全文获取类型
收费全文 | 9816篇 |
免费 | 196篇 |
国内免费 | 55篇 |
专业分类
化学 | 6294篇 |
晶体学 | 85篇 |
力学 | 307篇 |
数学 | 1834篇 |
物理学 | 1547篇 |
出版年
2021年 | 101篇 |
2020年 | 99篇 |
2019年 | 83篇 |
2018年 | 73篇 |
2017年 | 63篇 |
2016年 | 154篇 |
2015年 | 140篇 |
2014年 | 163篇 |
2013年 | 550篇 |
2012年 | 389篇 |
2011年 | 502篇 |
2010年 | 277篇 |
2009年 | 249篇 |
2008年 | 499篇 |
2007年 | 471篇 |
2006年 | 474篇 |
2005年 | 451篇 |
2004年 | 352篇 |
2003年 | 346篇 |
2002年 | 372篇 |
2001年 | 152篇 |
2000年 | 139篇 |
1999年 | 112篇 |
1998年 | 104篇 |
1997年 | 125篇 |
1996年 | 159篇 |
1995年 | 99篇 |
1994年 | 113篇 |
1993年 | 114篇 |
1992年 | 123篇 |
1991年 | 111篇 |
1990年 | 109篇 |
1989年 | 87篇 |
1988年 | 100篇 |
1987年 | 97篇 |
1986年 | 78篇 |
1985年 | 167篇 |
1984年 | 159篇 |
1983年 | 132篇 |
1982年 | 153篇 |
1981年 | 163篇 |
1980年 | 165篇 |
1979年 | 139篇 |
1978年 | 144篇 |
1977年 | 147篇 |
1976年 | 129篇 |
1975年 | 112篇 |
1974年 | 111篇 |
1973年 | 110篇 |
1972年 | 67篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
101.
The growth of crystals in solution 总被引:3,自引:0,他引:3
George H. Nancollas 《Advances in colloid and interface science》1979,10(1):215-252
The crystallization of sparingly soluble salts from their aqueous supersaturated solutions is discussed from the standpoint of two important applications; scale formation and biological mineralization. Theories of crystal growth are outlined and the importance of kinetic factors in determining the nature of the growing phases is discussed. The kinetic factors can be studied by using a highly reproducible seeded growth technique and under certain conditions secondary nucleation can also be induced on the surface of the inoculating seed crystals. The kinetics of crystallization of the alkaline earth surfaces and the calcium phosphates is discussed. In the latter systems, temperature, supersaturation, surface concentration, pH, ionic strength and the presence of foreign ions are important in determining the nature of the phase which grows on the added seed crystals. The mechanism of the retardation of crystal growth by added crystallization inhibitors is illustrated by the influence of organic phosphonate molecules upon the precipitation of calcium carbonate. 相似文献
102.
Summary The use ofp-methylaminophenol sulphate (metol) at 100 for the reduction of phosphomolybdic acid in the determination of phosphate in sea-water has a number of advantages over stannous chloride. The molybdenum blue colour once formed, is stable for several hours, and the calibration curve is not dependent upon the batches of reagent used; Beer's law is obeyed up to concentrations of at least 1 mg PO4-P/l. The salt error is very small and the method has approximately 30% greater sensitivity in sea-water than has the stannous chloride method. Arsenic does not interfere at concentrations five times greater than its sea-water concentration. Iron and copper in moderate amounts do not interfere.Evaporation to dryness with a mixture of concentrated nitric and perchloric acids, followed by colorimetric determination of inorganic phosphate, is employed for the determination of total phosphorus in sea-water and marine muds. The method shows a coefficient of variation of ca. 2% with sea-water containing 60g P/l.
Zusammenfassung Die Anwendung von p-Methylaminophenolsulfat (Metol) bei 100 für die Reduktion von PhosphomolybdÄnsÄure bei der Bestimmung der Phosphate in Meerwasser hat gegenüber Zinn(II)chlorid eine Reihe von Vorteilen. Das einmal gebildete MolybdÄnblau ist für einige Stunden stabil und die Eichkurve nicht von der angewendeten Menge Reagens abhÄngig; das Beersche Gesetz ist für Konzentrationen bis zu 1 mg Phosphat-Phosphor/l gültig. Der Salzfehler ist sehr klein und die Methode für Meerwasser etwa um 30% empfindlicher als die Zinn(II)chloridmethode. Arsen stört bei Konzentrationen, die fünfmal größer sind als in Meerwasser, nicht. Eisen und Kupfer in mÄßigen Mengen stören gleichfalls nicht.Für die Bestimmung des Gesamtphosphors in Meerwasser und Seeschlamm wird mit einer Mischung von konz. SalpetersÄure und PerchlorsÄure zur Trockne verdampft und das anorganische Phosphat kolorimetrisch gemessen. Die Methode zeigt eine Schwankungsbreite von etwa 2% für Meerwasser mit 60g P/l.
