全文获取类型
收费全文 | 2547篇 |
免费 | 88篇 |
国内免费 | 40篇 |
专业分类
化学 | 1061篇 |
晶体学 | 12篇 |
力学 | 86篇 |
数学 | 724篇 |
物理学 | 354篇 |
无线电 | 438篇 |
出版年
2023年 | 29篇 |
2022年 | 64篇 |
2021年 | 91篇 |
2020年 | 100篇 |
2019年 | 103篇 |
2018年 | 116篇 |
2017年 | 86篇 |
2016年 | 146篇 |
2015年 | 65篇 |
2014年 | 109篇 |
2013年 | 180篇 |
2012年 | 150篇 |
2011年 | 121篇 |
2010年 | 98篇 |
2009年 | 73篇 |
2008年 | 128篇 |
2007年 | 124篇 |
2006年 | 91篇 |
2005年 | 81篇 |
2004年 | 77篇 |
2003年 | 51篇 |
2002年 | 55篇 |
2001年 | 30篇 |
2000年 | 34篇 |
1999年 | 30篇 |
1998年 | 21篇 |
1997年 | 24篇 |
1996年 | 26篇 |
1995年 | 24篇 |
1994年 | 26篇 |
1993年 | 16篇 |
1992年 | 20篇 |
1991年 | 24篇 |
1990年 | 22篇 |
1989年 | 12篇 |
1988年 | 14篇 |
1987年 | 12篇 |
1985年 | 29篇 |
1984年 | 14篇 |
1983年 | 7篇 |
1982年 | 15篇 |
1981年 | 12篇 |
1980年 | 9篇 |
1979年 | 14篇 |
1978年 | 12篇 |
1977年 | 17篇 |
1976年 | 13篇 |
1975年 | 13篇 |
1974年 | 11篇 |
1973年 | 9篇 |
排序方式: 共有2675条查询结果,搜索用时 15 毫秒
71.
In the copolymerization of vinyl acetate (A) with either vinyl chloride (C) or vinylidene chloride (V), an internal transfer (backbiting) reaction—of the C- or V-ended radi-cals on an antepenultimate A unit—is proposed to be responsible for the deviation of the copolymerization kinetics from the Lewis and Mayo theory. The deviations disappear if A is replaced by isopropenylacetate [Ip], Then one gets, for the Ip -C copolymerization. rI p =0.35 and :rc=2.4, and for I -V copolymerization, rI p=0.13 and rv=5.9. The internal transfer reaction causes the formation of branches which may be evidenced by NMR analysis of constant composition suspension A-C copolymers. A kinetic scheme is proposed and the corresponding reactivity ratios derived rA=0.29, rc=1.60, r=0.3 (radical resulting from the transfer reaction), and kT=1500 (rate constant of the transfer reaction at 50°C). The distribution of branches is calculated together with the sequence distribution functions for the .A. or Cunits. 相似文献
72.
α-n-amylcinnamaldehyde (jasminaldehyde) was obtained with 82 % yield by solid-liquid phase transfer catalysis without solvent within 3 days at room temperature. By use of domestic microwave irradiation, the same yield was obtained within 1 minute at a power of 600 W. 相似文献
73.
Regioselective hydrolysis of cocaine led, according to the reaction conditions, either to benzoylecgonine or to ecgonine methyl ester. Acylation with benzoylecgonine was readily achieved when benzotriazolyloxytrisdimethylamino-phosphonium (BOP) was used as a coupling agent. 相似文献
74.
Reactions of (eta5-C5H(5-x)Brx)M(CO)3(M = Re, Mn; x= 1, 3, 4, 5) and IZn(CH2)2R(f8) in the presence of Cl2PdL2 catalysts give the title complexes (eta5)-C5H(5-x)(CH2)2R(f8)x)M(CO3), accompanied in the case of x= 5 by hydride-transfer byproducts. Extremely high fluorophilicities are realized, and the cyclopentadienyl ligands are readily detached (hnu) from the manganese complexes. 相似文献
75.
