全文获取类型
收费全文 | 11566篇 |
免费 | 232篇 |
国内免费 | 95篇 |
专业分类
化学 | 7992篇 |
晶体学 | 224篇 |
力学 | 248篇 |
综合类 | 1篇 |
数学 | 2023篇 |
物理学 | 1405篇 |
出版年
2022年 | 83篇 |
2021年 | 104篇 |
2020年 | 122篇 |
2019年 | 118篇 |
2018年 | 92篇 |
2017年 | 94篇 |
2016年 | 226篇 |
2015年 | 189篇 |
2014年 | 201篇 |
2013年 | 563篇 |
2012年 | 532篇 |
2011年 | 608篇 |
2010年 | 316篇 |
2009年 | 276篇 |
2008年 | 578篇 |
2007年 | 609篇 |
2006年 | 584篇 |
2005年 | 552篇 |
2004年 | 487篇 |
2003年 | 388篇 |
2002年 | 455篇 |
2001年 | 122篇 |
2000年 | 129篇 |
1999年 | 124篇 |
1998年 | 121篇 |
1997年 | 153篇 |
1996年 | 193篇 |
1995年 | 123篇 |
1994年 | 115篇 |
1993年 | 125篇 |
1992年 | 126篇 |
1991年 | 107篇 |
1990年 | 128篇 |
1989年 | 111篇 |
1988年 | 111篇 |
1987年 | 90篇 |
1986年 | 100篇 |
1985年 | 179篇 |
1984年 | 191篇 |
1983年 | 138篇 |
1982年 | 223篇 |
1981年 | 190篇 |
1980年 | 167篇 |
1979年 | 154篇 |
1978年 | 148篇 |
1977年 | 134篇 |
1976年 | 143篇 |
1975年 | 126篇 |
1974年 | 146篇 |
1973年 | 127篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
81.
Goldschmidt RJ Wetzel SJ Blair WR Guttman CM 《Journal of the American Society for Mass Spectrometry》2000,11(12):1095-1106
Various secondary series are observed in matrix-assisted laser desorption/ionization (MALDI) time-of-flight mass spectra of polystyrene. The number and positions of the series depend on the choice of matrix and added cation. For a given treatment, series observed in linear mode are not necessarily observed in reflectron mode, and vice versa. Post-source decay analysis was used to determine that the secondary series arise at least in part from formation and decay of adducts of polystyrene with matrix species. There is some treatment-to-treatment variation, but adduct formation and decay were observed for all tested treatments. The multiplicity of secondary series makes it unclear whether post-source decay occurs for the main series (polystyrene + cation)+ ions under the conditions normally used for polystyrene analysis. Such ions do undergo post-source decay at laser fluences greater than normally used. Although only polystyrene was investigated in this work, other polymers may also produce adduct and decay series in MALDI analysis. Their presence can mask the presence of minor components in a sample, but at least as observed here, do not have a strong influence on molecular mass determinations. 相似文献
82.
When core ionization of an atom in a molecule causes significant changes in bond orders, the core-hole ion is formed in a strained configuration. This strain causes vibrational broadening of the core line. The core-hole ion can be represented as an ordinary chemical species by applying the equivalent cores approximation. Then simple rules of classical valence bond theory can be used to predict changes in the weighting of resonance structures and corresponding changes in bond orders. Thus qualitative changes in relative linewidths can be predicted. 相似文献
83.
The wavefunctions and various partitions of the energy are examined for a variety of small molecules (H2, H3, H4, HeH, HeH2, He2, LiH, and BH) in order to isolate the factors crucial for bond formation. We find that a natural partition of the energy leads to the conclusion that the crucial factor is the exchange, or nonclassical, part of the kinetic energy, T
x. The change in T
xupon pushing the atoms towards one another is the dominant term in the binding energy; it is negative when the resulting molecule is stable and positive when it is unstable. We show that T
x is related to the interference kinetic energy considered by Ruedenberg.
Partially supported by a grant (GP-15423) from the National Science Foundation. This paper is based on a portion of the PhD thesis (California Institute of Technology, 1970) by CWW.
National Science Foundation Predoctoral Trainee.
Alfred P. Sloan Foundation Research Fellow.
Contribution No. 3917. 相似文献
Zusammenfassung Die Wellenfunktionen und verschiedene Zerlegungen der Energie werden für eine Reihe kleiner Moleküle untersucht (H2, H3, H4, HeH, HeH2, He2, LiH und BH), um die Faktoren zu finden, die für die Bindungsbildung ausschlaggebend sind. Die natürliche Zerlegung der Energie läßt die Folgerung zu, daß der bestimmende Faktor der Austauschanteil T x(oder nichtklassische Anteil) der kinetischen Energie ist. Die Änderung von T xbeim Zusammenführen der Atome ist der dominierende Term für die Bindungsenergie; er ist negativ, wenn das resultierende Molekül stabil ist, und positiv, falls es instabil ist. Es wird gezeigt, daß T x im Zusammenhang zum Wechselwirkungsanteil der kinetischen Energie nach Ruedenberg steht.
Partially supported by a grant (GP-15423) from the National Science Foundation. This paper is based on a portion of the PhD thesis (California Institute of Technology, 1970) by CWW.
National Science Foundation Predoctoral Trainee.
Alfred P. Sloan Foundation Research Fellow.
Contribution No. 3917. 相似文献
84.
