全文获取类型
收费全文 | 1225篇 |
免费 | 76篇 |
国内免费 | 305篇 |
专业分类
化学 | 1464篇 |
晶体学 | 9篇 |
力学 | 3篇 |
综合类 | 8篇 |
物理学 | 122篇 |
出版年
2024年 | 1篇 |
2023年 | 10篇 |
2022年 | 22篇 |
2021年 | 25篇 |
2020年 | 35篇 |
2019年 | 22篇 |
2018年 | 23篇 |
2017年 | 35篇 |
2016年 | 44篇 |
2015年 | 40篇 |
2014年 | 46篇 |
2013年 | 122篇 |
2012年 | 86篇 |
2011年 | 91篇 |
2010年 | 75篇 |
2009年 | 71篇 |
2008年 | 83篇 |
2007年 | 94篇 |
2006年 | 94篇 |
2005年 | 76篇 |
2004年 | 78篇 |
2003年 | 70篇 |
2002年 | 48篇 |
2001年 | 36篇 |
2000年 | 46篇 |
1999年 | 34篇 |
1998年 | 27篇 |
1997年 | 25篇 |
1996年 | 28篇 |
1995年 | 20篇 |
1994年 | 15篇 |
1993年 | 20篇 |
1992年 | 8篇 |
1991年 | 9篇 |
1990年 | 6篇 |
1989年 | 5篇 |
1988年 | 7篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1985年 | 3篇 |
1983年 | 1篇 |
1982年 | 4篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1979年 | 5篇 |
1978年 | 6篇 |
1977年 | 4篇 |
1976年 | 1篇 |
排序方式: 共有1606条查询结果,搜索用时 15 毫秒
41.
Vnira R. Akhmetova Guzel R. Nadyrgulova Tat'yana V. Tyumkina Mikhail Yu. Antipin Usein M. Dzhemilev 《Tetrahedron》2007,63(47):11702-11709
Cyclocondensation of aliphatic diamines with CH2O and H2S (1:3:2 ratio, 0 °C) was carried out to give thiadiazabicyclanes and dithiadiazabicyclanes (1:6:4 ratio), which were previously difficult to synthesize. Symmetric α,ω-bis-1,3,5-dithiazinanes were synthesized at 80 °C by this reaction. The stereochemistry of thiadiazabicyclanes was assigned by 1H and 13C NMR spectroscopy and by theoretical DFT calculations, and of bis-dithiazinanes by X-ray diffraction study in the solid state. 相似文献
42.
催化光度法测定痕量甲醛 总被引:24,自引:2,他引:24
基于磷酸介质中甲醛催化溴酸钾氧化溴甲酚紫的褪色反应 ,建立了测定痕量甲醛的方法。方法的检出限为 1.0× 10 - 5g·L- 1,线性范围为 0 .0 2 0~ 0 .4 8μg·ml- 1,方法简便 ,用于空气中测定痕量甲醛 ,结果满意。 相似文献
43.
Ion/molecule reactions were explored in a newly developed miniature mass spectrometer fitted with a rectilinear ion trap (RIT) mass analyzer. The tandem mass spectrometry performance of this instrument is demonstrated using collision induced dissociation (CID) and ion/molecule reactions. The latter includes Eberlin transacetalization reactions and electrophilic additions. Selective detection of the chemical warfare simulant dimethyl methyl phosphonate (DMMP) was achieved through selective Eberlin reactions of its characteristic phosphonium fragment ion CH3OP(+)(O)CH3 (m/z 93), with 1,4-dioxane or 1,3-dioxolane. Efficient adduct formation as a result of electrophilic attack by the phosphonium ion on various nucleophilic reagents, including 1,1,3,3-tetramethyl urea, methanesulfonic acid methyl ester, dimethyl sulfoxide and methyl salicylate, was also observed using the RIT device. The product ions of these reactions were analyzed using CID and the characteristic fragmentation patterns of the ionic addition products were recorded using multiple-stage experiments in the miniature RIT instrument. This study clearly demonstrates that a small, home-built, miniature RIT mass spectrometer can be used to perform analytically useful ion/molecule reactions and also that instruments like this have the potential to provide a portable platform for in situ detection of organophosphorus esters and related compounds with high specificity using tandem mass spectrometry. 相似文献
44.
Dimitrios V. Stergiou Spyros C. Karkabounas Panayotis G. Veltsistas Nicholaos P. Evmiridis Athanasios G. Vlessidis 《Mikrochimica acta》2007,158(1-2):59-64
A kinetic-potentiometric method is described for the quantitative assay of formaldehyde (HCHO) in pharmaceutical and industrial
preparations. It is based on the reaction of HCHO with (ethylenediamine)-Cu(II)-sulfate [Cu(CH2NH2)2(H2O)2] · SO4. The changes in potential, resulting from the release of the Cu(II) cations, are monitored with a Cu(II)-ion selective electrode.
The calibration curve for the HCHO is linear in the concentration range 50–250 mg L−1, with a limit of detection of 8.5 mg L−1. The method shows very good reproducibility with an RSD of 2.6% for successive injections (n = 5) of 150 mg L−1 HCHO primary solution, while it is interference free. The method was successfully tested in various industrial and pharmaceutical
preparations. 相似文献
45.
