全文获取类型
收费全文 | 929篇 |
免费 | 24篇 |
国内免费 | 7篇 |
专业分类
化学 | 678篇 |
晶体学 | 8篇 |
力学 | 20篇 |
数学 | 138篇 |
物理学 | 116篇 |
出版年
2023年 | 6篇 |
2022年 | 11篇 |
2021年 | 13篇 |
2020年 | 18篇 |
2019年 | 13篇 |
2018年 | 12篇 |
2017年 | 14篇 |
2016年 | 14篇 |
2015年 | 19篇 |
2014年 | 24篇 |
2013年 | 57篇 |
2012年 | 70篇 |
2011年 | 61篇 |
2010年 | 38篇 |
2009年 | 12篇 |
2008年 | 47篇 |
2007年 | 58篇 |
2006年 | 50篇 |
2005年 | 42篇 |
2004年 | 46篇 |
2003年 | 47篇 |
2002年 | 31篇 |
2001年 | 11篇 |
2000年 | 13篇 |
1998年 | 5篇 |
1997年 | 10篇 |
1996年 | 12篇 |
1995年 | 13篇 |
1994年 | 12篇 |
1993年 | 4篇 |
1992年 | 11篇 |
1991年 | 11篇 |
1990年 | 8篇 |
1989年 | 6篇 |
1988年 | 4篇 |
1987年 | 7篇 |
1985年 | 4篇 |
1984年 | 9篇 |
1982年 | 7篇 |
1981年 | 7篇 |
1980年 | 6篇 |
1979年 | 5篇 |
1978年 | 13篇 |
1977年 | 8篇 |
1976年 | 12篇 |
1975年 | 9篇 |
1974年 | 7篇 |
1973年 | 8篇 |
1972年 | 6篇 |
1970年 | 7篇 |
排序方式: 共有960条查询结果,搜索用时 15 毫秒
151.
Donovan N. Leonard Phillip E. Russell Steven D. Smith Richard J. Spontak 《Macromolecular rapid communications》2002,23(3):205-209
Ultrathin films of a low‐molecular‐weight block copolymer spontaneously dewet after several days at ambient temperature. Film rupture produces macroscopic holes and a residual pancake brush layer ≈ 2 nm thick with intermittent mounds measuring up to 25 nm in thickness. Multiscale dewetting likewise occurs when the films are heated and returned to ambient temperature. Regardless of the surface pattern that forms during heating, submicron mounds develop on the dewetted copolymer film, and fine holes emerge along the substrate surface, after cooling. 相似文献
152.
153.
Guyan Liang Xiannong Chen J. A. Dustman Anita H. Lewin J. Phillip Bowen 《Journal of computational chemistry》1997,18(11):1371-1391
The geometries and vibrational frequencies of 11 training molecules containing the ammonium ion moiety were calculated at the MP2/6-31+G* level of theory. Various torsional energy profiles were also calculated using this basis set. From those ab initio calculations, a molecular mechanics (MM3) force field was developed using our Parameter Analysis and Refinement Toolkit System (PARTS). Using this set of parameters, the MM3 force field was found to well reproduce the molecular geometries and vibrational spectra for the all training molecules. CPU time was reduced from days to seconds. The availability of this new force field dramatically increases the feasibility of the computer-assisted drug design involving ammonium and protonated amino groups. © 1997 by John Wiley & Sons, Inc. J Comput Chem 18 : 1371–1391, 1997 相似文献
154.
