全文获取类型
收费全文 | 4627篇 |
免费 | 258篇 |
国内免费 | 27篇 |
专业分类
化学 | 3228篇 |
晶体学 | 20篇 |
力学 | 99篇 |
数学 | 648篇 |
物理学 | 917篇 |
出版年
2024年 | 6篇 |
2023年 | 48篇 |
2022年 | 65篇 |
2021年 | 97篇 |
2020年 | 137篇 |
2019年 | 133篇 |
2018年 | 90篇 |
2017年 | 73篇 |
2016年 | 217篇 |
2015年 | 158篇 |
2014年 | 188篇 |
2013年 | 258篇 |
2012年 | 392篇 |
2011年 | 489篇 |
2010年 | 227篇 |
2009年 | 143篇 |
2008年 | 312篇 |
2007年 | 323篇 |
2006年 | 290篇 |
2005年 | 273篇 |
2004年 | 193篇 |
2003年 | 125篇 |
2002年 | 110篇 |
2001年 | 46篇 |
2000年 | 34篇 |
1999年 | 31篇 |
1998年 | 24篇 |
1997年 | 23篇 |
1996年 | 41篇 |
1995年 | 36篇 |
1994年 | 32篇 |
1993年 | 34篇 |
1992年 | 28篇 |
1991年 | 9篇 |
1990年 | 10篇 |
1989年 | 11篇 |
1987年 | 6篇 |
1986年 | 10篇 |
1985年 | 11篇 |
1984年 | 7篇 |
1983年 | 11篇 |
1982年 | 16篇 |
1981年 | 7篇 |
1980年 | 7篇 |
1979年 | 17篇 |
1978年 | 9篇 |
1977年 | 10篇 |
1976年 | 11篇 |
1974年 | 8篇 |
1973年 | 34篇 |
排序方式: 共有4912条查询结果,搜索用时 15 毫秒
101.
Population balance equations (PBEs) for reversible aggregation-fragmentation processes are important to particle agglomeration and dissolution, polymerization and degradation, liquid droplet coalescence and breakup, and floc coagulation and disintegration. Moment solutions provide convenient solutions to the PBEs, including steady state and similarity solutions, but may not be feasible for complex forms of size-dependent rate coefficients and stoichiometric kernels. Numeric solutions are thus necessary not only for applications, but also for the study of the mathematics of PBEs. Here we propose a numerical method to solve PBEs and compare the results to moment solutions. The numeric results are consistent with known steady state and asymptotic long-time similarity solutions and show how processes can be approximated by self-similar formulations. 相似文献
102.
Photosensitized oxidation through stearate monomolecular films 总被引:1,自引:0,他引:1
Abstract— The photosensitized oxidations of rubrene by methylene blue and of diphenylan-thracene by eosin have been studied where the sensitizer and the oxidizable substrate are separated by oxygen permeable layers of barium or cadmium stearate monomolecular films. The rate of the photosensitized oxidation reaction was followed by measurements of the hydrocarbon fluorescence, as a function of the stearate layer thickness. It has been found that the sensitized reaction is observable for thickness up to 500 Å and depends only on the deactivation process of the excited species (singlet oxygen) diffusing through the layers. It has been found also that half of the excited oxygen molecules are deactivated after a diffusion path of 115 A. The starting hydrocarbon can be regenerated by heating the sample after the photoreaction to approximately 120°C showing the transannular peroxide nature of the oxidation product. 相似文献
103.
Carré V Gaud O Sylvain I Bourdon O Spiro M Blais J Granet R Krausz P Guilloton M 《Journal of photochemistry and photobiology. B, Biology》1999,48(1):57-62
A series of neutral meso-arylglycosylporphyrins has been tested in order to evaluate their potency as antifungal agents against the yeast Saccharomyces cerevisiae. Photodynamic activity of these molecules results in intracellular damage as evidenced by the loss of clonogenicity and DNA fragmentation. The ability of these photosensitizers to permeate yeast cells is determined by microspectrofluorimetry and is correlated with their antifungal potency. Amphiphilic porphyrin derivatives are shown to exhibit the more pronounced photoactivity. 相似文献
104.
Jun Liu Kelton A. Schleyer Tyrel L. Bryan Changjian Xie Gustavo Seabra Yongmei Xu Arjun Kafle Chao Cui Ying Wang Kunlun Yin Benjamin Fetrow Paul K. P. Henderson Peter Z. Fatland Jian Liu Chenglong Li Hua Guo Lina Cui 《Chemical science》2021,12(1):239
Heparanase (HPA) is a critical enzyme involved in the remodeling of the extracellular matrix (ECM), and its elevated expression has been linked with diseases such as various types of cancer and inflammation. The detection of heparanase enzymatic activity holds tremendous value in the study of the cellular microenvironment, and search of molecular therapeutics targeting heparanase, however, no structurally defined probes are available for the detection of heparanase activity. Here we present the development of the first ultrasensitive fluorogenic small-molecule probe for heparanase enzymatic activity via tuning the electronic effect of the substrate. The probe exhibits a 756-fold fluorescence turn-on response in the presence of human heparanase, allowing one-step detection of heparanase activity in real-time with a picomolar detection limit. The high sensitivity and robustness of the probe are exemplified in a high-throughput screening assay for heparanase inhibitors.Heparanase, a critical enzyme involved in the remodeling of the extracellular matrix, activates a disaccharide probe HADP to give a strong fluorescence signal. 相似文献
105.
