全文获取类型
收费全文 | 1222篇 |
免费 | 52篇 |
国内免费 | 14篇 |
专业分类
化学 | 783篇 |
力学 | 18篇 |
数学 | 272篇 |
物理学 | 215篇 |
出版年
2023年 | 12篇 |
2022年 | 10篇 |
2021年 | 19篇 |
2020年 | 23篇 |
2019年 | 31篇 |
2018年 | 30篇 |
2017年 | 19篇 |
2016年 | 44篇 |
2015年 | 27篇 |
2014年 | 45篇 |
2013年 | 72篇 |
2012年 | 89篇 |
2011年 | 87篇 |
2010年 | 66篇 |
2009年 | 56篇 |
2008年 | 76篇 |
2007年 | 81篇 |
2006年 | 64篇 |
2005年 | 80篇 |
2004年 | 62篇 |
2003年 | 39篇 |
2002年 | 48篇 |
2001年 | 16篇 |
2000年 | 16篇 |
1999年 | 22篇 |
1998年 | 16篇 |
1997年 | 9篇 |
1996年 | 22篇 |
1995年 | 11篇 |
1994年 | 19篇 |
1993年 | 10篇 |
1992年 | 11篇 |
1991年 | 6篇 |
1990年 | 3篇 |
1989年 | 6篇 |
1988年 | 3篇 |
1987年 | 2篇 |
1985年 | 6篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1981年 | 2篇 |
1980年 | 4篇 |
1979年 | 3篇 |
1978年 | 2篇 |
1958年 | 1篇 |
1931年 | 1篇 |
1930年 | 1篇 |
1926年 | 1篇 |
1922年 | 1篇 |
1903年 | 1篇 |
排序方式: 共有1288条查询结果,搜索用时 46 毫秒
21.
22.
Tcholakova S Denkov ND Danner T 《Langmuir : the ACS journal of surfaces and colloids》2004,20(18):7444-7458
A systematic experimental study of the effect of several factors on the mean drop diameter, d32, during emulsification, is performed with soybean oil-in-water emulsions. These factors are (1) type of used emulsifier; (2) emulsifier concentration, CS; and (3) ionic strength of the aqueous solution. Three different types of emulsifier, anionic (sodium dodecyl sulfate, SDS), nonionic (polyoxyethylene-20 cetyl ether, Brij 58), and protein (whey protein concentrate), are studied. For all of the studied systems, two well-defined regions are observed in the dependence of d32 on CS: at low surfactant concentration, d32 increases significantly with the decrease of CS (region 1), whereas d32 does not depend on CS at high surfactant concentration (region 2). The model, proposed by Tcholakova et al. (Langmuir 2003, 19, 5640), is found to describe well the dependence of d32 on CS in region 1 for the nonionic surfactant and for the protein emulsifier at high electrolyte concentration, 150 mM NaCl. According to this model, a well defined minimal surfactant adsorption (close to that of the dense adsorption monolayer) is needed for obtaining an emulsion. On the other hand, this model is found inapplicable to emulsions stabilized by the ionic surfactant, SDS, and by the nonionic surfactant, Brij 58, at low electrolyte concentration. The performed theoretical analysis of drop-drop interactions, in the emulsification equipment, shows that a strong electrostatic repulsion between the colliding drops impedes the drop-drop coalescence in the latter systems, so that smaller emulsion drops are obtained in comparison with the theoretically predicted ones. The results for SDS-stabilized emulsions in region 1 are explained by a quantitative consideration of this electrostatic repulsion. The drop size in region 2 (surfactant-rich regime) is described very well by the Kolmogorov-Hinze theory of turbulent emulsification. 相似文献
23.
Watson MD Jäckel F Severin N Rabe JP Müllen K 《Journal of the American Chemical Society》2004,126(5):1402-1407
Cyclophanes with the largest-to-date polycyclic aromatic hydrocarbon (hexa-peri-hexabenzocoronene, HBC) to be entrained in such a structural motif are reported. The two disks are covalently captured by intermolecular ring-closing olefin metathesis of dienes in good yield. DSC, optical microscopy, and WAXD show the new cyclophanes to self-assemble to thermotropic columnar liquid crystal mesophases similar to monomeric analogues. Solution spectroscopic studies reveal that the two disks within a single unit lie face-to-face, with a small average lateral offset. Self-assembly into two-dimensional crystals at a solid-liquid interface was visualized by STM, and the electrical properties of single molecules were assessed by scanning tunneling spectroscopy revealing a diode-like behavior which is similar to that previously reported for single HBC disks, laying the groundwork for future electrical interrogations of dynamic molecular complexes. 相似文献
24.
