全文获取类型
收费全文 | 1208篇 |
免费 | 42篇 |
国内免费 | 7篇 |
专业分类
化学 | 875篇 |
晶体学 | 24篇 |
力学 | 46篇 |
数学 | 120篇 |
物理学 | 192篇 |
出版年
2024年 | 3篇 |
2023年 | 7篇 |
2022年 | 21篇 |
2021年 | 56篇 |
2020年 | 40篇 |
2019年 | 43篇 |
2018年 | 34篇 |
2017年 | 20篇 |
2016年 | 47篇 |
2015年 | 23篇 |
2014年 | 45篇 |
2013年 | 102篇 |
2012年 | 84篇 |
2011年 | 108篇 |
2010年 | 55篇 |
2009年 | 42篇 |
2008年 | 58篇 |
2007年 | 42篇 |
2006年 | 50篇 |
2005年 | 46篇 |
2004年 | 36篇 |
2003年 | 26篇 |
2002年 | 28篇 |
2001年 | 12篇 |
2000年 | 21篇 |
1999年 | 12篇 |
1998年 | 8篇 |
1997年 | 5篇 |
1996年 | 7篇 |
1995年 | 11篇 |
1994年 | 9篇 |
1993年 | 6篇 |
1992年 | 16篇 |
1991年 | 7篇 |
1990年 | 10篇 |
1989年 | 16篇 |
1988年 | 13篇 |
1987年 | 10篇 |
1986年 | 4篇 |
1985年 | 4篇 |
1984年 | 3篇 |
1983年 | 7篇 |
1982年 | 3篇 |
1981年 | 9篇 |
1980年 | 11篇 |
1979年 | 10篇 |
1978年 | 3篇 |
1977年 | 3篇 |
1976年 | 4篇 |
1973年 | 3篇 |
排序方式: 共有1257条查询结果,搜索用时 31 毫秒
41.
A microwave-assisted sequential extraction of water and dilute acid soluble arsenic species from marine plant and animal tissues 总被引:1,自引:0,他引:1
This paper describes the use of dilute nitric acid for the extraction and quantification of arsenic species. A number of extractants (e.g. water, 1.5 M orthophosphoric acid, methanol-water and dilute nitric acid) were tested for the extraction of arsenic from marine biological samples, such as plants that have proved difficult to quantitatively extract. Dilute 2% (v/v) nitric acid was found to give the highest recoveries of arsenic overall and was chosen for further optimisation. The optimal extraction conditions for arsenic were 2% (v/v) HNO3, 6 min−1, 90 °C. Arsenic species were found to be stable under the optimised conditions with the exception of the arsenoriboses which degraded to a product eluting at the same retention time as glycerol arsenoribose. Good agreement was found between the 2% (v/v) HNO3 extraction and the methanol-water extraction for the certified reference material DORM-2 (AB 17.1 and 16.2 μg g−1, respectively, and TETRA 0.27 and 0.25 μg g−1, respectively), which were in close agreement with the certified concentrations of AB 16.4 ± 1.1 μg g−1 and TETRA 0.248 ± 0.054 μg g−1.To preserve the integrity of arsenic species, a sequential extraction technique was developed where the previously methanol-water extracted pellet was further extracted with 2% (v/v) HNO3 under the optimised conditions. Increases in arsenic recoveries between 13% and 36% were found and speciation of this faction revealed that only inorganic and simple methylated species were extracted. 相似文献
42.
Hamed M. Abu El-Nader 《Transition Metal Chemistry》1995,20(3):316-319
Summary The kinetics of the thermal decomposition of thetris-oxalactocobaltate(III) complex has been investigated in the presence of EtOH and (CH2OH)2 spectrophotometrically in the 50–70 ± 0.1 ° C range. The rate of the reaction decreases upon the addition of either of the alcohols to the reaction medium, whereas the activation energy increases. The thermodynamic parameters were calculated and are discussed in terms of the solvation effects. The influence of the dielectric constants of the solvent mixtures on the rate has been studied. A free radical mechanism is proposed and discussed. 相似文献
43.
Gaber M. Abu El-Reash 《Transition Metal Chemistry》1993,18(5):493-496
Summary The synthesis and characterization of CrIII, MnII, FeIII, CoII, NiII, CuII, ZnII, CdII and UO
inf2
sup2+
complexes of N-isonicotinamido-N-benzoylthiocarbamide (H2IBTC) are reported. I.r. spectral data show that the ligand behaves in a bidentate, tridentate and/or tetradentate manner. Different stereochemistries are proposed for CrIII, MnII, FeIII, CoII, NiII and CuII complexes on the basis of spectral and magnetic studies. The i.r. data indicate that the carbonyl oxygen of the benzoyl moiety is the backbone of chelation in most complexes. 相似文献
44.
