全文获取类型
收费全文 | 4857篇 |
免费 | 127篇 |
国内免费 | 22篇 |
专业分类
化学 | 2995篇 |
晶体学 | 53篇 |
力学 | 65篇 |
数学 | 240篇 |
物理学 | 1108篇 |
无线电 | 545篇 |
出版年
2022年 | 33篇 |
2021年 | 28篇 |
2020年 | 48篇 |
2019年 | 66篇 |
2018年 | 43篇 |
2017年 | 35篇 |
2016年 | 69篇 |
2015年 | 86篇 |
2014年 | 81篇 |
2013年 | 245篇 |
2012年 | 216篇 |
2011年 | 252篇 |
2010年 | 143篇 |
2009年 | 170篇 |
2008年 | 262篇 |
2007年 | 279篇 |
2006年 | 281篇 |
2005年 | 229篇 |
2004年 | 199篇 |
2003年 | 184篇 |
2002年 | 189篇 |
2001年 | 125篇 |
2000年 | 139篇 |
1999年 | 92篇 |
1998年 | 62篇 |
1997年 | 69篇 |
1996年 | 83篇 |
1995年 | 66篇 |
1994年 | 44篇 |
1993年 | 62篇 |
1992年 | 88篇 |
1991年 | 67篇 |
1990年 | 62篇 |
1989年 | 54篇 |
1988年 | 75篇 |
1987年 | 49篇 |
1986年 | 62篇 |
1985年 | 72篇 |
1984年 | 78篇 |
1983年 | 32篇 |
1982年 | 47篇 |
1981年 | 44篇 |
1980年 | 47篇 |
1979年 | 45篇 |
1978年 | 41篇 |
1977年 | 45篇 |
1976年 | 25篇 |
1975年 | 32篇 |
1974年 | 34篇 |
1973年 | 28篇 |
排序方式: 共有5006条查询结果,搜索用时 109 毫秒
71.
A method has been developed for highly sensitive determination of haloperidol in human serum involving a simple extraction procedure followed by gas chromatographic separation. Target components were separated from the extracting solvents with a Van den Berg type solventless sample injector before introduction Into a DB-1 capillary separation column. A surface ionization detector (SID), which has highly selective sensitivity for Substituted amines, was employed for quantitation using bromperidol as an internal standard. Chloroform proved to be the best extracting solvent, yielding a quantitative detection limit of 5 ng/ml (S/N = 2). Comparison of the response to target compounds obtained by the SID, FTD (flame thermionic detector), and FID (flame ionization detector) showed the SID to be superior. 相似文献
72.
An automatic method for the determination of metabolites of Ropivacaine in urine was set up. It utilizes supported liquid membrane extraction for sample clean-up and enrichment, followed by ion-pair chromatography determination using UV detection. The extraction was very selective with no observed interfering compounds from the urine matrix, permitting simple isocratic chromatographic analysis. The detection limits for spiked urine samples were 2–18 nM for the different compounds. The repeatability was 1–3% (RSD) with an internal standard that was also extracted, and about twice without this standard. A throughput of 3.3 samples per hour was achieved and the liquid membrane was stable for more than a week. 相似文献
73.
A supersonic jet instrument for fluorescence spectrometry is described. It consists of a high-temperature free expansion nozzle for continuous sample introduction and a vacuum chamber equipped with a high-speed pumping system. Rotationally cooled spectra obtained with the supersonic jet are compared with gas-phase spectra measured at high temperature for perylene and benzo[a]pyrene molecules. Each component of the unresolved band structure in the high-temperature spectra was found to be composed of a rotational congestion of several vibrational bands. For a 1:1 mixture of perylene and benzo[a]pyrene, selective detection is possible by using supersonic jet spectrometry. The detection limit for perylene is 100 ng. The advantage of this technique over other low-temperature spectrometric methods based on Shpol'skii and matrix isolation effects are discussed. 相似文献
74.
S. Takahashi H. Morimoto E. Murata S. Kataoka K. Sonogashira N. Hagihara 《Journal of polymer science. Part A, Polymer chemistry》1982,20(2):565-573
Metal-polyyne polymers consisting of palladium and conjugated acetylenic systems, where PD and R represent the —Pd(PBu3)2—moiety and alkyl groups, respectively, were prepared by polycondensation between palladium chlorides and α,ω-diethynyl compounds in amines using a catalytic amount of cuprous iodide. The molecular weights of the polymers formed were greatly affected by the basicity of the amines and the addition of free phosphines to the polymerization system. Under the optimum conditions, i.e., in the presence of CuI and PBu3 (in molar ratio 1/4) in piperidine at room temperature, polymer Ia (R1 = R2 = H) having M?w = 29,000 was obtained. 相似文献
75.
