全文获取类型
收费全文 | 8286篇 |
免费 | 261篇 |
国内免费 | 24篇 |
专业分类
化学 | 5517篇 |
晶体学 | 54篇 |
力学 | 266篇 |
综合类 | 1篇 |
数学 | 1128篇 |
物理学 | 1605篇 |
出版年
2023年 | 62篇 |
2022年 | 135篇 |
2021年 | 268篇 |
2020年 | 164篇 |
2019年 | 177篇 |
2018年 | 168篇 |
2017年 | 159篇 |
2016年 | 344篇 |
2015年 | 259篇 |
2014年 | 283篇 |
2013年 | 505篇 |
2012年 | 564篇 |
2011年 | 593篇 |
2010年 | 445篇 |
2009年 | 406篇 |
2008年 | 543篇 |
2007年 | 503篇 |
2006年 | 400篇 |
2005年 | 358篇 |
2004年 | 289篇 |
2003年 | 272篇 |
2002年 | 218篇 |
2001年 | 159篇 |
2000年 | 139篇 |
1999年 | 100篇 |
1998年 | 90篇 |
1997年 | 69篇 |
1996年 | 81篇 |
1995年 | 67篇 |
1994年 | 58篇 |
1993年 | 56篇 |
1992年 | 55篇 |
1991年 | 48篇 |
1990年 | 38篇 |
1989年 | 30篇 |
1988年 | 34篇 |
1987年 | 23篇 |
1986年 | 30篇 |
1985年 | 52篇 |
1984年 | 38篇 |
1983年 | 26篇 |
1982年 | 22篇 |
1981年 | 21篇 |
1980年 | 35篇 |
1979年 | 19篇 |
1978年 | 26篇 |
1976年 | 20篇 |
1975年 | 18篇 |
1974年 | 14篇 |
1973年 | 17篇 |
排序方式: 共有8571条查询结果,搜索用时 62 毫秒
161.
de Magalhães Padilha P Rocha JC Moreira JC de Sousa Campos JT do Carmo Federici C 《Talanta》1997,45(2):317-323
Cellulose phosphate (CELLPHOS) was studied as a collector for analytical preconcentration of traces of Cd(II), Cr(III), Cu(II) and Ni(II) from aqueous sample solution. It has been proved that using chromatographic columns packed with CELLPHOS for preconcentration and 1.0 mol 1(-1) HCl for elution the adsorbed analytes are quantitatively enriched. An enrichment factor of 20 (100 ml sample, 5 ml concentrate) was achieved by this separation procedure, which was applied to a series of water analyses (river, sea, bog water). 相似文献
162.
Crespo A Martí MA Estrin DA Roitberg AE 《Journal of the American Chemical Society》2005,127(19):6940-6941
A novel technique for computing free energy profiles in enzymatic reactions using the multiple steering molecular dynamics approach in the context of an efficient QM-MM density functional scheme is presented. The conversion reaction of chorismate to prephenate catalyzed by the Bacillus subtilis enzyme chorismate mutase has been chosen as an illustrative example. 相似文献
163.
João Paulo R.F. André Hugh D. Burrows Carlos F.G.C. Geraldes Maria Da Graça M. Miguel M.Helena S.F. Teixeira L.F. Vilas Boas 《Polyhedron》1996,15(24):4331-4340
Complexation of europium(III) with glyceryl-1- and -2-phosphates has been studied by metal ion luminescence, 1H and 13C NMR spectroscopy and potentiometry. From the luminescence and NMR studies, the formation of a 1:1 inner-sphere complex, in which the glyceryl phosphate is directly bound to the metal, is confirmed. Similar apparent binding constants at pH 2 were obtained by the three methods. Values obtained by NMR at pH 2 are 53 M−1 and 12 M−1 for glyceryl-1- and -2-phosphate, respectively. By comparison with literature data on related systems it is suggested that the ligands bind through the phosphate group. To obtain structural information from the NMR data, complexation has also been studied with the lanthanide ions Dy(III), Er(III) and Gd(III) using both chemical shift and relaxation data. From this, metal-proton distance ratios have been calculated. Comparison of 1H and 13C NMR spectral data in the presence of paramagnetic lanthanides suggests conformational equilibria in the solutions. From the potentiometric studies, global formation constants have been determined, and speciation diagrams obtained over the pH range 1.5pH7.0 for ligand/metal ratios of 1 and 30. Implications of these results on lanthanide induced fusion of phospholipid membranes are discussed. 相似文献
164.