Résumé L'emploi du sulfate de p-méthylaminophenol (métol) à 100 pour la réduction de l'acide phosphomolybdique lors du dosage des phosphates contenus dans l'eau de mer présente de multiples avantages sur celui du chlorure stanneux. Après sa formation, le bleu de molybdène reste stable pendant plusieurs heures et la courbe d'étalonnage ne varie pas avec le lot de réactif employé; la loi deBeer est applicable jusqu'à des concentrations au moins égales à 1 mg de phosphore phosphorique par litre. L'erreur de sel est très faible et la sensibilité de la méthode appliquée à l'eau de mer est environ 30% plus élevée que la méthode au chlorure stanneux. L'arsenic ne gÊne pas mÊme pour des concentrations cinq fois supérieures à celle qu'il atteint dans l'eau de mer. Des teneurs modérées de fer et de cuivre n'apportent pas de perturbation. On évapore à siecité en présence d'un mélange d'acides nitrique et perchlorique concentrés puis on effectue une détermination colorimétrique des phosphates minéraux pour doser le phosphore total de l'eau de mer et des boues marines. La méthode est sujette à des variations d'environ 2% pour leau de mer contenant 60 g de phosphore par litre.相似文献
103.
Commodari F Sclavos G Ibrahimi S Khiat A Boulanger Y 《Magnetic resonance in chemistry : MRC》2005,43(6):444-450
The NMR-derived structure of estrogen (17beta-estradiol, E2), the drug of choice for postmenopausal women, was compared with a recent literature crystal x-ray structure of Fab-bound E2. 1H and 13C NMR spectra of E2 were acquired in DMSO-d6. Assignments were obtained from an analysis of DQF-COSY, TOCSY, HETCOR, HMQC and HMBC 2D NMR spectra. The 1H and 13C NMR assignments are the first reported for E2 in DMSO-d6. Two solution structures, S1 and S2, were obtained with molecular modeling using NOE constraints. S1 overlaps with the crystal structure for all rings. S2 shows prominent differences in the C-ring (C9--C11--C12--C13) segment, which deviates from a chair conformation, and excellent overlap in the A-, B- and D-rings of E2. The C-ring in S2 adopts a boat conformation as opposed to a chair conformation in the x-ray and S1 structures. The S2 structure is about 6 degrees more twisted than the bound x-ray and S1 models. The S1, S2 and x-ray structures had ring bowing values of 10.1 +/- 0.3, 11 +/- 1 and 10.37 degrees , respectively. Of the 100 solution conformers generated, 83 had S1 conformation and 17 had S2 conformation, with average internal energies of 112 +/- 2 and 141 +/- 2 kcal mol(-1), respectively. The 100 S1- and S2- derived conformers showed a r.m.s.d. of 0.72 A for all atoms. The x-ray, S1 and S2 C18--O17 distances were 2.93, 2.92 +/- 0.01 and 2.93 +/- 0.01 A, respectively, and the O3--O17 distances were 11.06, 11.18 +/- 0.12, and 10.89 +/- 0.05 A, respectively. 相似文献
104.
Micellar electrokinetic capillary chromatography (MECC) involves the application of a high voltage (10 to 40 kV) across a capillary column (25 to 75 microns i.d.) that is filled with a solution containing micelles. The mobile phase in this work consists of sodium dodecyl sulfate in an aqueous phosphate/borate buffer system. Pyridoxine (vitamin B6) and five of its metabolites are separated, with efficiencies as high as 60,000 theoretical plates/meter. Pyridoxic acid, a metabolite of B6, is separated and quantitated in human urine using laser-excited fluorescence detection. Limits of detection are less than a picogram injected. 相似文献
105.
