全文获取类型
收费全文 | 112066篇 |
免费 | 1701篇 |
国内免费 | 402篇 |
专业分类
化学 | 47753篇 |
晶体学 | 1084篇 |
力学 | 7306篇 |
综合类 | 1篇 |
数学 | 36245篇 |
物理学 | 21780篇 |
出版年
2023年 | 284篇 |
2022年 | 235篇 |
2021年 | 447篇 |
2020年 | 600篇 |
2019年 | 581篇 |
2018年 | 10907篇 |
2017年 | 10721篇 |
2016年 | 7226篇 |
2015年 | 1910篇 |
2014年 | 1410篇 |
2013年 | 2643篇 |
2012年 | 6116篇 |
2011年 | 12799篇 |
2010年 | 6987篇 |
2009年 | 7146篇 |
2008年 | 8627篇 |
2007年 | 10679篇 |
2006年 | 2127篇 |
2005年 | 2991篇 |
2004年 | 2902篇 |
2003年 | 3021篇 |
2002年 | 1987篇 |
2001年 | 976篇 |
2000年 | 941篇 |
1999年 | 647篇 |
1998年 | 556篇 |
1997年 | 424篇 |
1996年 | 628篇 |
1995年 | 427篇 |
1994年 | 377篇 |
1993年 | 429篇 |
1992年 | 358篇 |
1991年 | 272篇 |
1990年 | 262篇 |
1989年 | 225篇 |
1988年 | 228篇 |
1987年 | 222篇 |
1986年 | 205篇 |
1985年 | 283篇 |
1984年 | 246篇 |
1983年 | 210篇 |
1982年 | 208篇 |
1981年 | 192篇 |
1980年 | 179篇 |
1979年 | 186篇 |
1978年 | 179篇 |
1977年 | 152篇 |
1976年 | 171篇 |
1975年 | 149篇 |
1973年 | 157篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
991.
Martín-Matute B Bogár K Edin M Kaynak FB Bäckvall JE 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(20):5832-5842
A range of ruthenium cyclopentadienyl (Cp) complexes have been prepared and used for isomerization of allylic alcohols to the corresponding saturated carbonyl compounds. Complexes bearing CO ligands show higher activity than those with PPh3 ligands. The isomerization rate is highly affected by the substituents on the Cp ring. Tetra(phenyl)methyl-substituted catalysts rapidly isomerize allylic alcohols under very mild reaction conditions (ambient temperature) with short reaction times. Substituted allylic alcohols have been isomerized by employing Ru-Cp complexes. A study of the isomerization catalyzed by [Ru(Ph5Cp)(CO)2H] (14) indicates that the isomerization catalyzed by ruthenium hydrides partly follows a different mechanism than that of ruthenium halides activated by KOtBu. Furthermore, the lack of ketone exchange when the isomerization was performed in the presence of an unsaturated ketone (1 equiv), different from that obtained by dehydrogenation of the starting allylic alcohol, supports a mechanism in which the isomerization takes place within the coordination sphere of the ruthenium catalyst. 相似文献
992.
Serrano MC Portolés MT Vallet-Regí M Izquierdo I Galletti L Comas JV Pagani R 《Macromolecular bioscience》2005,5(5):415-423
Tissue engineering offers the potential of providing vessels that can be used to replace diseased and damaged native blood vessels. The endothelization of a synthetic vascular graft minimizes the failures associated with blood clotting and platelet activation. The aim of this study was to culture vascular-derived endothelial and smooth muscle cells on both untreated and NaOH-treated poly(epsilon-caprolactone) (PCL) films, a biocompatible and bio-resorbable polymer, and to evaluate the behavior of both cell types as a preliminary study for vascular graft development. PCL films were prepared by hot pressing; characterized by DSC, IR, SEM, and scanning force microscopy; and treated with NaOH to increase the surface hydrophilicity before cell culture. Endothelial and smooth muscle cells, isolated from pig cava vein, were characterized by immunofluorescence and confocal microscopy studies of endothelial nitric oxide synthase and alpha-smooth muscle actin. Good adhesion, growth, viability and morphology of both the endothelial and smooth muscle cells on PCL films were obtained, but a light stimulation of mitochondrial activity was observed during short culture times. NaOH treatment improved the adhesion and enhanced the proliferation in both cell types. This verified the possible use of this modified polymer as a support in the preparation of a synthetic vascular graft. [Diagram: see text] SEM micrograph of smooth muscle cells cultured on NaOH-treated PCL film. (Original magnification: 1000x). 相似文献
993.
