全文获取类型
收费全文 | 3873篇 |
免费 | 142篇 |
国内免费 | 35篇 |
专业分类
化学 | 2704篇 |
晶体学 | 21篇 |
力学 | 194篇 |
数学 | 411篇 |
物理学 | 720篇 |
出版年
2023年 | 31篇 |
2022年 | 117篇 |
2021年 | 150篇 |
2020年 | 137篇 |
2019年 | 145篇 |
2018年 | 144篇 |
2017年 | 120篇 |
2016年 | 187篇 |
2015年 | 132篇 |
2014年 | 180篇 |
2013年 | 387篇 |
2012年 | 263篇 |
2011年 | 266篇 |
2010年 | 207篇 |
2009年 | 171篇 |
2008年 | 182篇 |
2007年 | 151篇 |
2006年 | 127篇 |
2005年 | 81篇 |
2004年 | 93篇 |
2003年 | 87篇 |
2002年 | 66篇 |
2001年 | 37篇 |
2000年 | 40篇 |
1999年 | 35篇 |
1998年 | 25篇 |
1997年 | 19篇 |
1996年 | 32篇 |
1995年 | 16篇 |
1994年 | 24篇 |
1993年 | 23篇 |
1992年 | 26篇 |
1991年 | 25篇 |
1990年 | 17篇 |
1989年 | 23篇 |
1988年 | 29篇 |
1987年 | 15篇 |
1986年 | 13篇 |
1985年 | 27篇 |
1984年 | 15篇 |
1983年 | 10篇 |
1982年 | 18篇 |
1981年 | 19篇 |
1980年 | 21篇 |
1979年 | 10篇 |
1978年 | 13篇 |
1976年 | 10篇 |
1975年 | 10篇 |
1974年 | 15篇 |
1973年 | 15篇 |
排序方式: 共有4050条查询结果,搜索用时 15 毫秒
71.
Ahmed R. Hassan Khadiga F. Amer Sayed A. El-Toumy John Nielsen 《Natural product research》2019,33(8):1135-1139
Isolation of flavonoids from the aerial parts of Taverniera aegyptiaca Bioss. (Fabaceae) led to identification of one new flavonol glycoside, isorhamnetin-3-O-α-l-rhamnopyranosyl-(1→2)-α-l-arabinopyranoside (1), along with eleven compounds, which previously have not been isolated from this plant quercetin-3-O-α-l-rhamnopyranosyl-(1→2)-[α-l-rhamnopyranosyl-(1→6)-β-d-galactopyranoside] (2), isorhamnetin-3-O-α-l-arabinopyranoside (3), quercetin-3-O-α-l-rhamnopyranosyl-(1→6)-β-d-glucopyranoside (4), isorhamnetin-3-O-α-l-rhamnopyranosyl-(1→6)-β-d-glucopyranoside (7), isorhamnetin 3-O-α-l-rhamnopyranosyl-(1→2)-[α-l-rhamnopyranosyl-(1→6)-β-d-galactopyranoside] (8), isorhamnetin 3-O-α-l-rhamnopyranosyl-(1→2)-[α-l-rhamnopyranosyl-(1→6)-β-d-glucopyranoside] (9), kaempferol 3-O-α-l-rhamnopyranosyl-(1→2)-[α-l-rhamnopyranosyl-(1→6)-β-d-galactopyranoside] (10), isorhamnetin (11), 4,4′-dihydroxy-2′-methoxychalcone (12), formononetin (13) and calycosin (15)] and some compounds already known from this plant [quercetin-3-O-robinobioside (5), isorhamnetin-3-O-robinobioside (6), afrormosin (14) and odoratin (16)]. 相似文献
72.
Hassan S. El Khadem Rodger L. Foltz Thomas Novinson Keitaro Senga 《Journal of heterocyclic chemistry》1975,12(6):1255-1263
High resolution electron impact mass spectrometric measurements have been made on twelve pyrazolo[1,5-a]-1,3,5-triazines. Substituents attached to carbon atoms 2, 4, 7, and 8 were used to label the various fragments. Three major ions were observed (a) the molecular ion, (b) an ion corresponding to M-RCN where R is the substituent attached to C-4 and (c) an aryl cyclopropenyl cation which was observed in 7-aryl derivatives. Intensities and accurate mass-measurements are given for all ions having intensities exceeding 2% of the base peak. Nine of the twelve pyrazolo-[1,5-a]-1,3,5-triazines included in this study are described here for the first time. 相似文献
73.
