全文获取类型
收费全文 | 5867篇 |
免费 | 152篇 |
国内免费 | 19篇 |
专业分类
化学 | 3618篇 |
晶体学 | 29篇 |
力学 | 246篇 |
数学 | 864篇 |
物理学 | 1281篇 |
出版年
2023年 | 47篇 |
2022年 | 145篇 |
2021年 | 187篇 |
2020年 | 160篇 |
2019年 | 128篇 |
2018年 | 114篇 |
2017年 | 88篇 |
2016年 | 235篇 |
2015年 | 180篇 |
2014年 | 154篇 |
2013年 | 332篇 |
2012年 | 366篇 |
2011年 | 432篇 |
2010年 | 248篇 |
2009年 | 176篇 |
2008年 | 358篇 |
2007年 | 360篇 |
2006年 | 338篇 |
2005年 | 282篇 |
2004年 | 262篇 |
2003年 | 206篇 |
2002年 | 151篇 |
2001年 | 93篇 |
2000年 | 58篇 |
1999年 | 50篇 |
1998年 | 42篇 |
1997年 | 60篇 |
1996年 | 55篇 |
1995年 | 47篇 |
1994年 | 53篇 |
1993年 | 40篇 |
1992年 | 49篇 |
1991年 | 25篇 |
1990年 | 23篇 |
1989年 | 19篇 |
1988年 | 24篇 |
1987年 | 20篇 |
1986年 | 20篇 |
1985年 | 45篇 |
1984年 | 42篇 |
1983年 | 34篇 |
1982年 | 33篇 |
1981年 | 33篇 |
1980年 | 23篇 |
1979年 | 26篇 |
1977年 | 21篇 |
1976年 | 17篇 |
1975年 | 18篇 |
1974年 | 14篇 |
1973年 | 12篇 |
排序方式: 共有6038条查询结果,搜索用时 15 毫秒
101.
The compound bis(di-micro-ethoxo-bis(3,5-di-tert-butylsemiquinonato)dicopper(II)) has been synthesized and its structure was determined by single-crystal X-ray diffraction. The compound crystallizes in the monoclinic system, space group C2/c, with a = 37.736(8) A, b = 9.173(2) A, c = 23.270(5) A, beta = 122.24(3) degrees. The structure can be described as a Lewis adduct between two dinuclear [Cu(DBSQ)(C(2)H(5)O)](2) units (DBSQ = 3,5-di-tert-butyl-semiquinonato). The temperature dependence of the magnetic susceptibility was efficiently analyzed by a combined DFT/experimental approach, showing that a rather strong ferromagnetic interaction exists between the DBSQ(-) and the copper(II) ions modulated by an antiferromagnetic interaction between the two copper(II) ions of the dinuclear units. Weak antiferromagnetism between the two units in the unit cell was measured. 相似文献
102.
Burley GA Fowler PW Soncini A Sandall JP Taylor R 《Chemical communications (Cambridge, England)》2003,(24):3042-3043
Ipsocentric current-density maps for a fluorofullerene derivative, C60F15H3, modelling the addition pattern of the experimentally characterised C60F15[CBr(CO2Et)2]3 which contains an [18]trans-annulene system, reveal a diamagnetic ring current dominated by the contribution of the four HOMO electrons, as in a classical (4n + 2) aromatic annulene. 相似文献
103.
Michelini Mdel C Russo N Alikhani ME Silvi B 《Journal of computational chemistry》2005,26(12):1284-1293
The interaction between molybdenum, atom, and dimer, with nitrous oxide has been investigated using density functional theory. The analysis of the potential energy surfaces for both reactions has revealed that a single molybdenum atom can activate the N--O bond of N2O requiring a small activation energy. However, the presence of several intersystem crossings between three different spin states, namely, septet, quintet and triplet states, seems to be the major constraint to the Mo + N2O reaction. Contrarily, the low-lying excited states (triplet and quintet) do not participate in the reaction between the molybdenum dimer and N2O. The latter reaction fully evolves on the singlet spin surface. Three different regions have been distinguished along the pathway: formation of an adduct complex, formation of an inserted compound, and the N2 detachment. The connection between the two first regions has been characterized by the formation of a special complex in which the N--O bond is so weakened that it could be considered as a first step in the insertion process. It has been shown that the topological changes along the pathways provide a clear explanation for the geometrical changes that occur along the reaction pathway. In summary, the detachment of the N2 molecule is found to be kinetically an effective process for both reactions, owing to the high exothermicity and consequently to the high internal energy of the insertion intermediates. However, in the case of Mo atom, the reaction should be a slow process due to the presence of spin-forbidden transitions. These results fully agree with previous experimental works. 相似文献
104.