Prados-Rosales RC Herrera MC Luque-García JL de Castro L 《Journal of chromatography. A》2002,946(1-2):133-140
A fast microwave-assisted dansylation procedure has been developed for the derivatization of N-nitrosamines prior to high-performance liquid chromatography determination. N-Nitrosomorpholine, N-nitrosodimethylamine, N-nitrosodiethylamine, N-nitrosopyrrolidine and N-nitrosopiperidine are first denitrosated by hydrobromic acid-acetic acid to produce secondary amines, which are then quantitatively dansylated in 5 min using radiation power of 378 W and a maximum pressure of 1.4 bar inside the reactor. The reaction mixture is separated on a C18 column with acetonitrile-water (55:45, v/v) as mobile phase with fluorimetric detection at 531 nm (excitation at 339 nm). The detection limits range from 8 to 75 pg for N-nitrosomorpholine and N-nitrosodiethylamine, respectively. The method was applied to study the recoveries of N-nitrosamines in beer and their determination in cigarette smoke. 相似文献
994.
Benítez IO Bujoli B Camus LJ Lee CM Odobel F Talham DR 《Journal of the American Chemical Society》2002,124(16):4363-4370
Organized monolayer films of a manganese tetraphenylporphyrin have been prepared and used as supported oxidation catalysts. Manganese 5,10,15,20-tetrakis(tetrafluorophenyl-4'-octadecyloxyphosphonic acid) porphyrin (1) has been immobilized as a monolayer film by a combination of Langmuir-Blodgett (LB) and self-assembled monolayer techniques that use zirconium phosphonate linkages to bind the molecule to the surface. Analysis by FTIR, XPS, UV-vis and polarized optical spectroscopy show that the films consist of noninteracting molecules effectively anchored and oriented nearly parallel to the surface. The monolayer films are stable to the solvent and temperature conditions needed to explore organic oxidations. The activity of films of 1 toward the epoxidation of cyclooctene using iodosylbenzene as the oxidant was compared to that of Manganese 5,10,15,20-tetrakis(pentafluorophenyl) porphyrin (2) and 1 under equivalent homogeneous conditions. The immobilized porphyrin 1 shows an enhanced activity relative to either homogeneous reaction. The main difference between 1 and 2 is the four alkyl phosphonate arms in 1 designed to incorporate the porphyrin within the films. The increased activity of immobilized 1 is a combination of the porphyrin structure, which prohibits the formation of mu-oxo dimers even in solution, and a change in conformation when anchored to the surface. The study demonstrates that careful monolayer studies can provide useful models for the design and study of supported molecular catalyst systems. 相似文献
995.
Fernández-Rivas C Méndez M Nieto-Oberhuber C Echavarren AM 《The Journal of organic chemistry》2002,67(15):5197-5201
The intramolecular reaction of allylsilanes and allylstannanes with alkynes proceeds catalytically in the presence of Pt(II), Pd(II), Ru(II), and Au(III) chlorides. Although more limited, AgOTf also catalyzes the cyclization. Usually, PtCl2 as the catalyst in methanol or acetone gives the best results. The reaction proceeds by exo attack of the allyl nucleophile on the alkyne to form five- or six-membered ring carbocycles. The reaction generally proceeds with anti stereoselectivity. However, a terminally substituted trimethylsilyl derivative reacts by a syn-type addition. The intermediate alkenylpalladium complex has been trapped with allyl chloride to form an allylated derivative with an additional carbon-carbon bond. 相似文献
996.
