全文获取类型
收费全文 | 6902篇 |
免费 | 282篇 |
国内免费 | 63篇 |
专业分类
化学 | 4757篇 |
晶体学 | 67篇 |
力学 | 265篇 |
综合类 | 2篇 |
数学 | 728篇 |
物理学 | 1428篇 |
出版年
2024年 | 44篇 |
2023年 | 93篇 |
2022年 | 515篇 |
2021年 | 440篇 |
2020年 | 293篇 |
2019年 | 271篇 |
2018年 | 277篇 |
2017年 | 227篇 |
2016年 | 324篇 |
2015年 | 254篇 |
2014年 | 283篇 |
2013年 | 510篇 |
2012年 | 425篇 |
2011年 | 480篇 |
2010年 | 278篇 |
2009年 | 250篇 |
2008年 | 265篇 |
2007年 | 272篇 |
2006年 | 196篇 |
2005年 | 187篇 |
2004年 | 114篇 |
2003年 | 125篇 |
2002年 | 122篇 |
2001年 | 89篇 |
2000年 | 63篇 |
1999年 | 65篇 |
1998年 | 34篇 |
1997年 | 31篇 |
1996年 | 51篇 |
1995年 | 47篇 |
1994年 | 29篇 |
1993年 | 37篇 |
1992年 | 37篇 |
1991年 | 43篇 |
1990年 | 21篇 |
1989年 | 26篇 |
1988年 | 33篇 |
1987年 | 30篇 |
1986年 | 29篇 |
1985年 | 42篇 |
1984年 | 25篇 |
1983年 | 25篇 |
1982年 | 24篇 |
1981年 | 14篇 |
1980年 | 29篇 |
1979年 | 23篇 |
1978年 | 28篇 |
1977年 | 28篇 |
1976年 | 21篇 |
1973年 | 12篇 |
排序方式: 共有7247条查询结果,搜索用时 15 毫秒
81.
M. Mohammad A. Y. Khan M. S. Subhani N. Bibi Safeer Ahmad Saba Saleemi 《Research on Chemical Intermediates》2001,27(3):259-267
Rate constants for the reaction of superoxide O-
2 with various substrates were obtained through stationary electrode polarography theory and technique. In solvent acetonitrile, the substrate and the rate constants of the reaction O-
2 + AH-
k2Product, are, AH = isopropanol (k2 < 0.01 M-1 s-1); ethanol (k2 = 1.42 × 102 M-1 s-1); methanol (k2 = 1.1 × 107 M-1 s-1), H2O (k2 = 1.0 × 105 M-1 s-1). In MeCN, O-2 was found to be rather unreactive towards glucose and acetone but it reacts with fructose and sucrose catalytically. However, in DMF2, O-
2reacts with glucose and fructose with k2 order of 105 M-1 s-1. The mechanism of the reaction of O-
2 with the substrates (AH) is proposed as O-
3 + AH k2O, AHk2
k-1 k [O2H + AH]-, k-2O2H + A- with k1 = 109 M-1 s-1 and k-1 = 108 -109 s-1. With these values of k-1 and k1, k k2(obs). The reversible E1/2 for O2 + e O-
2 in various solvents: MeCN, acetone, isopropanol, methanol, H2O were obtained either directly from the reversible voltammogram or from experimental voltammograms and the rate constants obtained (as above) using stationary electrode polargraphy theory; E1/2 being -0.82 (MeCN),-0.85 (acetone),-0.72 (isopropanol);-0.66 (MeOH),-0.56 (H2O) vs SCE. 相似文献
82.
A highly atom-efficient synthetic protocol for hydroarylation of terminal-aryl alkynes and styrene through the regioselective CC bond formation via the electrophilic addition of naphthols and substituted phenols has been developed using alumina-sulfuric acid as a heterogeneous supported solid acid catalyst. This methodology shows excellent regioselectivity and affords the desired product in good to excellent yield. The heterogeneous catalyst can also be recycled efficiently without much loss of activity. 相似文献
83.
Rudolf F. X. Bauer Ikhlas A. Khan Hermann Lotter Hildebert Wagner Victor Wray 《Helvetica chimica acta》1985,68(8):2355-2358
The structure elucidation of four new constituents from the roots of Echinacea purpurea is described. They are shown to be cinnamoyl esters of sesquiterpene alcohols with a germacrane or a guaiane skeleton. First pharmacological results indicate immunological activities. 相似文献
84.