Janet E. Del Bene 《Journal of computational chemistry》1987,8(6):810-815
Basis set expansion and correlation effects on computed hydrogen bond energies of the positive ion complexes AHn · AHn + 1+1, for AHn = NH3, OH2 and FH, have been evaluated. The addition of diffuse functions on nonhydrogen atoms is the single most important enhancement of split-valence plus polarization basis sets for computing hydrogen bond energies. Basis set enhancement effects appear to be additive in these systems. The correlation energy contribution to the stabilization energies of these complexes is significant, with the second order term being the largest term and having a stabilizing effect. The third order term is smaller and of opposite sign, while the fourth order term is smaller yet and stabilizing. As a result, computed MP4 stabilization energies are bracketed by the MP2 and MP3 energies. The overall effect of basis set enhancement is to decrease hydrogen bond energies, whereas the addition of electron correlation increases stabilization energies. 相似文献
105.
Stereochemical effects in supramolecular self-assembly at surfaces: 1-D versus 2-D enantiomorphic ordering for PVBA and PEBA on Ag(111) 总被引:2,自引:0,他引:2
Barth JV Weckesser J Trimarchi G Vladimirova M De Vita A Cai C Brune H Günter P Kern K 《Journal of the American Chemical Society》2002,124(27):7991-8000
We present investigations on noncovalent bonding and supramolecular self-assembly of two related molecular building blocks at a noble metal surface: 4-[trans-2-(pyrid-4-yl-vinyl)]benzoic acid (PVBA) and 4-[(pyrid-4-yl-ethynyl)]benzoic acid (PEBA). These rigid, rodlike molecules comprising the same complementary moieties for hydrogen bond formation are comparable in shape and size. For PVBA, the ethenylene moiety accounts for two-dimensional (2-D) chirality upon confinement to a surface; PEBA is linear and thus 2-D achiral. Molecular films were deposited on a Ag(111) surface by organic molecular beam epitaxy and characterized by scanning tunneling microscopy. At low temperatures (around 150 K), both species form irregular networks of flat lying molecules linked via their endgroups in a diffusion-limited aggregation process. In the absence of kinetic limitations (adsorption or annealing at room temperature), hydrogen-bonded supramolecular assemblies form which are markedly different. With PVBA, enantiomorphic twin chains in two mirror-symmetric species running along a high-symmetry direction of the substrate lattice form by diastereoselective self-assembly of one enantiomer. The chirality signature is strictly correlated between neighboring twin chains. Enantiopure one-dimensional (1-D) supramolecular nanogratings with tunable periodicity evolve at intermediate coverages, reflecting chiral resolution in micrometer domains. In contrast, PEBA assembles in 2-D hydrogen-bonded islands, which are enantiomorphic because of the orientation of the supramolecular arrangements along low-symmetry directions of the substrate. Thus, for PVBA, chiral molecules form 1-D enantiomorphic supramolecular structures because of mesoscopic resolution of a 2-D chiral species, whereas with PEBA, the packing of an achiral species causes 2-D enantiomorphic arrangements. Model simulations of supramolecular ordering provide a deeper understanding of the stability of these systems. 相似文献
106.
Alessandro Lezzi Sandra Cobianco Arnaldo Roggero 《Journal of polymer science. Part A, Polymer chemistry》1994,32(10):1877-1883
A series of chelating resins, derived from a macroreticular styrene-divinylbenzene (2%) copolymer beads grafted with various poly(ethylene glycols) HO? (? CH2? CH2? O? )n? H(n = 0, 4, 9, 13) and containing thiol groups as chelating functions, have been synthesized in a three-step reaction sequence. The structure of the functionalized resins was confirmed by IR spectrophotometry, elemental analysis, and differential scanning calorimetry. The complexation behavior of these thiol resins was investigated towards Hg(II), Cu(II), and Pb(II) ions in aqueous solution by a batch equilibration technique. The influence of pH on adsorption capacity was also examined. The adsorption values for metal ions' intake followed the order Hg(II) > Cu(II) > Pb(II). The affinity of these polymers towards Hg(II) ions was so high that the total mercury level in the liquid decreased from 20 ppm to below 10 ppb after 2 h of treatment. Polymers can be regenerated by washing with a solution of hydrochloric acid (6N) and 10% by weight of an aqueous solution of thiourea. © 1994 John Wiley & Sons, Inc. 相似文献
107.