Toshikazu Kurosaki Osamu Takahashi Makoto Okawara 《Journal of polymer science. Part A, Polymer chemistry》1974,12(7):1407-1420
Polymers having stable pendant . radicals were synthesized through their precursor polymers by oxidizing them in air or by H2O2–Na2WO4. Hydrochlorides and sulfates of 4-methacryloylamino- and 4-methacryloyloxy-1-hydroxy-2,2,6,6-tetramethylpiperidines were synthesized as precursor monomers and polymerized by using α,α′-azobisisobutyronitrile under appropriate conditions to precursor polymers of high molecular weight: poly-4-methacryloylamino-/oxy-1-hydroxy-2,2,6,6-tetramethylpiperidinehydrochlorides and sulfates. The precursor polymers were converted to polymers having nitroxyl stable radicals, i.e., poly-4-methacryloylamino-/oxy-2,2,6,6-tetramethylpiperidine-1-oxyls, by oxidation in air or with H2O2–Na2WO4 without any main-chain scission. The structure of the resultant stable radical polymers was determined by infrared, ultraviolet, and ESR spectroscopy. Based on the results of spectroscopic analysis and Kjeldahl analysis, the transformation from precursors to nitroxyl stable radical polymers was found to be quantitative. Investigations on the applicability of polymeric nitroxyl radicals to oxidation-reduction reactions were attempted by means of polarography; the reduction half-wave potential was found to be ?1.16 V for the mercury pool. 相似文献
76.
Kimura T Takahashi S Akiyama S Uzawa T Ishimori K Morishima I 《Journal of the American Chemical Society》2002,124(39):11596-11597
The helix formation dynamics of poly-L-glutamic acids (PGAs) were observed by the microsecond-resolved Fourier transform infrared (FTIR) and circular dichroism (CD) spectroscopies. The helix formation of 34-residue PGA from random coil at pH (or pD for FTIR) 8.0 was initiated by a pH jump to 4.9 using the rapid solution mixer whose mixing dead time is 50 micros. The amide I' line in the time-resolved FTIR spectra exhibited the fast (<100 micros) increase of the total helical content. The time-resolved CD spectra of the same process also showed the fast (<150 micros) formation of short helical segments (5 +/- 1 residues), which was followed by the slower (<1 ms) elongation of the short helices to longer helices (>10 residues). Similar dynamics were observed for the same pH jump of approximately 190-residue PGA, although there were additional steps that made the helix formation of approximately 190-residue PGA more complex. The observed multistep helix formation is likely caused by the strong hydrogen-bonding interactions between the protonated side chains of PGAs. 相似文献
77.
T. Kimura Y. Takahashi T. Kamiyama M. Fujisawa 《Journal of Thermal Analysis and Calorimetry》2007,88(2):587-595
Excess enthalpies (H
E)
of 17 binary mixtures of o- and m-isomers of dichlorobenzene, difluorobenzene, methoxymethylbenzene,
dimethylbenzene, dimethoxybenzene, aminofluorobenzene, fluoronitrobenzene,
diethylbenzene, chlorofluorobenzene, fluoroiodobenzene, bromofluorobenzene,
chloromethylbenzene, fluoromethylbenzene, bromomethylbenzene, iodomethylbenzene,
fluoromethoxybenzene, dibromobenzene at 298.15 K were measured. All excess
enthalpies measured were very small, and those of o-+m-isomers of aminofluorobenzene, dibromobenzene and
iodomethylbenzene were negative but 14 other binary mixtures of isomers were
positive over the whole range of mole fractions. H
E
of o-+m-isomers
of dimethoxybenzene showed the largest enthalpic instability and those of
aminofluorobenzene showed the largest enthalpic stability. There was a correlation
between dipole–dipole interaction, dipole–induced dipole interaction
or entropies of vaporization and excess partial molar enthalpies at infinite
dilution. 相似文献
78.
79.
Fujii H Hirano N Uchiro H Kawamura K Nagase H 《Chemical & pharmaceutical bulletin》2004,52(6):747-750
7beta-Carbamoyl-4,5alpha-epoxymorphinans 5 were stereoselectively synthesized from the 7alpha-carboxylate intermediate 3 in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and amines under reflux conditions in mesitylene via a novel and reactive gamma-lactone 7. These were the first examples of the stereoselective syntheses of 7beta-substituted 4,5alpha-epoxymorphinans. The mechanism of the reaction process was elucidated as follows: 1) epimerization of 7alpha-carboxylate 3, 2) intramolecular lactonization of 7beta-carboxylate 6, and 3) aminolysis of the resultant gamma-lactone 7. The aminolysis of the isolated reactive gamma-lactone 7 with allylamine and the alcoholysis with MeOH in the presence of NaBH(4) proceeded at room temperature. The gamma-lactone 7 can be a useful intermediate for the preparation of 7beta-substituted 4,5alpha-epoxymorphinans that would be potent selective delta opioid receptor ligands. The stereoselective syntheses of the 7alpha-carbamoyl-4,5alpha-epoxymorphinans 9 from 7alpha-carboxylate 3 via 7alpha-carboxylic acid were also successful. 相似文献
80.
Some water-soluble organic iodine compounds (aqueous solution) can be analyzed for iodine by isotopically exchanging with labelled elementary iodine (organic solution). The method is applicable to exchange systems in which the rate of the exchange is rather small but measurable, before the exchange equilibrium is attained. The iodine content of iodoaromatic amino acids such as 5-iodouracil and 3,5-diiodotyrosine can be determined within an error of ±4%. 相似文献