Part I of the present work outlined the rigorous application of information theory to a quantum mechanical system in a thermodynamic equilibrium state. The general formula developed there for the best-guess density operator \(\hat \rho\) was indeterminate because it involved in an essential way an unspecified prior probability distribution over the continuumD H of strong equilibrium density operators. In Part II mathematical evaluation of \(\hat \rho\) is completed after an epistemological analysis which leads first to the discretization ofD H and then to the adoption of a suitable indifference axiom to delimit the set of admissible prior distributions. Finally, quantal formulas for information-theoretic and thermodynamic entropies are contrasted, and the entire work is summarized. 相似文献
85.
Peggy E. Chatham Gary M. Karp MichaeL J. Kaufman William Nyitray Robert C. Kerber 《Journal of organometallic chemistry》1982,236(2):257-266
Although , (Fp η-C5H5Fe(CO)2) (I) is stable and characterizable, the lower homologue FpCH2CH(CO2CH3)2 (II) is not; this we attribute to a facile elimination reaction resulting from the relatively acidic β-hydrogen of II. Formation of I from Fp? and XCH2CE2CH3 (X Br, Cl; E CO2CH2CH3) and cleavage of its FeC bonds (using H+, Br2, CeIV and HgII) occur without major amounts of ester group migrations, even though ·CH2CE2CH3 radicals are involved in some of these reactions. 相似文献
86.
Use of a hard sphere model and the concept of an effective hard sphere diameter of a colloidal particle with its associated double layer is reported. This method allows rapid determination of the order-disorder transition in colloidal dispersions and yields reasonable estimates of the osmotic pressures compared with “exact” Monte Carlo calculations. 相似文献
87.
A new spectrophotometric determination of the sulphate ion is described which uses 2-aminoperimidine hydrochloride as a precipitating reagent. The excess of the reagent is measured at 305 nm. The procedure deals with sulphate in the range 4–120 p.p.m., and relies on simple calibration. The relative standard deviation for 50 p.p.m. of sulphate is 3.7%. The interference of 100 p.p.m. of phosphate, fluoride and nitrate is only slight in the determination of 50 p.p.m. of sulphate. The method is recommended for the determination of sulphate in rain and surface waters. 相似文献
88.
13C NMR data for a series of arylthallium trifluoroacetates (ArTlX2, X = OCOCF3) are reported and assigned. The range of carbon—thallium couplings to be expected, the dependence on the disposition of coupled nuclei, and chemical shift effects are discussed. The Tl(OCOCF3)2 group is shown to be a powerful electron withdrawing group, from both the 13C data and 19F substituent chemical shifts of the p-fluorophenyl derivative. 相似文献
89.
Bristow AW Nichols WF Webb KS Conway B 《Rapid communications in mass spectrometry : RCM》2002,16(24):2374-2386
Mass spectral libraries provide a tool for identifying unknown compounds using both molecular weight and fragmentation information. Mass spectrometers with electrospray ionisation (ESI) and atmospheric chemical ionisation (ApCI) sources have the capability to produce data of this type using in-source collisionally induced dissociation (CID), and in-source CID libraries can be created. Due to the variation in electrospray source design from different instrument manufacturers, the production of reproducible in-source CID spectra that can be used in libraries for all instrument types is not a trivial task. To date, the evaluation of the production of in-source CID libraries has tended to focus on similar instruments from one manufacturer. The studies have also tended to focus on specific compound classes, with a limited molecular weight range.This report describes the findings from the investigation of protocols for the creation of mass spectral libraries using ESI in-source CID on six instruments from four different manufacturers. The overall goal was to create a spectral library for the identification of unknowns. The library could then be applied across all manufacturers' electrospray instruments.Two different experimental protocols were attempted. The first used a tuning compound to establish standard ESI source conditions, with fixed fragmentation potentials. The second involved the attenuation of the [M + H](+) ion to a known degree. A diverse range of compounds (pharmaceutical, photographic, pesticides) was tested to establish the reproducibility of the spectra on the six instruments. Both protocols produced spectra on the various instruments that in many cases were very similar. In other examples, the spectra differed not only in their relative ion abundances, but also in terms of the spectral content. Important observations regarding the effect of ion source design are also reported.The degree of spectral reproducibility was calculated off-line by comparing the five most abundant ions (20% for each ion that matches) from each spectrum on each instrument. This approach was adopted, as we do not possess a software package that met our requirements for spectral comparison. Match factors (% fit) were calculated by comparing each spectrum against the spectra recorded for the same compound and then for all other compounds, on each instrument. The % fit values derived by the off-line approach gave a clear view of the spectral reproducibility from instrument to instrument and also discriminated the spectra of the various compounds from each other. The applicability of this approach was tested using a blind trial in which several compounds were presented as unknowns, their in-source CID spectra recorded and the five-ion approach used for identification. 相似文献
90.
CD data for a variety of N-nitrosamino acids and N-nitrosopyrrolidines are presented. The effects of nitrosamino group conformation, pyrrolidine ring geometry, different perturbing substituents, and especially intramolecular H-bonding upon the n → π* CD band are discussed. Stereochemical conclusions can be made with confidence in many cases, although no sector diagram, as yet published, successfully correlates all the available chiroptical data in this series of compounds. However, a negative CD band due to the π → π* transition was observed tor all N-nitrosamines having the L-proline configuration at C-2, regardless of nitroso group conformation; it is suggested that this band be used whenever possible for stereochemical correlations. 相似文献