全文获取类型
收费全文 | 2201篇 |
免费 | 83篇 |
国内免费 | 8篇 |
专业分类
化学 | 1411篇 |
晶体学 | 58篇 |
力学 | 60篇 |
数学 | 200篇 |
物理学 | 563篇 |
出版年
2023年 | 27篇 |
2022年 | 46篇 |
2021年 | 42篇 |
2020年 | 57篇 |
2019年 | 55篇 |
2018年 | 33篇 |
2017年 | 33篇 |
2016年 | 70篇 |
2015年 | 57篇 |
2014年 | 82篇 |
2013年 | 174篇 |
2012年 | 129篇 |
2011年 | 168篇 |
2010年 | 88篇 |
2009年 | 83篇 |
2008年 | 127篇 |
2007年 | 141篇 |
2006年 | 84篇 |
2005年 | 78篇 |
2004年 | 63篇 |
2003年 | 40篇 |
2002年 | 33篇 |
2001年 | 30篇 |
2000年 | 18篇 |
1999年 | 10篇 |
1998年 | 14篇 |
1997年 | 11篇 |
1996年 | 20篇 |
1995年 | 22篇 |
1994年 | 24篇 |
1993年 | 29篇 |
1992年 | 20篇 |
1991年 | 8篇 |
1990年 | 11篇 |
1989年 | 12篇 |
1988年 | 19篇 |
1987年 | 17篇 |
1986年 | 20篇 |
1985年 | 21篇 |
1984年 | 21篇 |
1983年 | 24篇 |
1982年 | 20篇 |
1981年 | 21篇 |
1980年 | 19篇 |
1979年 | 17篇 |
1978年 | 23篇 |
1977年 | 13篇 |
1976年 | 19篇 |
1974年 | 16篇 |
1973年 | 13篇 |
排序方式: 共有2292条查询结果,搜索用时 328 毫秒
51.
[reaction: see text] In cases where both reactants in a phase-vanishing reaction are less dense than the fluorous phase, an alternative to the U-tube method is to employ a solvent with greater density than the fluorous phase, such as 1,2-dibromoethane. This modification has been successfully applied to the methylation of a phenol derivative with dimethyl sulfate and to the m-CPBA-induced epoxidation of alkenes, N-oxide formation from nitrogen-containing compounds, and S-oxide or sulfone formation from organic sulfides. 相似文献
52.
This work describes the results of the Cd(II) isopropylxanthate-stabilized and Mn(III) isopropylxanthate-sensitized photo-oxidation of poly(2,6-dimethyl-1,4-phenylene oxide) film in air at low temperatures (?10 to 80°). The oxidation was followed by light scattering, potassium ferri-oxalate actinometry and by measuring gel formation. The weight-average molecular weight, degree of degradation, rate of scission of links, energy of activation and quantum yield of the process depend on several factors, e.g. temperature, xanthate concentration. Various oxygen-containing groups (hydroperoxides, carbonyls, etc.) are formed in the polymer. For the determination of the content of these groups, iodometry and spectroscopy were applied. The initially present or photo-induced hydroperoxides are directly responsible for subsequent oxidative reactions which occur during 254-nm irradiation. The absorption spectra of the degraded materials in the u.v. and i.r. regions were also studied to substantiate a possible mechanism of the oxidation process. 相似文献
53.
Chandra S Gupta LK 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,62(4-5):1125-1130
Manganese(II), cobalt(II), nickel(II) and copper(II) complexes have been synthesized with a new tetradentate ligand viz. 1,3,7,9-tetraaza-2,4,8,10-tetraketo-6,12-diphenyl-cyclododecane (L) and characterized by the elemental analysis, molar conductance measurements, magnetic susceptibility measurements, mass, 1H NMR, IR, electronic and EPR spectral studies. The molar conductance measurements of the complexes in DMF correspond to be nonelectrolytic nature for Mn(II), Co(II) and Cu(II) while 1:2 electrolytes for Ni(II) complexes. Thus, these complexes may be formulated as [M(L)X2] and [Ni(L)]X2 (where M = Mn(II), Co(II) and Cu(II) and X = Cl− and NO3−).On the basis of IR, electronic and EPR spectral studies an octahedral geometry has been assigned for Mn(II) and Co(II) complexes, square-planar for Ni(II) whereas tetragonal for Cu(II) complexes. The ligand and its complexes were also evaluated against the growth of bacteria and pathogenic fungi in vitro. 相似文献
54.