2,6-Diacetylpyridine bis(benzoylhydrazone) (H2DPBH) is proposed as a ligand for the extraction of uranium(VI). Complete extraction from aqueous solutions into dichloromethane is achieved with a ligand/metal mole ratio of < for 10?5?10?4 M uranyl ion. Potentiometric measurements indicate that the extracted species is UO2 (DPBH). Uranium can be determined in the extract by spectrophotometric measurements at 420 nm and by differentail pulse polarography (Ep = ?0.67 V) with tetraethylammonium bromide as supporting electrolyte. For both methods, the detection limit is about 2 × 10?6 M in the extract. 相似文献
108.
109.
Raffaele Sacchi Giandomenico Corrado Boris Basile Daniele Mandarello Maria Luisa Ambrosino Antonello Paduano Maria Savarese Nicola Caporaso Maria Aponte Alessandro Genovese 《Molecules (Basel, Switzerland)》2022,27(22)
‘Oliva di Gaeta’ is almost certainly the most important and well-known PDO denomination for table olives in Italy. Their production is based on a specific two-stage trade preparation called the ‘Itrana’ method. In this work, we investigated how variations in the duration of the initial water fermentation (i.e., 15 and 30 days) and the salt concentration (i.e., 6% and 8% NaCl) influence the chemical features, microbial dynamics, polyphenols, volatile organic compounds, and sensory features of ‘Oliva di Gaeta’. The time of the addition of salt did not affect the final concentration in the brine, but a longer initial water fermentation (before salt addition) led to lower pH values. The bacterial count constantly increased until the salt addition (i.e., either 15 or 30 days), while the yeast population peaked on day 30. Generally, the two different salt concentrations did not affect the count of microorganisms at the end of fermentation, with the only exception being a higher lactic acid bacteria count for the treatment with 6% salt added at 30 days. At commercial maturity, the crucial bitter tastant oleuropein was not completely removed from the drupes, and differences in salt concentration and the length of the first-stage water fermentation did not influence its content at the end of olive curing. Richer volatile profiles of olives were detected with higher-salt treatments, while the combination of low salt and early saline treatment provided a more distinct profile. Longer initial water fermentation caused a small increase in some phenolic compounds (e.g., iso-verbascoside, verbascoside, and hydroxytyrosol-glucoside). A panel test indicated that salt application at 30 days resulted in a more “Sour” and “Bitter” taste, irrespective of the salt concentration. The low salt concentration coupled with the late saline treatment resulted in more “Fruity” notes, probably due to the higher production of esters by lactobacilli. The slightly bitter perception of the olives was consistent with the partial removal of oleuropein. Our work revealed the characteristics of the ‘Itrana’ method and that the variation in salt concentration and its time of application changes parameters ranging from the microbial dynamics to the sensory profile. Specifically, our data indicate that 6% NaCl coupled with a longer initial water fermentation is the most different condition: it is less effective in blocking microbial growth but, at the same time, is more potent in altering the nutritional (e.g., polyphenols) and sensorial qualities (e.g., bitterness and fruitiness) of ‘Oliva di Gaeta’. 相似文献
110.
Lung cancer is the leading cause of cancer-related deaths globally. Despite current treatment approaches that include surgery, chemotherapy, radiation and immunotherapies, lung cancer accounted for 1.79 million deaths worldwide in 2020, emphasizing the urgent need to find novel agents and approaches for more effective treatment. Traditionally, chemicals derived from plants, such as paclitaxel and docetaxel, have been used in cancer treatment, and in recent years, research has focused on finding other plant-derived chemicals that can be used in the fight against lung cancer. Ursolic acid is a polyphenol found in high concentrations in cranberries and other fruits and has been demonstrated to have anti-inflammatory, antioxidant and anticancer properties. In this review, we summarize recent research examining the effects of ursolic acid and its derivatives on lung cancer. Data from in vitro cell culture and in vivo animal studies show potent anticancer effects of ursolic acid and indicate the need for clinical studies. 相似文献