The sorptive potential of sunflower stem (180-300 μm) for Cr(III) ions has been investigated in detail. The maximum sorption (≥85%) of Cr(III) ions (70.2 μM) has been accomplished using 30 mg of high density sunflower stem in 10 min from 0.001 M nitric and 0.0001 M hydrochloric acid solutions. The accumulation of Cr(III) ions on the sorbent follows Dubinin-Radushkevich (D-R), Freundlich and Langmuir isotherms. The isotherm yields D-R saturation capacity Xm = 1.60 ± 0.23 mmol g−1, β = −0.00654 ± 0.00017 kJ2 mol−2, mean free energy E = 8.74 ± 0.12 kJ mol−1, Freundlich sorption capacity KF = 0.24 ± 0.11 mol g−1, 1/n = 0.90 ± 0.04 and of Langmuir constant KL = 6800 ± 600 dm3 mol−1 and Cm = 120 ± 18 μmol g−1. The variation of sorption with temperature (283-323 K) gives ΔH = −23.3 ± 0.8 kJ mol−1, ΔS = −64.0 ± 2.7 J mol−1 K−1 and ΔG298k = −4.04 ± 0.09 kJ mol−1. The negative enthalpy and free energy envisage exothermic and spontaneous nature of sorption, respectively. Bisulphate, Fe(III), molybdate, citrate, Fe(II), Y(III) suppress the sorption significantly. The selectivity studies indicate that Cr(III), Eu(III) and Tb(III) ions can be separated from Tc(VII) and I(I). Sunflower stem can be used for the preconcentration and removal of Cr(III) ions from aqueous medium. This cheaper and novel sorbent has potential applications in analytical and environmental chemistry, in water decontamination, industrial waste treatment and in pollution abatement. A possible mechanism of biosorption of Cr(III) ions onto the sunflower stem has been proposed. 相似文献
85.
Muhammad Ashram 《Journal of inclusion phenomena and macrocyclic chemistry》2007,59(3-4):315-321
Two novel chromogenic cone calix[4]dibenzothiacrown ethers 3 and 4 in which nitrophenylazo groups attached at the phenyl ring of dibenzothiacrown unit were described. The extraction properties
of 3 and 4 toward different transition metal ions have been studied using conductometric technique and found to exhibit Cu2+ and Hg2+ selectivity with very high stability constants range from log K
assoc
= 5.19 to log K
assoc
= 8.72. 相似文献
86.
Bedir E Calis I Piacente S Pizza C Khan IA 《Chemical & pharmaceutical bulletin》2000,48(12):1994-1995
A new flavonol glycoside, isorhamnetin 3-O-beta-D-apiofuranosyl-(1-->2)-alpha-L-rhamnopyranosyl-(1-->6)]-beta-D-galactopyranoside, and the known diglycoside, isorhamnetin 3-O-alpha-L-rhamnopyranosyl-(1-->6)-beta-D-galactopyranoside were isolated from the aerial parts of Astragalus vulneraria. Characterization of the two compounds was done by spectroscopic methods (1D and 2D NMR, and FAB-MS). 相似文献
87.
Theoretical elucidation of kinetic and thermodynamic control of radical addition regioselectivity 总被引:1,自引:0,他引:1
Leach AG Wang R Wohlhieter GE Khan SI Jung ME Houk KN 《Journal of the American Chemical Society》2003,125(14):4271-4278
The cyclizations of two structurally similar 2-oxo-5-hexenyl-type radicals have been investigated by ab initio and density functional (UB3LYP/6-31+G**//UHF/6-31G* and UB3LYP/6-31G*//UB3LYP/6-31G*) calculations. The origin of apparently contradictory reports of 6-endo and 5-exo cyclizations is determined. Kinetic control favors 6-endo cyclization, while thermodynamic control gives 5-exo cyclization, and the observation of different products from different research groups arises from the difference in experimental conditions used by the two groups. The outcome of a new cyclization reaction was predicted by using these theoretical techniques. Kinetic control is predicted to yield exclusively the products of 6-endo cyclization, while thermodynamic control would lead to an approximately equal mixture of one 6-endo and one 5-exo cyclized product. Experimental studies revealed that the reaction yields only the products of 6-endo cyclization through kinetic control. 相似文献
88.
The carbamoyl methyl sulfoxide compounds of uranyl bis(β-diketonate) of the types [UO2(DBM)2CMSO] and [{UO2(DBM)2}2CMSO] (where HDBM = C6H5COCH2COC6H5; CMSO = C6H5CH2SOCH2CONHC6H5 or C6H5SOCH2CONiPr2) have been synthesized and characterized by IR and NMR spectroscopic techniques and elemental analysis. Spectral studies show that CMSO acts as a monodentate ligand in [UO2(DBM)2CMSO] compounds and bonds through the sulfoxo oxygen atom to the uranyl group. It acts as a bridging bidentate ligand in [{UO2(DBM)2}2CMSO] compounds and bonds through both the sulfoxo and carbamoyl oxygen atoms to two different uranyl groups. The structure of the compound [{UO2(DBM)2}2C6H5CH2SOCH2CONHC6H5] confirms the bridging bidentate mode of coordination for the CMSO ligand. Extraction studies show an enhancement in solvent extraction for the uranyl ion from nitric acid medium when a mixture of thenoyl trifluoroacetone (HTTA) and CMSO was employed. 相似文献
89.
90.
Mehmood A Malik A Anis I Khan PM Riaz M Makhmoor T Choudhary MI 《Natural product letters》2002,16(6):371-376
Two new oleanane triterpenes; 2alpha,3alpha,24-trihydroxyolean-12-ene-28,30-dioic acid ([structure: see text]) and 2alpha,3alpha,24,28-tetrahydroxyolean-12-ene ([structure: see text]) have been isolated from the roots of Atropa acuminata. Anti-oxidant p-hydroxyphenethyl trans-ferulate ([structure: see text]), beta-sitosterol-3-O-beta-D-glucopyranoside ([structure: see text]) and oleanolic acid ([structure: see text]) have also been reported for the first time from this species. The structures were determined by spectroscopic studies including 2D-NMR. 相似文献