Thermal and Temporal Aging of Two Step Acid-Base Catalyzed Silica Gels in Water/Ethanol Solutions 总被引:1,自引:0,他引:1
Haereid S. Nilsen E. Ranum V. Einarsrud M.-A. 《Journal of Sol-Gel Science and Technology》1997,8(1-3):153-157
Dissolution and reprecipitation of silica during aging in water improve the wet gels mechanical stiffness and strength, and hence shrinkage during supercritical drying is reduced. We have investigated how the strength and stiffness of a 2-step TEOS acid-base catalyzed wet gel can be improved by aging in a solution of water/ethanol (20–40 vol%) at various temperatures (20–70°C) and time (2 h and 24 h) and how this influences the aerogels properties. The linear shrinkage during supercritical drying was reduced from 29% to 2% by introducing the aging step in the 20 vol% water/ethanol solution for 24 h at 60°C.We have also in previous works introduced the idea of preparing ambient pressure dried silica aerogels by increasing the wet gels stiffness by aging in a TEOS solution until shrinkage during drying is almost eliminated. The gels aged in the water/ethanol solutions were further aged in a TEOS/ethanol solution and the effect of the increasing water content in the pore liquid was studied. A xerogel density of 0.20 g/cm3 is reported for gels with a shear modulus (G) of 30 MPa. 相似文献
25.
Development of quantitative vitellogenin-ELISAs for fish test species used in endocrine disruptor screening 总被引:5,自引:0,他引:5
Nilsen BM Berg K Eidem JK Kristiansen SI Brion F Porcher JM Goksøyr A 《Analytical and bioanalytical chemistry》2004,378(3):621-633
The yolk protein precursor vitellogenin (Vtg) in plasma has proved to be a simple and sensitive biomarker for assessing exposure of fish to environmental estrogens. Within international bodies such as the Organization for Economic Cooperation and Development (OECD) work is ongoing to develop screening and testing programmes for endocrine disrupting effects of new chemicals, and in the focus of this development are the fish test species common carp (Cyprinus carpio), fathead minnow (Pimephales promelas), zebrafish (Danio rerio) and Japanese medaka (Oryzias latipes). In this study we have developed quantitative enzyme linked immunosorbent assays (ELISAs) for Vtg in common carp/fathead minnow, zebrafish and Japanese medaka. The assays were developed using a combination of monoclonal and polyclonal fish Vtg antibodies in a sandwich format, using stabilized Vtg from the test species as a standard. The carp Vtg ELISA has a working range of 1–63 ng/mL, a minimal detection limit of 0.6 ng/mL, and may also be used for quantification of Vtg in fathead minnow. In fathead minnow whole-body homogenate samples, the practical detection limit is 400 ng/mL due to the matrix effect. The zebrafish Vtg ELISA has a working range of 0.5–63 ng/mL, a minimal detection limit of 0.4 ng/mL, and a practical detection limit of 200 ng/mL in whole-body homogenate samples. The medaka Vtg ELISA has a working range of 0.25–16 ng/mL, a minimal detection limit of 0.1 ng/mL, and a practical detection limit of 125 ng/mL in whole-body homogenate samples. The intra- and inter-assay variations were below 20% for all assays. The assays were evaluated with sets of representative samples spanning the wide dynamic range of Vtg-levels found in fish exposed to environmental estrogens, and all three assays are currently undergoing international inter-laboratory validation. 相似文献
26.
Ab initio calculations of core-ionization spectra of the anion-molecule Cl-CO cluster are performed. Particular attention is paid to the investigation of charge-transfer screening processes accompanying core ionization of the CO molecule in the cluster. The charge-transfer processes are very efficient and favored by the presence of a low-lying unoccupied pi* orbital in CO capable of accepting an electron from Cl-. The O1s(-1) and C1s(-1) core-ionization spectra are calculated and compared. Both reveal a breakdown of the quasiparticle picture of core ionization caused by the charge-transfer processes. Remarkable differences between these two spectra are found which manifest themselves in distinct intensity distributions in the prominent low-energy spectral bands. The underlying reason for these differences is elucidated and linked with the preference of the pi* orbital to localize mainly on carbon. Core-ionization spectra of anion-molecule clusters are very sensitive to the type of the molecule involved as the comparative analysis of the O1s(-1) core-ionization spectra of the Cl-CO and Cl-H(2)O clusters show. 相似文献
27.
