全文获取类型
收费全文 | 728篇 |
免费 | 33篇 |
国内免费 | 3篇 |
专业分类
化学 | 479篇 |
晶体学 | 3篇 |
力学 | 16篇 |
数学 | 138篇 |
物理学 | 128篇 |
出版年
2023年 | 6篇 |
2021年 | 11篇 |
2020年 | 11篇 |
2019年 | 12篇 |
2018年 | 9篇 |
2017年 | 8篇 |
2016年 | 29篇 |
2015年 | 13篇 |
2014年 | 17篇 |
2013年 | 32篇 |
2012年 | 23篇 |
2011年 | 40篇 |
2010年 | 28篇 |
2009年 | 30篇 |
2008年 | 36篇 |
2007年 | 37篇 |
2006年 | 30篇 |
2005年 | 27篇 |
2004年 | 20篇 |
2003年 | 19篇 |
2002年 | 24篇 |
2001年 | 5篇 |
2000年 | 7篇 |
1999年 | 5篇 |
1994年 | 6篇 |
1993年 | 9篇 |
1989年 | 7篇 |
1987年 | 5篇 |
1986年 | 11篇 |
1985年 | 6篇 |
1984年 | 5篇 |
1983年 | 5篇 |
1979年 | 6篇 |
1978年 | 5篇 |
1959年 | 5篇 |
1932年 | 12篇 |
1931年 | 6篇 |
1930年 | 5篇 |
1928年 | 9篇 |
1927年 | 6篇 |
1926年 | 5篇 |
1915年 | 4篇 |
1913年 | 4篇 |
1901年 | 4篇 |
1900年 | 4篇 |
1898年 | 4篇 |
1896年 | 4篇 |
1895年 | 4篇 |
1893年 | 13篇 |
1892年 | 4篇 |
排序方式: 共有764条查询结果,搜索用时 15 毫秒
11.
Bibal C Pink M Smurnyy YD Tomaszewski J Caulton KG 《Journal of the American Chemical Society》2004,126(8):2312-2313
The reaction of [(Cymene)RuCl2]2 with the chelate LiHC(PPh2NPh)2 occurs to remove both chloride ligands, to furnish a cationic Ru(II) complex with the monoanionic ligand bound eta3, through two N and an sp3 carbon. This cation is also produced from the conjugate acid of the ligand H2C(PPh2NPh)2 because this molecule can serve as a Br?nsted base, to deprotonate the acidic carbon of another molecule of H2C(PPh2NPh)2. DFT calculations show an energy surface where (Cymene)RuHC(PPh2NPh)2L is more stable with a Ru-CH(PPh2NPh)2 bond and with L = Cl- or MeCN not coordinated to Ru, than to an eta2-HC(PPh2NPh)2 structure with coordinated L; this is tested experimentally. The greater tendency for this ligand to be coordinated eta3 vs analogous diketiminates is discussed. The nucleophilicity of Cgamma in structure 1, vs that of donors L = Cl- or MeCN, is evaluated to understand the preference of the bis(phosphinimino)methanide to be bidentate or tridentate. 相似文献
12.
Zusammenfassung In der vorliegenden Arbeit wird das Sedimentations-gleichgewicht des Systems Na6[H2W12O40]-NaClO4-H2O bei 25 °C untersucht. Die scheinbare Ladungszahl des Natriummetawolframats wird als Funktion der NaClO4-MolalitätmNaClO4 ermittelt. Aus dieser Abhängigkeit kann für die summarische Dissoziation des NatriummetawolframatsNa2[H2W12O4o] 6Na+ + [H2W12O40]6– die DissoziationskonstanteK in Gegenwart von NaClO4 als Fremdelektrolyt zuK=0,08 mol6·kg–6 bestimmt werden.Der Kreuzdifferentialquotient
(
PXz
, ist der Trace-Aktivitätskoeffizient des Natriummetawolframats) wird ebenfalls als Funktion der NaClO4-Molalität ermittelt.Die Konzentrationsabhängigkeit des Trace-Aktivitätskoeffizienten zeigt einen Verlauf, wie er unseres Wissens nach noch nicht von anderen Autoren beobachtet wurde.