The complexes of the reagent 5-Br-PADAP with the metal ions La(III), Ce(III), and Y(III) have been studied.The composition and stability of these complexes have been determined. A sensitive spectrophotometric procedure for the determination of the metal ions La(III), Ce(III), and Y(III) has been proposed. The limitations of this procedure and the effect of other ions have been studied. 相似文献
45.
Till?R?hrich Bassam?Abu Thaher Nico?Manicone Hans-Hartwig?OttoEmail author 《Monatshefte für Chemie / Chemical Monthly》2004,135(8):979-999
Summary. (RS)-2-tert-Butyldimethylsilyl-1,2-thiazetidine-3-acetic acid 1,1-dioxide prepared from (RS)-S-benzyl--homocysteine was condensed via DCC/NHS with various L-amino acid esters or dipeptide esters yielding N-silylated -sultam peptides. A -sultam active ester was isolated as an intermediate. Desilylation with TBAF in THF yielded stable N-unsubstituted products, and deprotection of the benzyl esters was achieved by catalytic hydrogenation. (S)-S-Benzyl--homocysteine was obtained by fractional crystallization of the brucine salt of the racemate and transformed into benzyl (S)-1,2-thiazetidine-3-acetate, which was on the other hand synthesized by an enantiospecific route from -benzyl Boc-L-aspartate. Some -sultam peptides were prepared from the (S)-enantiomer, and finally some -sultam peptides containing D-Ala units were obtained. 相似文献
46.
J. Korkisch und Maher Osman 《Fresenius' Journal of Analytical Chemistry》1959,171(5):349-353
Zusammenfassung In der vorliegenden Arbeit wird eine rasche und genaue spektrophotometrische Bestimmung von Mikrogrammengen MolybdÄn beschrieben. Als Reagens wird der Azofarbstoff Solochrome Violet R verwendet. Dieser bildet mit MolybdÄn in sehwach salzsaurem Medium einen rotgefÄrbten Komplex, der selbst bei Anwesenheit von ÄDTA bestÄndig ist. Dadurch ist es möglich, den störenden Einflu\ anderer Ionen, z. B. den des Zirkoniums, auszuschalten. Mit dieser Methode lassen sich noch 2,0 g MolybdÄn/10 ml Me\lösung mit relativ hoher Genauigkeit bestimmen.Wir danken Herrn Prof. Dr. F. Hecht für seine Unterstützung, die für das Zustandekommen dieser Arbeit von gro\em Nutzen war. 相似文献
47.
Hanan Al-Awadi Maher R. Ibrahim Nouria A. Al-Awadi Yehia A. Ibrahim 《Tetrahedron》2007,63(52):12948-12953
Gas-phase thermolysis of thieno[2,3-e][1,2,4]triazines gave benzonitrile, isothiazole, pyridazine, and thieno[2,3-d]thiazole derivatives. Similar transformation of benzo[1,2,4]triazine and phenanthro[9,10-e][1,2,4]triazine derivatives into their corresponding condensed thiazoles has been achieved by heating at 350 °C with sulfur. A mechanism for these pyrolytic transformations was proposed. 相似文献
48.
Various alcohols and phenols can be smoothly converted to the corresponding THP ethers using 20 mol % CuSO4·5H2O under mild reaction conditions at room temperature. Some of the major advantages of this procedure are nonaqueous work-up, very good yields, less expensive catalyst and compatibility with other protecting groups. 相似文献
49.
A review with 159 references is presented on the applications of adsorptive stripping voltammetry (AdSV) for determining
trace metal ions in different environmental samples (e.g. water, soil, plant, biological fluids). The analytical applications
of AdSV to biologically active organic compounds (e.g. pharmaceuticals, pesticides, biomolecules) are also discussed.
Received: 18 December 1995/Revised: 8 January 1997/Accepted: 12 January 1997 相似文献
50.
Kristian Lappalainen Katariina Yliheikkil Adnan S. Abu‐Surrah Mika Polamo Markku Leskel Timo Repo 《无机化学与普通化学杂志》2005,631(4):763-768
Iron(II) and cobalt(II) complexes ( 7 ‐ 15 ) based on new aldimine 2, 6‐bis[(imino)methyl]pyridine ( 1 , 2 , 4 , 6 ) and ketimine (2, 6‐bis[(imino)ethyl]pyridine ( 3 , 5 ) ligands with bulky chiral aliphatic or aromatic terminal groups have been prepared and characterized by 1H NMR, 13C NMR, IR‐, mass spectroscopy (EI), and elemental analysis. The complex [CoCl2(BBoMP)]·1/2 CHCl3 ( 13 ) (BBoMP: 2, 6‐bis{(R‐(+)‐(bornylimino)‐methyl}pyridine) crystallizes in monoclinic space group P21 with cell dimensions: a = 7.6603(11) Å, b = 28.3153(14) Å, c = 13.537(2) Å, V = 2908.1(6) Å3, Z = 4. The coordination sphere around Co is distorted trigonal bipyramidal. 相似文献