Henry DJ Yiapanis G Evans E Yarovsky I 《The journal of physical chemistry. B》2005,109(36):17224-17231
This study examines the adhesion of graphite to functionalized polyester surfaces using a range of qualitative and quantitative measures of theoretical adhesion. Modifications to the polyester surfaces include the addition of hydroxyl, carboxyl, or fluorine substituents with coverages of 0.4 and 0.9 groups per nm(2). In each case, the introduction of substituents to the surface of the polyester was calculated to lead to reduced adhesion to graphite. Effects of surface relaxation on adhesion are studied by employing different simulation protocols. The theoretical results suggest one mechanism to reduce adhesion to carbonaceous solids is to increase atomic roughness using strongly hydrophilic or alternatively strongly hydrophobic substituents. 相似文献
106.
Love JC Urbach AR Prentiss MG Whitesides GM 《Journal of the American Chemical Society》2003,125(42):12696-12697
Metallic rods with submicron diameters that contain disklike ferromagnetic sections self-assemble into highly stable, hexagonally close-packed arrays of rods. The rods were fabricated by electrodeposition in porous alumina membranes and comprised alternating sections of gold and nickel. The thicknesses of the ferromagnetic nickel sections were approximately one-half the diameter of the rods (400 nm); this geometry orients the "easy" axis of magnetization perpendicular to the long axis of the rod. After magnetization of the rods with a rare-earth magnet, followed by sonication of the suspension, the rods spontaneously assembled into three-dimensional (3D) bundles that, on average, contained 15-30 rods. A macroscopic model of the rods suggests that the most stable orientation of the magnetic dipoles for rods in a defect-free, hexagonally close-packed arrangement is in concentric rings with the dipoles oriented head-to-tail. This configuration minimizes the energy of the bundle and does not generate a net dipole for the structure. This work provides a simple demonstration that magnetic interactions between ferromagnetic objects can direct and stabilize the formation of ordered, 3D structures by self-assembly. 相似文献
107.
Akira Matsumoto Hisako Mano Masayoshi Oiwa George B. Butler 《Journal of polymer science. Part A, Polymer chemistry》1989,27(6):1811-1816
The radical polymerization of tetraallyl ammonium chloride (TAAC) was carried out in water using azo-initiator as compared to that of diallyl dimethyl ammonium chloride (DADMAC); the rate of polymerization was quite low for TAAC, around one-third of DADMAC. Kinetic discussion revealed the importance of degradative chain transfer in the polymerization of TAAC. The cyclopolymerizability of TAAC was estimated kinetically as the ability of 5-membered monocyclic radical to form a bicyclic ring, giving the cyclization constant of 21 mol/L at [M] = 2 mol/L. Gelation occurred at around 20% conversion. 相似文献
108.
The o-, m-, and p-phenylene bis(1,3-dioxolanium) dications (4-6) and 2,4,6-triphenylene tris(1,3-dioxolanium) trication (7) have been prepared by the ionization of the corresponding 2-methoxyethyl benzoates in FSO(3)H or CF(3)SO(3)H at 40 and 60 degrees C, respectively. The charge delocalization in these carbocations was probed by (13)C NMR chemical shifts and substantiated by GIAO/DFT calculations. Relatively less charge is delocalized into the aromatic ring of the carbotrication 7. The rotational barrier around the C(+)-Ar bond for carbodications 4 and 5 was also estimated to be 8-10 kcal/mol. 相似文献
109.
K. Adibi M. H. George J. A. Barrie 《Journal of polymer science. Part A, Polymer chemistry》1981,19(1):57-64
A relatively high-molecular-weight polyurethane based on MDI and ethylene glycol was prepared and characterized. This polymer was metalated with sodium hydride in N,N-dimethylformamide (DMF) at about 0°C. Metalation was confirmed principally by spectroscopic identification of the N-methyl derivative obtained by coupling the metalated polymer with methyl iodide. Under appropriate reaction conditions the metalated polyurethane was used for the anionic graft polymerization of the reactive monomers acrylonitrile and ethylene and propylene sulfides. Attempted anionic graft polymerizations with other monomers, including styrene and ethylene and propylene oxides, were unsuccessful. The polyurethane grafted with acrylonitrile was separated by fractionation from accompanying small amounts of polyacrylonitrile, a low-molecular-weight homopolymer. One sample of polyurethane grafted with acrylonitrile was identified by microanalysis, IR, NMR, and increase in weight and was also characterized by differential thermal analysis. 相似文献
110.
1,1-Difluoroethysilanes (R3SiCF2CH3, R = Me or Et) were synthesized from 1,1-difluoroethyl phenyl sulfone and chlorosilanes using magnesium metal via reductive 1,1-difluoroethylation. It was confirmed that 1,1-difluoroethylsilanes were effective 1,1-difluoroethylating reagents for carbonyl compounds. 相似文献