Mit 5 Abbildungen und 1 Tabelle 相似文献
Summary An ultracentrifugal study of the sedimentation equilibrium of the system Na2[H2W12O40]-NaClO4-H2Oat 25 °C is presented. The dependency of the apparent charge of the sodium metatungstate on NaClO4-molality is investigated. From these data the dissociation constant for the dissociation of the sodium metatungstate in the presence of NaClO4 according to the equationNa[H2W12O40] 6Na+ + [H2W12O40]6– is calculated toK=0.08 mol6·kg–6. The cross differential quotient ( PXz is the trace activity coefficient of the sodium metatungstate) shows a behavior in its dependence on NaClO4-molality which to our knowledge has not yet been reported by other authors.
Mit 5 Abbildungen und 1 Tabelle 相似文献
13.
Kremser L Brückner A Heger A Grunert T Buchacher A Josic D Allmaier G Rizzi A 《Electrophoresis》2003,24(24):4282-4290
The isoforms distribution of the glycoprotein antithrombin III (ATIII) derived from human plasma was investigated by means of isoelectric focusing (IEF) in polyacrylamide gels with immobilized pH gradients (IPG) and two-dimensional gel electrophoresis (2-DE) as well as capillary electrophoretic methods. It turned out that the presence of high concentrations of chaotropics (urea, thiourea) and zwitterionic detergents (3-[(3-cholamidepropyl)dimethylammonio]-1-propanesulfonate (CHAPS)) was decisive for attaining good resolution of the protein isoforms. Resolution by IPG-IEF was obtained with excellent reproducibility and pI differences down to 0.01 pH units could be distinguished. ATIII-alpha and ATIII-beta-fractions preseparated by heparin affinity chromatography showed an analogous but shifted spot pattern consisting each of one major and three minor isoforms. The main isoforms of ATIII-alpha and ATIII-beta exhibit pI values of 5.18 and 5.32, respectively, both values determined in the presence of high concentrations of urea. The pI difference of 0.14 pH units correspond to the effect of two sialic acids absent in ATIII-beta. The formation and occurrence of ATIII dimers and trimers turned out to be dependent on the sample preparation. The results obtained by 2-DE were compared with those of capillary zone electrophoresis (CZE) and capillary IEF (CIEF). Quantitative analysis regarding the CZE separated isoforms of plasma derived ATIII yielded a content of about 70% ATIII-alpha main isoform and about 6.6% of ATIII-beta. The pI values of ATIII determined by CIEF with internal calibration were in fair agreement with the pI values of the main isoforms achieved with 2-DE. 相似文献
14.
Brake JM Daschner MK Abbott NL 《Langmuir : the ACS journal of surfaces and colloids》2005,21(6):2218-2228
This paper reports an experimental investigation of the self-assembly of phospholipids (l-alpha-phosphatidylcholine-beta-oleoyl-gamma-palmitoyl (l-POPC), dipalmitoyl phosphatidylcholine (DPPC), and l-alpha-dilauroyl phosphatidylcholine (l-DLPC)) at interfaces between aqueous phases and the nematic liquid crystal (LC) 4'-pentyl-4-cyanobiphenyl. Stable planar interfaces between the aqueous phases and LCs were created by hosting the LCs within gold grids (square pores with widths of 283 microm and depths of 20 microm). At these interfaces, the presence and lateral organization of the phospholipids leads to interface-driven orientational transitions within the LC. By doping the phospholipids with a fluorescently labeled lipid (Texas Red-1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine (TR-DPPE)), quantitative epifluorescence microscopy revealed the saturation coverage of phospholipid at the interface to be that of a monolayer with an areal density of approximately 49 +/- 8% relative to hydrated lipid bilayers. By adsorbing phospholipids to the aqueous-LC interface from either vesicles or mixed micelles of dodecyltrimethylammonium and phospholipid, control of the areal density of phospholipid from 42 +/- 10 to 102 +/-18% of saturation monolayer coverage was demonstrated. Fluorescence recovery after photobleaching (FRAP) experiments performed by using laser scanning confocal microscopy (LSCM) revealed the lateral mobility of fluorescently labeled DPPE in l-DLPC assembled at the interface with the liquid crystal to be (6 +/- 1) x 10(-12) m(2)/s for densely packed monolayers. Variation of the surface coverage and composition of phospholipid led to changes in lateral diffusivity between (0.2 +/- 0.1) x 10(-12) and (15 +/- 2) x 10(-12) m(2)/s. We also observed the phospholipid-laden interface to be compartmentalized by the gold grid, thus allowing for the creation of patterned arrays of phospholipids at the LC-aqueous interface. 相似文献
15.