Vukadin M. Leovac Vladimir Divjaković Ana F. Petrović Nikolai V. Gerbeleu 《Monatshefte für Chemie / Chemical Monthly》1989,120(3):181-186
Summary The reaction of warmDMF solutions of Cu(II) perchlorate, 5-nitrosalicylaldehyde S-methylisothiosemicarbazone (H2
L) and piperidine (Pip) yielded the paramagnetic (eff=2.19 B.M.) Cu(L)Pip complex, whereL is the dianionic form of H2
L, formed as a result of deprotonation of the phenolic hydroxyl and NH2 group. Crystal data of the complex are: monoclinic P21,a=11.902(4),b=6.765(3),c=11.343(4)Å; =112.92°,V=841.20(8)Å3,M=400.9,Z=2,d
0=1.60 gcm–3,d
c
=1.58 gcm–3,F(000)=424. The structure was refined to a residualR=0.047. The copper(II) ion is coordinated in a square-planar arrangement by the piperidine nitrogen and the NNO set of donor atoms ofL.
Komplexe der Übergangsmetalle mit Thiosemicarbazid-Liganden, IV. Synthese und molekulare Struktur von 5-Nitrosalicylaldehyd-S-methylisothiosemicarbazonato-piperidin-kupfer(II)
Zusammenfassung Durch die Reaktion in warmenDMF-Lösungen von Cu(II) Perchlorat, 5-Nitrosalicylaldehyd-S-methylisothiosemicarbazon (H2 L) und Piperidin (Pip) wurde ein paramagnetischer Komplex (eff=2.19 B.M.) Cu(L)Pip erhalten, wobeiL nach doppelter Deprotonierung (NH2- und Phenolhydroxyl-Gruppe) als dianionische Form von H2 L vorliegt. Die kristallographischen Daten des Komplexes sind: monokline Raumgruppe P21,a=11.902(4),b=6.765(3),c=11.343(4)Å, =112.92°;V=841.20Å3,M=400.9,Z=2,d 0=1.60 gcm–3,d c =1.58 gcm–3,F(000)=424. Die struktur wurde bis zu einemR-Wert von 0.047 verfeinert. Die Koordination des Kupfers wird quadratisch-planar über den Piperidin-Stickstoff und die NNO-Donorhülle der Chelatliganden gebildet.相似文献
28.
The role of acid catalysis in oxacalix[3]arene synthesis has been investigated. A range of acids were used to optimize the yield of tert-butyloxacalix[3]arene, the most efficient being p-toluenesulfonic acid, which, with local symmetry complementary with that of the lower rim of the calixarene, provides a templating effect. 相似文献
29.
J. C. Moreno J. Nilsen J. A. Koch B. J. MacGowan J. H. Scofield L. B. Da Silva 《Applied physics. B, Lasers and optics》1994,58(1):3-5
Neon-like niobium X-ray lasers have been studied using both slab and thin-foil target geometries. Niobium foils of various lengths were irradiated from both sides with two beams of the frequency-doubled Nova laser system using a line focus. We looked for gain by measuring spectrally integrated line intensities at different plasma lengths. Gain was observed in four neon-like niobium lines corresponding to 3s–3p transitions. The line profile of theJ = 0–1 line ( = 145.9 ) shows splitting due to the hyperfine effect. Improved contrast in the hyperfine structure is observed as the plasma length is increased. Hyperfine splitting may be relevant to other 3s–3p transitions in neon-like niobium as well as other neon-like X-ray laser systems. 相似文献
30.
J. Nilsen J. C. Moreno B. J. MacGowan J. A. Koch 《Applied physics. B, Lasers and optics》1993,57(5):309-311
We report lasing for the first time in nickel on the neon-like J=01, 3p3s transition at 231 Å as well as several weaker transitions including the J=2»1 lines at 298 Å and 304 Å. Amplification is seen only when the prepulse technique of using a low intensity prepulse before the main optical drive pulse is used to illuminate the nickel target. The prepulse technique is also shown to produce lasing in copper and dramatically improve the output of the germanium laser. 相似文献