A mutant strain ofPichia stipitis, FPL-061, was obtained by selecting for growth on L-xylose in the presence of respiratory inhibitors. The specific fermentation
rate of FPL-061, was higher than that of the parent,Pichia stipitis CBS 6054, because of its lower cell yield and growth rate and higher specific substrate uptake rate. With a mixture of glucose
and xylose, the mutant strain FPL-061 produced 29.4 g ethanol/L with a yield of 0.42 g ethanol/g sugar consumed. By comparison,
CBS 6054 produced 25.7 g ethanol/L with a yield of 0.35 gJg. The fermentation was most efficient at an aeration rate of 9.2
mmoles O2 L-1 h-1. At high aeration rates (22 mmoles O2 L-1 h-1), the mutant cell yield was less than that of the parent. At low aeration rates, (1.1 to 2.5 O2 L-1 h-1), cell yields were similar, the ethanol formation rates were low, and xylitol accumulation was observed in both the strains.
Both strains respired the ethanol once sugar was exhausted. We infer from the results that the mutant, P.stipitis FPL-061, diverts a larger fraction of its metabolic energy from cell growth into ethanol production. 相似文献
74.
Mantel C Hassan AK Pécaut J Deronzier A Collomb MN Duboc-Toia C 《Journal of the American Chemical Society》2003,125(40):12337-12344
The isolation, structural characterization and electronic properties of three new six-coordinated Mn(III) complexes, [Mn(bpea)(F)(3)] (1), [Mn(bpea)(N(3))(3)] (2), and [Mn(terpy)(F)(3)] (3) are reported (bpea = N,N-bis(2-pyridylmethyl)-ethylamine; terpy = 2,2':6',2' '-terpyridine). As for [Mn(terpy)(N(3))(3)] (4) (previously described by Limburg J.; Vrettos J. S.; Crabtree R. H.; Brudvig G. W.; de Paula J. C.; Hassan A.; Barra A-L.; Duboc-Toia C.; Collomb M-N. Inorg. Chem. 2001, 40, 1698), all these complexes exhibit a Jahn-Teller distortion of the octahedron characteristic of high-spin Mn(III) (S = 2). The analysis of the crystallographic data shows an elongation along the tetragonal axis of the octahedron for complexes 1 and 3, while complex 2 presents an unexpected compression. The electronic properties were investigated using a high-field and high-frequency EPR study performed between 5 and 15 K (190-575 GHz). The spin Hamiltonian parameters determined in solid state are in agreement with the geometry of the complexes observed in the crystal structures. A negative D value found for 1 and 3 is related to the elongated tetragonal distortion, whereas the positive D value determined for 2 is in accordance with a compressed octahedron. The high E/D values, in the range of 0.103 to 0.230 for all complexes, are correlated with the highly distorted geometry present around the Mn(III) ion. HF-EPR experiments were also performed on complex 1 in solution and show that the D value is the only spin Hamiltonian parameter which is slightly modified compared to the solid state (D = -3.67 cm(-1) in solid state; D = -3.95 cm(-1) in solution). 相似文献
75.
Anvarhusein A. Isab Abdul R. Al-Arfaj Mohammed Arab Mir M. Hassan 《Transition Metal Chemistry》1994,19(1):87-90
Summary Pd(CN)2 reacts with imidazolidine-2-thione (Imt), 1,3-diazinane-2-thione(Diaz), 1,3-diazipnane-2-thione (Diap) and their derivatives to yield complexes of stoichiometry [PdL2(CN)2] or [PdL(CN)2] (L = Imt, Diaz or Diap and L = Imt having N-Me, Et or Pr substituents), which were characterized by elemental analysis, i.r., 1H and 13C n.m.r. spectroscopy. Both mono- and bis ligand complexes are thought to be square planar with the monoligand binding to metal via sulphur (bridging) and the bis ligand via the monodentate thione group. The 13C enriched Pd(13CN)2 complex was prepared and the 13C n.m.r. recorded. The C-2 resonance of 13C n.m.r. of Imt, Diaz or Diap complexes of the copper(I), silver(I), gold(I) and palladium(II) were compared. 相似文献
76.
