全文获取类型
收费全文 | 6616篇 |
免费 | 316篇 |
国内免费 | 63篇 |
专业分类
化学 | 4521篇 |
晶体学 | 67篇 |
力学 | 265篇 |
综合类 | 2篇 |
数学 | 728篇 |
物理学 | 1412篇 |
出版年
2024年 | 37篇 |
2023年 | 82篇 |
2022年 | 284篇 |
2021年 | 438篇 |
2020年 | 293篇 |
2019年 | 271篇 |
2018年 | 277篇 |
2017年 | 227篇 |
2016年 | 323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6995条查询结果,搜索用时 46 毫秒
141.
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
142.
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
143.
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
144.
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
145.
ViqarUddin Ahmad MuhammadAthar Abbasi Muhammad Zubair Naheed Fatima Umar Farooq M.Iqbal Choudhary 《Helvetica chimica acta》2004,87(1):67-72
Phytochemical investigation of Symplocos racemosa resulted in the isolation of two new glycosides, symploracemoside ( 1 ) and symplomoside ( 2 ), which are structurally related to the reported benzoylsalireposide ( 3 ) and salireposide ( 4 ). The structure elucidation of the isolated compounds was based primarily on 1D‐ and 2D‐NMR analysis, including COSY, NOESY, HMQC, and HMBC correlations. These glycosides showed inhibitory activity against snake‐venom phosphodiesterase I. 相似文献
146.
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
147.
A novel kinetic method for the determination of trace amounts of Co(II) has been developed. The proposed method based on the catalytic effect of Co(II) on the oxidation of xylenol orange tetra sodium salt by H2O2 in the presence of cationic surfactant (N‐dodecylpyridinium chloride). Co(II) at μg.mL?1 was determined spectrophotometrically by measuring the decrease in the absorbance of xylenol orange at 577 nm by the differential method. The method is precise, selective, and sensitive. The detection limit of the procedure was 0.058 μg.mL?1. The relative standard deviation for the replicate determination (n = 6) of 0.7 μg.mL?1 was 1.285%. The results compared satisfactorily with those of atomic absorption spectrometry. The method was successful for the analysis of Co(II) in veterinary and synthetic samples. 相似文献
148.
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
149.
S. B. Halligudi M. M. Taqui Khan B. L. Moroz A. L. Chuvilin I. P. Prosvirin V. A. Likholobov 《Reaction Kinetics and Catalysis Letters》1991,44(1):139-146
Ru/SiO2 catalysts prepared by reduction of supported RuCl3·xH2O are active in gas-phase hydroformylation of propylene at low pressure (ca. 0.3 MPa) of H2+CO+C3H6 mixtured and show unexpectedly high selectivity towards unbranched oxo-products. Data concerning the effect of electronic state and dispersity of Ru on their catalytic behavior have been obtained.
Ru/SiO2, RuCl3·xH2O, (0,3 ) - . .相似文献
150.
M. Rafi K. Ahmed I. A. Khan M. R. Husain 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1991,18(4):379-382
The ultraviolet spectra of Na2 and K2 molecules have been investigated. These studies were made in absorption in the second order of a 3.4 m Ebert Spectrograph with a reciprocal dispersion of 2.6 Å/mm. A number of new bands in the spectra of both the molecules not previously reported have been observed. Computer methods have been used to calculate the term values and to evaluate molecular constants. 相似文献