Sally Noushini Soo Jean Park Jeanneth Perez Danielle Holgate Vivian Mendez Ian M. Jamie Joanne F. Jamie Phillip W. Taylor 《Molecules (Basel, Switzerland)》2021,26(16)
Pheromones are biologically important in fruit fly mating systems, and also have potential applications as attractants or mating disrupters for pest management. Bactrocera kraussi (Hardy) (Diptera: Tephritidae) is a polyphagous pest fruit fly for which the chemical profile of rectal glands is available for males but not for females. There have been no studies of the volatile emissions of either sex or of electrophysiological responses to these compounds. The present study (i) establishes the chemical profiles of rectal gland contents and volatiles emitted by both sexes of B. kraussi by gas chromatography–mass spectrometry (GC–MS) and (ii) evaluates the detection of the identified compounds by gas chromatography–electroantennogram detection (GC–EAD) and –electropalpogram detection (GC–EPD). Sixteen compounds are identified in the rectal glands of male B. kraussi and 29 compounds are identified in the rectal glands of females. Of these compounds, 5 were detected in the headspace of males and 13 were detected in the headspace of females. GC–EPD assays recorded strong signals in both sexes against (E,E)-2,8-dimethyl-1,7-dioxaspiro[5.5]undecane, 2-ethyl-7-mehtyl-1,6-dioxaspiro[4.5]decane isomer 2, (E,Z)/(Z,E)-2,8-dimethyl-1,7-dioxaspiro[5.5]undecane, and (Z,Z)-2,8-dimethyl-1,7-dioxaspiro[5.5]undecane. Male antennae responded to (E,E)-2,8-dimethyl-1,7-dioxaspiro[5.5]undecane, 2-methyl-6-pentyl-3,4-dihydro-2H-pyran, 6-hexyl-2-methyl-3,4-dihydro-2H-pyran, 6-oxononan-1-ol, ethyl dodecanoate, ethyl tetradecanoate and ethyl (Z)-hexadec-9-enoate, whereas female antennae responded to (E,E)-2,8-dimethyl-1,7-dioxaspiro[5.5]undecane and 2-methyl-6-pentyl-3,4-dihydro-2H-pyran only. These compounds are candidates as pheromones mediating sexual interactions in B. kraussi. 相似文献
155.
The present report examplifies a novel type of aromatic amine addition reactions at a ruthenium(II) complexed acetonitrile. The electrophilic cationic complex, cis-[L2Ru(CH3CN)2](ClO4)2 (1) [L = 2-(phenylazo)pyridine] reacts with aromatic primary amines only in neat to produce a violet amidinate complex, [L2Ru-N(Ar)-C(CH3)-N(Ar)]+ (2) of ruthenium(II). Along with it a blue ortho-metalated ruthenium(II) amidine complex, [L2Ru-N(H)C(CH3)-N(H)Ar]+ (3) is also formed. X-ray structures of the two representative complexes are reported. The transformation 1 → 2 is unprecedented, involves multiple steps and occurs with addition of two equivalents of ArNH2 across a coordinated nitrile function. In this complex, amidinate ligand binds to ruthenium(II) center as a σ,σ symmetrical bidentate chelate. The formation of 3 is a combination of nucleophilic amine addition and cyclometalation. 1H and 13C NMR spectra of the products are examined, which are consistent with their formulations and structures. Optical spectra and redox properties of the newly synthesized complexes are reported. Visible range spectra of 2 and 3 are dominated by moderately intense metal-to-ligand charge transfer transitions. The complexes show multiple redox responses. The anodic potential response occurs at a high positive potential, which is attributed to a Ru(II)/Ru(III) couple. The cathodic potential responses are due to reductions of the coordinated diazo ligands. 相似文献
156.
Kinetics and mechanism of tetrahydrofuran synthesis via 1,4-butanediol dehydration in high-temperature water 总被引:1,自引:0,他引:1
We conducted an experimental investigation into the kinetics and mechanism of tetrahydrofuran synthesis from 1,4-butanediol via dehydration in high-temperature liquid water (HTW) without added catalyst at 200-350 degrees C. The reaction was reversible, with tetrahydrofuran being produced at an equilibrium yield of 84% (at 200 degrees C) to 94% (at 350 degrees C). The addition of CO2 to the reaction mixture increased the reaction rate by a factor of 1.9-2.9, because of the increase in acidity resulting from the formation and dissociation of carbonic acid. This increase was much less than that expected (factor of 37-60) from a previously suggested acid-catalyzed mechanism. This disagreement prompted experiments with added acid (HCl) and base (NaOH) to investigate the influence of pH on the reaction rate. These experiments revealed three distinct regions of pH dependence. At high and low pH, the dehydration rate increased with increasing acidity. At near-neutral pH, however, the rate was essentially insensitive to changes in pH. This behavior is consistent with a mechanism where H2O, in addition to H+, serves as a proton donor. This work indicates that the relatively high native concentration of + (large KW), which has commonly been thought to lead to the occurrence of acid-catalyzed reactions in HTW without added catalyst, does not explain the dehydration of 1,4-butanediol in HTW without catalyst. Rather, H2O serves directly as the proton donor for the reaction. 相似文献
157.