Chandra S Gupta LK Sangeetika 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,62(1-3):453-460
The complexation of new mixed thia-aza-oxa macrocycle viz., 2,12-dithio-5,9,14,18-tetraoxo-7,16-dithia-1,3,4,10,11,13-hexaazacyclooctadecane containing thiosemicarba-zone unit with a series of transition metals Co(II), Ni(II) and Cu(II) has been investigated, by different spectroscopic techniques. The structural features of the ligand have been studied by EI-mass, (1)H NMR and IR spectral techniques. Elemental analyses, magnetic moment susceptibility, molar conductance, IR, electronic, and EPR spectral studies characterized the complexes. Electronic absorption and IR spectra of the complexes indicate octahedral geometry for chloro, nitrato, thiocyanato or acetato complexes. The dimeric and neutral nature of the sulphato complexes are confirmed from magnetic susceptibility and low conductance values. Electronic spectra suggests square-planar geometry for all sulphato complexes. The redox behaviour was studied by cyclic voltammetry, show metal-centered reduction processes for all complexes. The complexes of copper show both oxidation and reduction process. The redox potentials depend on the conformation of central atom in the macrocyclic complexes. Newly synthesized macrocyclic ligand and its transition metal complexes show markedly growth inhibitory activity against pathogenic bacterias and plant pathogenic fungi under study. Most of the complexes have higher activity than that of the metal free ligand. 相似文献
55.
Summary The products from the reaction oftrans-dioxobis(ethylenediamine)rhenium(V) halides with hydrogen halides have been investigated. Dilute (2M) and concentrated hydrochloric acid react with (ReO2en2)Cl in the cold to give ReO(OH)enCl2 and IRe(OH)2enCl2]Cl respectively, while with hot 6M HCl [ReOCl5]2– is formed. Dilute solutions of HX protonate [ReO2en2]X (X = Br and I) giving [ReO(OH)en2]X2 which are converted slowly into ReO(OH)enBr2 and [ReO(OH)en2](I3)2. Hot and concentrated solutions of HX reduce Rev in (ReO2en2 )X (X = Br and I) giving enH2(ReBr6) and ReI4en. The thermal decomposition of (ReO2en2)X (X = Cl, Br and I) has been studied by thermogravimetry and a polymeric compound, Re2O7en2, has been isolated by heating (ReO2en2)X at 200°. The compounds have been characterised by molecular conductivities, magnetic susceptibility and i.r. spectra. 相似文献
56.
57.
Evidence is presented which indicates that singlet → triplet intersystem crossing from the charge-transfer singlet state of electron donor-acceptor complexes is efficient only when a locally excited triplet state of a component molecule (donor or acceptor) lies below the charge-transfer singlet state. 相似文献
58.
Tripathi RP Rastogi SK Kundu B Saxena JK Reddy VJ Srivastava S Chandra S Bhaduri AP 《Combinatorial chemistry & high throughput screening》2001,4(3):237-244
A library of 24 glycoconjugates related to glycosylated beta-amino acid derivative (I) was been prepared and screened against DNA topoisomerase-II of the filarial parasite S. cervi. Among these, compound 6 was found to be a potent inhibitor of DNA topoisomerase-II with 95% inhibition at 1.09 microM. Furthermore, compound 6 was at least three times more potent than the lead compound, glycosylated beta-amino acid derivative I. 相似文献
59.
The photo-oxidative degradation and stabilization of poly(2,6-dimethyl-1,4-phenylene oxide) films have been examined in the temperature range 263–313 K in air with u.v. light of 253.7 nm. The changes in weight-average molecular weight, quantum efficiencies, carbonyl index, hydroperoxide concentration and i.r. spectra have been followed in the absence and presence of the stabilizer. The heats of activation of the systems have been calculated and the mechanism of stabilization has been postulated. A saturation limit in photostabilization of the polymer was achieved beyond 0.6 wt% of zinc di-n-hexyl dithiophosphate. 相似文献
60.
Ginotra SK Chhikara BS Singh M Chandra R Tandon V 《Chemical & pharmaceutical bulletin》2004,52(8):989-991
Mild, efficient and eco-friendly oxidation of 17alpha-methylandrostan-3beta-17beta-diol (1) has been studied with three different reagents viz. pentavalent iodine reagent 2-iodoxy benzoic acid (IBX) in DMSO at 65 degrees C, sodium hypochlorite and H2O2/Na2WO4 under phase transfer conditions to give 17beta-hydroxy-17alpha-methylandrostan-3-one (mestanolone 2), a drug intermediate as oxidized product. The H2O2/Na2WO4/PTC gave mestanolone in high yield and purity whereas sodium hypochlorite/PTC system yielded some chlorinated material along with the mestanolone. However, 1 with 2.5 equivalent of IBX gave 17beta-hydroxy-17alpha-methyl-Delta1-androsten-3-one (3) under the similar reaction conditions in good yield and single step reaction. 相似文献