Dany Brouillette Gérald Perron Jacques E. Desnoyers 《Journal of solution chemistry》1998,27(2):151-182
Lithium bis(trifluoromethylsulfone)imide (LiTFSI) is a promising electrolyte for high-energy lithium batteries due to its high solubility in most solvents and electrochemical stability. To characterize this electrolyte in solution, its conductance and apparent molar volume and heat capacity were measured over a wide range of concentration in glymes, tetraethylsulfamide (TESA), acetonitrile, -butyrolactone, and propylene carbonate at 25°C and were compared with those of LiClO4 in the same solvents. The glymes or n(ethylene glycol) dimethyl ethers (nEGDME), which have the chemical structure CH3–O–(CH2–CH2–O)
n
–CH3 for n = 1 to 4, are particularly interesting since they are electrochemically stable, have a good redox window, and are analogs of the polyethylene oxides used in polymer-electrolyte batteries. TESA is a good plasticizer for polymer-electrolyte batteries. Whenever required, the following properties of the pure solvents were measured: compressibilities, expansibilities, temperature and pressure dependences of the dielectric constant, acceptor number, and donor number. These data were used in particular to calculate the limiting Debye-Hückel parameters for volumes and heat capacities. The infinite dilution properties of LiTFSI are quite similar to those of other lithium salts. At low concentrations, LiTFSI is strongly associated in the glymes and moderately associated in TESA. At intermediate concentrations, the thermodynamic data suggests that a stable solvate of LiTFSI in EGDME exists in the solution state. At high concentrations, the thermodynamic properties of the two lithium salts approach those of the molten salts. These salts have a reasonably high specific conductivity in most of the solvents. This suggests that the conductance of ions at high concentration in solvents of low dielectric constant is due to a charge transfer process rather than to the migration of free ions. 相似文献
46.
47.
T. V. Golovko O. B. Smirnova N. P. Solov’eva O. S. Anisimova V. G. Granik 《Russian Chemical Bulletin》2007,56(5):1032-1040
Condensation of lactim ethers of 3,4-dihydrocarbostyril and 1H-2,3,4,5-tetrahydrobenz[b]azepin-2-one with malonodinitrile, cyanoacetamide, and ethyl cyanoacetate gave the corresponding 2-methylidene derivatives.
Their reactions with dimethylformamide diethyl acetal followed by cyclization into benzo[b][1,6]naphthyridines and pyrido[4,3-b]benz[f ]azepines were studied.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 995–1002, May, 2007. 相似文献
48.
Continuous chemiluminescence determination of formaldehyde in air based on Trautz-Schorigin reaction 总被引:1,自引:0,他引:1
A new continuous method for the determination of formaldehyde in air is described. A cylindrical wet effluent diffusion denuder is used for the collection of formaldehyde from air into a thin film of absorption liquid (distilled-deionized water). Formaldehyde in the denuder concentrate is on-line detected employing a chemiluminescence flow method based on a reaction of formaldehyde and gallic acid with hydrogen peroxide in an alkaline solution. The collection efficiency of formaldehyde is quantitative at the air flow rate of 0.5 L min−1 (absorption liquid flow rate of 336 μL min−1). The limit of detection (S/N = 3) is 0.60 μg m−3 HCHO (0.49 ppb). The calibration graph is linear up to 300 μg m−3 HCHO (244 ppb). The relative standard deviations of chemiluminescence method for 1 × 10−6 and 5 × 10−6 M HCHO are 2.87% and 1.49%, respectively. Acetaldehyde interferes negligible, other compounds do not interfere. The method was employed for formaldehyde measurement in ambient air. The comparison measurement illustrates the good agreement of results obtained by proposed method with those obtained by reference fluorimetric method. 相似文献
49.
XinBinMA ShengPingWANG HongLiGUO GenHuiXU 《中国化学快报》2003,14(5):461-464
Diphenyl oxalate was synthesized from transesterification of dimethyl oxalate with phenol over TS-1(2.5 wt% Ti)catalyst.TS-1 catalyst,as a beterogeneous catalyst,showed excellent selectivity of diphenyl oxalate and methylphenyl oxalate compared with other homogeneous catalysts.Lewis acid sites on TS-1 catalyst were the active sites for transesterification of dimethyl oxalate with phenol.the high selectivity was closely related to the weak acid sites over TS-1. 相似文献
50.
A new Sequiterpenoid from Eupatorium adenophorum Spreng 总被引:1,自引:0,他引:1
A new sequiterpenoid compound 8aα-hydroxy-1-isopropyl-4,7-dimethyl-1,2,3,4,6,8a-hexahydro-naphthalene-2,6-dione(1),together with seven known compounds anti-HH-dimer-coumarin(2),(-)-5-exo-hydroxy-bomeol(3),O-hydroxyl cinnamic acid(4),9β-hydroxy-ageraphorone(5),10Hα-9-oxo-ageraphorone(6),10Hβ-9-oxo-ageraphorone(7)and 9-oxo-10,11-dehydroageraphorone 8,was isolated from the leaves of Eupatorium adenopho-rum Spreng.The structures were elucidated by IR,~1H and ~(13)C NMR,EIMS,HMBC and single-crystal X-ray spec-tral data. 相似文献