Kadish KM Phan TD Giribabu L Shao J Wang LL Thuriere A Van Caemelbecke E Bear JL 《Inorganic chemistry》2004,43(3):1012-1020
Eleven different Ru(2)(4+) and Ru(2)(3+) derivatives are characterized by thin-layer FTIR and UV-visible spectroelectrochemistry under a CO atmosphere. These compounds, which were in-situ electrogenerated from substituted anilinopyridine complexes with a Ru(2)(5+) core, are represented as Ru(2)(L)(4)Cl where L = 2-CH(3)ap, ap, 2-Fap, 2,3-F(2)ap, 2,4-F(2)ap, 2,5-F(2)ap, 3,4-F(2)ap, 3,5-F(2)ap, 2,4,6-F(3)ap, or F(5)ap. The Ru(2)(5+) complexes do not axially bind CO while mono- and bis-CO axial adducts are formed for the Ru(2)(4+) and Ru(2)(3+) derivatives, respectively. Six of the eleven investigated compounds exist in a (4,0) isomeric form while five adopt a (3,1) geometric conformation. These two series of compounds thus provide a large enough number of derivatives to examine trends and differences in the spectroscopic data of the two types of isomers in their lower Ru(2)(4+) and Ru(2)(3+) oxidation states. UV-visible spectra of the Ru(2)(4+) derivatives and IR spectra of the Ru(2)(3+) complexes under CO are both isomer dependent, thus suggesting that these data can be used to reliably predict the isomeric form, i.e., (3,1) or (4,0), of diruthenium complexes containing four unsymmetrical substituted anilinopyridinate bridging ligands; this was confirmed by X-ray crystallographic data for seven compounds whose structures were available. 相似文献
76.
Yihua Li Wenge Yang Tuan Zhang Chaoyuan Wang Kai Wang Yonghong Hu 《Journal of solution chemistry》2013,42(12):2342-2353
Solubility data were measured for omeprazole sulfide in ethanol, 95 mass-% ethanol, ethyl acetate, isopropanol, methanol, acetone, n-butanol and n-propanol in the temperature range from 280.35 to 319.65 K by employing the gravimetric method. The solubilities increase with temperature and they are in good agreement with the calculated solubility of the modified Apelblat equation and the λh equation. The experimental solubility and correlation equation in this work can be used as essential data and model in the purification process of omeprazole sulfide. The thermodynamic properties of the solution process, including the Gibbs energy, enthalpy, and entropy were calculated using the van’t Hoff equation. 相似文献
77.
78.
Nguyen Huu Dinh Hoang Thi Tuyet Lan Tran Thi Thu Trang Pham Van Hoan 《Journal of heterocyclic chemistry》2012,49(4):814-822
A novel hydrazide, 2‐methoxy‐4‐(3‐methyfuroxan‐4‐yl)‐5‐nitrophenoxyacetylhydrazine, was prepared from isoeugenoxyacetic acid. The hydrazide was condensed with aromatic aldehydes to give a series of 20 hydrazide‐hydrazones incorporating the furoxan ring. The structure of obtained compounds was determined by analytical and spectral data. It was demonstrated that the two sets of resonance signals in the 1H‐NMR and 13C‐NMR spectra of the examined hydrazide‐hydrazones are caused by EN–C(O) and ZN–C(O) conformers. The energy barriers for the conformation exchange were determined by 1H‐NMR‐measurement at various temperatures. Among seven tested hydrazide‐hydrazones, four compounds exhibit inhibition activities in vitro on human epidermis carcinoma (KB‐cell) with IC50 = 47, 68, 79, and 103 μg/mL. 相似文献
79.
Pham TN Hinchley SL Rankin DW Liptaj T Uhrín D 《Journal of the American Chemical Society》2004,126(40):13100-13110
We have developed methodology for the determination of solution structures of small molecules from residual dipolar coupling constants measured in dilute liquid crystals. The power of the new technique is demonstrated by the determination of the structure of methyl beta-d-xylopyranoside (I) in solution. An oriented sample of I was prepared using a mixture of C(12)E(5) and hexanol in D(2)O. Thirty residual dipolar coupling constants, ranging from -6.44 to 4.99 Hz, were measured using intensity-based J-modulated NMR techniques. These include 15 D(HH), 4 (1)D(CH), and 11 (n)D(CH) coupling constants. The accuracy of the dipolar coupling constants is estimated to be < +/- 0.02 Hz. New constant-time HMBC NMR experiments were developed for the measurement of (n)D(CH) coupling constants, the use of which was crucial for the successful structure determination of I, as they allowed us to increase the number of fitted parameters. The structure of I was refined using a model in which the directly bonded interatom distances were fixed at their ab initio values, while 16 geometrical and 5 order parameters were optimized. These included 2 CCC and 6 CCH angles, and 2 CCCC and 6 CCCH dihedral angles. Vibrationally averaged dipolar coupling constants were used during the refinement. The refined solution structure of I is very similar to that obtained by ab initio calculations, with 11 bond and dihedral angles differing by 0.8 degrees or less and the remaining 5 parameters differing by up to 3.3 degrees . Comparison with the neutron diffraction structure showed larger differences attributable to crystal packing effects. Reducing the degree of order by using dilute liquid crystalline media in combination with precise measurement of small residual dipolar coupling constants, as shown here, is a way of overcoming the limitation of strongly orienting liquid crystals associated with the complexity of (1)H NMR spectra for molecules with more than 12 protons. 相似文献
80.