Benjamin Scharf 《Chemical physics letters》1983,98(1):81-85
We discuss the intricate Jahn—Teller-like and non-Jahn—Teller spectroscopic patterns which result via the recently revealed cross-quadratic terms involves modes of different symmetry which arise in the nuclear potential of degenerate electronic states of non-linear molecules. 相似文献
106.
Antonio Fernández-Ramos Benjamin A. Ellingson Rubén Meana-Pañeda Jorge M. C. Marques Donald G. Truhlar 《Theoretical chemistry accounts》2007,118(4):813-826
This article shows how to evaluate rotational symmetry numbers for different molecular configurations and how to apply them
to transition state theory. In general, the symmetry number is given by the ratio of the reactant and transition state rotational
symmetry numbers. However, special care is advised in the evaluation of symmetry numbers in the following situations: (i)
if the reaction is symmetric, (ii) if reactants and/or transition states are chiral, (iii) if the reaction has multiple conformers
for reactants and/or transition states and, (iv) if there is an internal rotation of part of the molecular system. All these
four situations are treated systematically and analyzed in detail in the present article. We also include a large number of
examples to clarify some complicated situations, and in the last section we discuss an example involving an achiral diasteroisomer. 相似文献
107.
The thermodynamics and dynamics of a model S(N)1 reaction: t-BuCl --> t-Bu+ + Cl- is studied at the water liquid/vapor interface using molecular-dynamics computer simulations. The empirical valence bond approach is used to couple two diabatic states, covalent and ionic, in the electronically adiabatic limit. Umbrella sampling calculations are used to calculate the potential of mean force along the reaction coordinate (defined as the t-Bu to Cl distance) in bulk water and in several locations at the interface. We find a significant increase of the dissociation barrier height and of the reaction free energy at the interface relative to the bulk. This is shown to be due to the reduced polarity of the interface. Reactive flux correlation function calculations show significant deviation of the rate constant from the transition-state theory: The transmission coefficients range from 0.49 in the bulk to 0.05 above the Gibbs surface. The low transmission coefficient at the interface despite the lower friction is shown to be due to slow vibrational relaxation. 相似文献
108.
Judit Sipos Benjamin Podnyi Istvn Hermecz Levente Pusztay Gbor Tth Lszl Szilgyi 《Journal of heterocyclic chemistry》1989,26(4):1061-1068
Ethyl 4-oxo-6,7,8,9-tetrahydro-4H-pyrido[1,2-a]pyrimidine-3-carboxylates 1–4 , their piperidine ring homologues 5–6 and their 2-oxo isomers 7–9 were reacted with benzaldehyde. At low temperature, kinetically stable addition products were formed. Thermodynamically stable condensation products were obtained at higher temperature, which were also formed when the addition products were refluxed in benzene. The 9-benzyl derivatives were prepared by the hydrogenation of the condensation products over Pd/C. The stereochemical features of the new compounds were determined via 1H and 13C nmr chemical shift and coupling constant analysis and NOE measurements. 相似文献
109.
Nous quantifions certaines inclusions d'algèbres de Lie semi-simpleshg. Nous calculons les homologies associées aux quantifications, surC((h)), d'une part des algèbres de fonctions formelles surG/H, pourHG une inclusion de groupes de Lie semi-simples associée, et d'autre part des fonctions algébriques sur SL(2,C)/T.We quantize certain inclusions of semisimple Lie algebrashg. We compute the cyclic and Hochschild homologies for theC((h))-quantizations of
相似文献
(1) | the ring of formal functions onG/H,G andH semisimple Lie groups associated to these inclusions, and |
(2) | the ring of algebraic functionsSL(2,C)/T (T being the nonquantized torus of SL(2, C)). |
110.
Phosphazene rings with (dimethylamino)ethoxy (1, 2), pyridylmethoxy (3), or (dimethylamino)propoxy (4) chains were synthesized and quaternized at the substitutent nitrogen by treatment with methyl iodide at 35 degrees C over 3-6 h to give polyiodo salts, 5-8. Subsequent metathesis with LiN(SO(2)CF(3))(2) or NaBF(4) gave the respective ionic salts, 9-13. The amide salts, 9-12, were viscous liquids with pour points at 55-100 degrees C, and the tetrafluoroborate salt, 13, was a solid, mp 168 degrees C. The compositions of 2 and 5-13 were confirmed by elemental analysis and spectroscopic methods. Compounds 1, 2, and 4 were viscous liquids (d(25) = 1.67 g cm(-3); eta(25) = 0.76-1.56 mPa s(-1) ) with pour points at approximately 15 degrees C. The solid polyquaternary salts, 5-8, melted at 130-194 degrees C. The ionic liquids, 9-12, had an average density of approximately 1.73 g cm(-3) at 25 degrees C, and viscosities (25 degrees C) ranged between 68.3 and 139.2 mPa s(-1). A plot of the viscosities of 9-12 vs temperature revealed an almost linear correlation between 55 and 120 degrees C. Friction and wear properties of water with 0.25 wt % of 9-12 as boundary lubricant additives were evaluated on Si(3)N(4)/Si(3)N(4) ceramic interfaces. The most significant observation is that they caused a decrease in the running-in period. 相似文献