, a 2,3,3a,4-tetra-hydrobenzo[3,2-d]pyran derivative, was a stable, easily purified and characterized substance. 4-Vinyl-2H-benzo[b]thiopyran was more stable than the pyran, but the phospholo derivative from reaction with methylphosphonous dichloride was more difficult to purify. All products were characterized by 13C-nmr spectroscopy. 相似文献
124.
James P. Kutney Eugene Dimitriadis Gary M. Hewitt Philip J. Salisbury Mahatam Singh James A. Servizi Dennis W. Martens Robert W. Gordon 《Helvetica chimica acta》1982,65(5):1343-1350
One of the fish-toxic chlorinated resin acids, 14-chlorodehydroabietic acid ( 5 ), found in kraft mill effluent is examined. When exposed to the fungus Mortierella isabellina, 5 is converted into a number of hydroxylated derivatives which show low levels of toxicity to fish. These biotransformation products were isolated and characterized. 相似文献
125.
The analytical utility of several ionization techniques, which are known for their abilities to produce molecular ions of non-volatile/thermally labile compounds, is compared for the determination of the composition of quaternary ammonium salt mixtures derived from beef tallow. The ionization techniques include direct-exposure chemical ionization, field desorption, and fast atom bombardment. While all three techniques produce molecular cations from the salts, fast atom bombardment produces these in greatest relative abundance. Both fast atom bombardment and direct-exposure chemical ionization can be used for characterization of the composition of chain lengths in the mixture. Fast atom bombardment also produces different fragmentation/decomposition ions (imminium ions) than direct-exposure chemical ionization (protonated tertiary amines). 相似文献
126.
Felix Barz Joseph G. Gordon Michael R. Philpott Michael J. Weaver 《Chemical physics letters》1982,91(4):291-295
The intensity of surface-enhanced Raman scattering (SERS) from thiocyanate and chloride adsorbed on silver electrodes is shown to depend critically on whether the electrode is illuminated during the oxidation-reduction cycle used to pretreat the electrode. The value and magnitude of the photoeffect is dependent upon the type of surface vibrational mode, the adsorbate and the wavelength of the radiation during the ORC. The effects are attributed to the production of SERS active clusters of Ag atoms by photoreduction of the Ag(I) phase films during the ORC. 相似文献
127.
Summary Pentacoordinated molecules are thought to undergo intramolecular isomerization by the widely accepted Berry pseudorotation mechanism. Through our investigations, we have found that the actual pseudorotation for the PH4F system is more complex than that envisioned by Berry. The potential energy surface of PH4F is mapped out at the RHF/6-311G(d, p) level. According to the Berry mechanism, this system is expected to have two minima and two maxima; however, the system actually has two transition states and one global minimum. The minimum energy path from the highest transition state is followed to the second transition state, which in turn has a minimum energy path leading to the global minimum. Along the path between the two transition states there is a branching region. This portion of the potential energy surface is probed extensively.Dedicated to Prof. Klaus Ruedenberg 相似文献
128.
Cheol Ho Choi Klaus Ruedenberg Mark S. Gordon 《Journal of computational chemistry》2001,22(13):1484-1501
The three key translation equations of the fast multipole method (FMM) are deduced from the general polypolar expansions given earlier. Simplifications are introduced for the rotation‐based FMM that lead to a very compact FMM formalism. The optimum‐parameter searching procedure, a stable and efficient way of obtaining the optimum set of FMM parameters, is established with complete control over the tolerable error (ε). This new procedure optimizes the linear scaling with respect to the number of particles for a given ε. In addition, a new parallel FMM algorithm, which requires virtually no internode communication, is suggested that is suitable for the parallel construction of Fock matrices in electronic structure calculations. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1484–1501, 2001 相似文献
129.
This paper continues the study of quantised function algebrasO[G] of a semisimple group G at an lth root of unity . Thesealgebras were introduced by De Concini and Lyubashenko in 1994,and studied further by De Concini and Procesi and by Gordon,amongst others. Our main purpose here is to increase understandingof the finite-dimensional factor algebras O[G](g), for g G.We determine the representation type and block structure ofthese factors, and (for many g) describe them up to isomorphism.A series of parallel results is obtained for the quantised Borelalgebras and . 2000 Mathematical Subject Classification: 16W35,17B37. 相似文献
130.
Donald F. Mullica T. Gordon Scott J. Matt Farmer Jason A. Kautz 《Journal of chemical crystallography》1999,29(7):845-848
Adamantan-1-ammonium 1-adamantanecarboxylate, C21H33NO2 (I) is a novel dispiro-type compound. Aminoadamantane derivatives, in which the spiro carbon atoms are part of heterocyclic rings, are of potential interest as biological active substances and antiviral agents. Complex (I) crystallizes in the centrosymmetric space group C2/c (No. 15) with eight molecules in the unit cell with a = 25.227(4), b = 6.527(1), c = 22.489(4) Å, and = 90.75(1)°. The two spiro units are a 1-adamantylammonium cation and a 1-adamantane carbonyloxy anion. The complex units are stabilized by a network of intermolecular carbonyloxy-to-amine hydrogen bonding and van der Waals cohesive forces. Germane bond lengths are: C—N = 1.479(9) and C—O (mean) = 1.25(2) Å. 相似文献