Capillary zone electrophoretic separation and determination of imidazolic antifungal drugs 总被引:1,自引:0,他引:1
Capillary zone electrophoresis (CZE) was adapted to the simultaneous determination of a mixture of three imidazolic antifungal drugs. Separation was achieved by using a fused-silica capillary column with an acetic acid-Tris buffer at pH 5.18 and UV detection at 196 nm. Several electrophoretic parameters were investigated: pH and buffer concentration, applied voltage, temperature and injection conditions. The optimized CZE method was applied to the individual determination of ketoconazole, clotrimazole and econazole in pharmaceutical forms, after a previous single extraction step in methanol, with recoveries of 98.00, 99.96 and 99.58% respectively. The antifungal drugs can be determined at a concentration level lower than 1.0 x 10(-7) M. 相似文献
997.
The oxidation of glyceraldehyde with manganese(III) sulfate was studied. The reaction stoichiometry was found and a procedure for an indirect determination of 5–17 mg of the test substance has been proposed. The recommended procedure is based on the oxidation of glyceraldehyde with the reagent, the excess of which is back-titrated with standard solution of ferrous sulfate. 相似文献
998.
Pérez-Prieto J Galian RE Miranda MA Catalina F Martín-Vargas N López-Ortiz F 《Organic letters》2004,6(4):561-564
[reaction: see text] Several benzo[d]-1,2-oxaphosphole 2-oxides were examined as potential precursors of stabilized C-centered radicals. The transient absorption spectra obtained after laser flash photolysis in the presence of di-tert-butyl peroxide showed the features of benzylic radicals with formation and decay kinetics not significantly influenced by the presence of oxygen. In the case of compounds with two possible diastereomeric forms, the C-H bond of the trans-isomers [corrected] is more reactive toward hydrogen abstraction. 相似文献
999.
Heating rate effect on the DSC kinetics of oil shales 总被引:1,自引:0,他引:1
M. V. Kök 《Journal of Thermal Analysis and Calorimetry》2007,90(3):817-821
This research was aimed to investigate the combustion and kinetics of oil shale samples (Mengen and Himmetoğlu) by differential
scanning calorimetry (DSC). Experiments were performed in air atmosphere up to 600°C at five different heating rates. The
DSC curves clearly demonstrate distinct reaction regions in the oil shale samples studied. Reaction intervals, peak and burn-out
temperatures of the oil shale samples are also determined. Arrhenius kinetic method was used to analyze the DSC data and it
was observed that the activation energies of the samples are varied in the range of 22.4–127.3 kJ mol−1 depending on the oil shale type and heating rate. 相似文献
1000.
The equilibrium constants, K
2, have been determined for the proton-transfer reactions of 1-phenacylquinolinium ion, PHQ+, with several amines {triethylamine (TEA), N,N,N′,N′-tetramethylethylenediamine (ED), N,N,N′, N′-tetramethylpropanediamine (PD), N,N,N′,N′-tetramethylbutanediamine (BD), and 1,8-bis(dimethylamino-naphthalene (DMAN)} in acetonitrile (AN), AN-tetrahydrofuran (THF)
and AN-ethanol (EtOH) mixtures. The reaction was followed spectrophotometrically using a stopped-flow technique. The K
2 value decreased for DMAN and increased for TEA with increasing vol-% of THF in AN-THF mixtures. The changes in the K
2 value for ED, PD and BD changed in the order: ED, PD and BD from a pattern similar to TEA to a pattern similar to DMAN. The
change in the K
2 value for DMAN with increasing vol-% of THF in AN-THF mixtures was explained by the effect of polarity on the stability of
P−Q+ (the deprotonated product of PHQ+). The effect of THF on the K
2 value is consistent with that of the peak wavelength of the absorption spectrum of P−Q+. The change in the K
2 value for TEA, ED, PD and BD depended on the structures of the protonated bases, one of the products for this reaction. The
effect of EtOH on the K
2 value for DMAN was examined in ternary EtOH-THF-AN mixtures that contain different amounts of EtOH and whose relative permittivities
were adjusted to that of EtOH. The K
2 value increased with increasing vol-% of EtOH because of the stabilization of P−Q+ upon the formation of the hydrogen-bonded complex with EtOH. The absorption spectrum of P−Q+ demonstrated a blue shift as the vol-% of EtOH increased. 相似文献