Summary New complexes of chromium(III), manganese(II) and nickel(II) with methylhydrazinecarboxylate (MeCz) and of manganese(II) and
nickel(II) with 1,1-dimethylhydra-zinecarboxylate (Me2Cz) were prepared by reacting salts of the metals with CO2-saturated solutions of the hydrazines in EtOH. The compounds [Cr(MeCz)3]·2H2O, Ni(MeCz)2(H2O)3·MMH, Mn(MeCz)2(H2O)2(MMH = monomethylhydrazine) and M(Me2Cz)2(H2O)2 (M = Mn or Ni) were investigated using d.t.a., t.g.a., electronic and i.r. spectroscopy and by magnetic susceptibility measurements. 相似文献
77.
78.
Hassan Sheibani 《Tetrahedron》2004,60(28):5931-5934
2-Pyrone derivatives were prepared in a one step procedure from readily available (chlorocarbonyl)phenyl ketene and 1,3-diketones such as 2,4-pentanedione, 1,3-diphenyl-1,3-propanedione, 1-phenyl-1,3-butanedione, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, 1,3-dimethyl-pyrimidine-2,4,6-trione and ethyl 2,4-dioxopentanoate. A mechanism is presented to account for the formation of the products. This method provides an easy route to prepare 3,4,5,6-tetrasubstituted 2-pyrones in good to excellent yields and in a short experimental time. 相似文献
79.
A novel chelating polymeric material was synthesized by chemical anchoring of N,N′-dimethyl-N,N′-dibutyl malonamide (DMDBMA) with chloromethylated polystyrene-divinyl benzene polymer. The polymeric material thus prepared was characterized by 13C NMR, FT-IR spectroscopy and CHN elemental analysis. The fabricated polymeric material exhibited superior binding for hexa-valent and tetra-valent metal ions such as U(VI) and Th(IV). Various physico-chemical properties of the functionalized polymer like phase adsorption kinetics, metal sorption mechanism and metal sorption capacity was studied in the static method. Adsorption kinetics studies show that <20 min was sufficient for >99.99% adsorption of Th(IV) and U(VI). The kinetics for adsorption of U(VI) and Th(IV) was found to follow the first order Lagergren rate kinetics. Adsorption of U(VI) on the malonamide functionalized polymer followed the Langmuir adsorption isotherm. The Langmuir monolayer adsorption phenomenon was also confirmed by the theoretical approach calculated based on the adsorption kinetics. The metal sorption capacities for uranium and thorium were found to be 18.78 ± 1.53 mg and 15.74 ± 1.59 mg/g of the chelating polymer at 3 M HNO3, respectively. 相似文献
80.
M. S. K. Youssef Kh. M. Hassan F. M. Atta M. S. Abbady 《Journal of heterocyclic chemistry》1984,21(5):1565-1568
3-Hydrazino-7-methyl-5-phenyl-5H-pyrazolo[3,4-c]-as-triazine 1 underwent ring closure and/or condensation reaction with formic acid, acetic acid, acetic anhydride and benzoyl chloride to afford 1H-pyrazolo-[3,4-d]-s-triazolo[3,4-c]-as-triazines 2, 5 and 7a and/or N-acyl derivatives 3, 4 and 6 . N-Acyl derivatives 3 and 6 underwent cyclisation reaction on treatment with phosphoryl chloride to give 5 and 7a . 3-Methyl-1-phenyl-8-aryl-1H-pyrazolo[3,4-e]-s-triazolo[34,-c]-as-triazines 7 were also prepared by the reaction of the hydrazono derivatives 8 wit thionyl chloride. On treatment of 1 with nitrous acid gave the 8H-pyrazolo[3,4-e]tetrazolo-[5,1-c]-as-triazine 9 . Compound 1 underwent ring closure with carbon disulphide or ethyl chloroformate to 1,7-dihydro-8H-pyrazolo[3,4-e]-s-triazolo[3,4-c]-as-triazine derivatives 10 and 12 . Reaction of 1 with ethyl acetoacetate or acetylacetone gave 3-pyrazolo derivatives 13 and 14 . 相似文献