Yuhan Lee Haeshin Lee Phillip B. Messersmith Tae Gwan Park 《Macromolecular rapid communications》2010,31(24):2109-2114
A precise control of metallic‐nanoparticle assembly is highly critical for the realization of tangible, high‐performance devices or materials. Until recently, nanoparticle assembly using 1D templates had been limited to a narrow spectrum of nanoparticles as it was mostly dependent on the surface chemistry of the nanoparticles used. Inspired by the universal adhesive properties of mussels, we demonstrate a universal polymeric template for 1D assembly of various nanoparticles including, gold nanoparticles, iron oxide nanoparticles, and quantum dots. We find that the length of the 1D assembly is tunable using hyaluronic acid‐graft‐catechol templates with various contour lengths.
158.
Caio T. Inácio Alberto M. T. Magalhães Paulo O. Souza Phillip M. Chalk Segundo Urquiaga 《Isotopes in environmental and health studies》2018,54(2):185-195
Variations in the relative isotopic abundance of C and N (δ13C and δ15N) were measured during the composting of different agricultural wastes using bench-scale bioreactors. Different mixtures of agricultural wastes (horse bedding manure?+?legume residues; dairy manure?+?jatropha mill cake; dairy manure?+?sugarcane residues; dairy manure alone) were used for aerobic–thermophilic composting. No significant differences were found between the δ13C values of the feedstock and the final compost, except for dairy manure?+?sugarcane residues (from initial ratio of ?13.6?±?0.2?‰ to final ratio of ?14.4?±?0.2?‰). δ15N values increased significantly in composts of horse bedding manure?+?legumes residues (from initial ratio of +5.9?±?0.1?‰ to final ratio of +8.2?±?0.5?‰) and dairy manure?+?jatropha mill cake (from initial ratio of +9.5?±?0.2?‰ to final ratio of +12.8?±?0.7?‰) and was related to the total N loss (mass balance). δ13C can be used to differentiate composts from different feedstock (e.g. C3 or C4 sources). The quantitative relationship between N loss and δ15N variation should be determined. 相似文献
159.
160.
The synthesis, characterization, and reactivity of the homoleptic uranium(IV) alkyls U(CH(2)C(6)H(5))(4) (1-Ph), U(CH(2)-p-CH(3)C(6)H(4))(4) (1-p-Me), and U(CH(2)-m-(CH(3))(2)C(6)H(3))(4) (1-m-Me(2)) are reported. The addition of 4 equiv of K(CH(2)Ar) (Ar = Ph, p-CH(3)C(6)H(4), m-(CH(3))(2)C(6)H(3)) to UCl(4) at -108 °C produces 1-Ph in good yields and 1-p-Me and 1-m-Me(2) in moderate yields. Further characterization of 1-Ph by X-ray crystallography confirmed η(4)-coordination of each benzyl ligand to the uranium center. Magnetic studies produced an effective magnetic moment of 2.60 μ(B) at 23 °C, which is consistent with a tetravalent uranium 5f(2) electronic configuration. Addition of 1 equiv of the redox-active α-diimine (Mes)DAB(Me) ((Mes)DAB(Me) = [ArN═C(Me)C(Me)═NAr]; Ar = 2,4,6-trimethylphenyl (Mes)) to 1-Ph results in reductive elimination of 1 equiv of bibenzyl (PhCH(2)CH(2)Ph), affording ((Mes)DAB(Me))U(CH(2)C(6)H(5))(2) (2-Ph). Treating an equimolar mixture of 1-Ph and 1-Ph-d(28) with (Mes)DAB(Me) forms the products from monomolecular reductive elimination, 2-Ph, 2-Ph-d(14), bibenzyl, and bibenzyl-d(14). This is confirmed by (1)H NMR spectroscopy and GC/MS analysis of both organometallic and organic products. Addition of 1 equiv of 1,2-bis(dimethylphosphino)ethane (dmpe) to 1-Ph results in formation of the previously synthesized (dmpe)U(CH(2)C(6)H(5))(4) (3-Ph), indicating the redox-innocent chelating phosphine stabilizes the uranium center in 3-Ph and prevents reductive elimination of bibenzyl. Full characterization for 3-Ph, including X-ray crystallography, is reported. 相似文献