Reaction of Telluriumhexafluoride and Trimethylamine, Structures of the TeF5? and SeF5? Anions The reaction of TeF6 and (CH3)3N is of the redox kind, resulting in reduction of tellurium: X-ray single crystal analysis reveals the compounds (CH3)2N? CH2? N(CH3)2+TeF5? and [(CH3)3NH+]5(TeF5?)3(HF2?)2. By comparison with published data it can be shown that this mixture is identical to previously published [(CH3)3N]2TeF6. The latter was supposed to be one of the few examples of tellurium in a coordination state of eight. (CH3)4N+TeF5? and (CH3)4N4SeF5? are obtained and their structure is investigated by single crystal x-ray methods also. The anions SF5?, SeF5? and TeF5? are discussed in terms of weak interactions. 相似文献
16.
[reaction: see text] Whereas cyclopentenylcarbenes resulting from photocycloaddition of 4-alk-1-ynylcoumarins to 2,3-dimethylbut-2-ene undergo tandem cyclization to hitherto unknown tetracyclic (4-hetera)cyclopent[b,c]acenaphthylenes, the corresponding cyclopentenylnitrenes stemming from 4-cyanocoumarins and the same alkene are converted into tricyclic imines via H-abstraction. 相似文献
17.
Ozerov OV Pink M Watson LA Caulton KG 《Journal of the American Chemical Society》2004,126(7):2105-2113
Both (PNP)Re(H)(4) and (PNP)ReH(cyclooctyne) (PNP(i)(Pr) = ((i)Pr(2)PCH(2)SiMe(2))(2)N) react with alkylpyridines NC(5)H(4)R to give first (PNP)ReH(2)(eta(2)-pyridyl) and cyclooctene and then, when not sterically blocked, (PNP)Re(eta(2)-pyridyl)(2) and cyclooctane. The latter are shown by NMR, X-ray diffraction, and DFT calculations to have several energetically competitive isomeric structures and pyridyl N donation in preference to PNP amide pi-donation. DFT studies support NMR solution evidence that the most stable bis pyridyl structure is one that is doubly eta(2)- with the pyridyl N donating to the metal center. When both ortho positions carry methyl substituents, cyclooctane and the carbyne complex (PNP)ReH(tbd1;C-pyridyl) are produced. Excess 2-vinyl pyridine reacts with (PNP)Re(H)(4) preferentially at the vinyl group, to give 2-ethyl pyridine and the sigma-vinyl complex (PNP)ReH[eta(2)-CH=CH(2-py)]. The DFT and X-ray structures show, by various comparisons, the ability of the PNP amide nitrogen to pi-donate to an otherwise unsaturated d(4) Re(III) center, showing short Re-N distances consistent with the presence of pi-donation. 相似文献
18.
19.
Fabrication of three-dimensional photonic crystals with tunable photonic properties by biotemplating
Daniel Van Opdenbosch Maren Johannes Xia Wu Helge Fabritius Cordt Zollfrank 《Photonics and Nanostructures》2012,10(4):516-522
Photonic crystals with tunable D-surface structures for possible high-temperature gas- and temperature-sensing applications were prepared by a biotemplating method. This included infiltrating colored scales of the beetle Entimus imperialis with an organopolysiloxane mixture followed by simultaneous combustion of the template and calcination of the cured organopolysiloxane. A high-yield inorganic silica-based replica of the original structure was obtained, which is capable of withstanding temperatures up to 600 °C. Light- and scanning electron microscopy combined with focused ion beam milling showed a precise replication of the whole scales and their internal D-surface structure. Fourier-transform infrared spectroscopy and X-ray diffraction analysis confirmed the complete curing of the organopolysiloxanes and their transformation into amorphous silica during calcination. The dielectric constant of the manufactured materials determined by Abbé refractometry was ? = 2.3180 and used to perform band structure calculations utilizing the plane wave expansion method. By changing the chain length and degree of crosslinking of the organopolysiloxane precursor mixture, the lattice parameters and filling factors, and therefore the photonic properties of the replicas, could be tuned. 相似文献
20.
This paper presents a special use of the linear poroelasticity theory to describe tidally induced groundwater oscillations. Two models of oscillation inducing mechanism make use of this theory to predict groundwater level fluctuations. The numerical solutions of both models are presented and compared with well water level measurement obtained in Police Basin, north-east Bohemia. 相似文献