Preconcentration Systems Using Polyurethane Foam/Me-BDBD for Determination of Copper in Food Samples
Valfredo Azevedo Lemos Daniel Rodrigues Vieira Cleber Galvão Novaes Marcelo Eça Rocha Moacy Selis Santos Regina Terumi Yamaki 《Mikrochimica acta》2006,153(3-4):193-201
A new reagent, 6-[2′-(6′-methyl-benzothiazolylazo)]-1,2-dihydroxy-3,5-benzenedisulfonic acid (Me-BDBD), was synthesised and
used in on-line and off-line systems for copper preconcentration by solid-phase extraction. Spectrophotometry and Flame Atomic
Absorption Spectrometry (FAAS) were the detection techniques. Polyurethane foam loaded with Me-BDBD packed in a minicolumn
was used as sorbent in both systems. The spectral characteristics of Me-BDBD were investigated. The optimum pH values for
maximum sorption of the metal are between 7.0 and 8.5. Copper was desorbed with 0.05 and 0.50 mol L−1 hydrochloric acid solutions, for on-line and off-line systems, respectively. The effects of several foreign substances on
the adsorption of copper are reported. The enrichment factors obtained were 7 (on-line) and 26 (off-line) for the systems.
The proposed procedures allowed the determination of copper with detection limits of 3.4 and 1.4 μg L−1 (0.85 and 0.35 μg per gram of sample) for on-line and off-line systems, respectively. The precision of the procedures was
also calculated: 3.2 (on-line) and 1.9% (off-line). The validation of the procedures was carried out by analysis of certified
reference material. The copper contents in corn and rice flour and black tea samples were determined by applying the proposed
procedures. 相似文献
165.
The protolytic behavior of d-gluconic-delta-lactone acid has been studied by means of automated potentiometric titrations at different ionic strengths in the range 0.1=I=3.0 mol dm(-3) in NaClO(4) at 25 degrees C. This study reveals a protolytic equilibrium of gluconic acid as well as a distribution equilibrium between gluconic acid (HG) and its lactone form (L). The values of the stoichiometric constants obtained have been correlated by means of the modified Bromley methodology. The thermodynamic constants obtained were logbeta(0)=3.92+/-0.10 for the protolytic equilibrium H(+)+G(-)right harpoon over left harpoonHG and logK(r)(0)=-0.81+/-0.09 for the distribution equilibrium HGright harpoon over left harpoonL. 相似文献
166.
167.
Derivatization procedures for the detection of beta(2)-agonists by gas chromatographic/mass spectrometric analysis 总被引:2,自引:0,他引:2
An evaluation of derivatization procedures for the detection of beta(2)-agonists is presented. The study was performed with the beta(2)-agonists bambuterol, clenbuterol, fenoterol, formoterol, salbutamol, salmeterol and terbutaline. Different derivatizating agents were employed, aiming to obtain derivatives with high selectivity to be used in the gas chromatographic/mass spectrometric analysis of beta(2)-agonists in biological samples. Trimethylsilylation was compared with different agents and the role of some catalysts was evaluated. Acylation, combined trimethylsilylation and acylation, and the formation of cyclic methylboronates were also studied. Sterical hindrance caused by different substituents at the nitrogen atom of the beta-ethanolamine lateral chain of beta(2)-agonist molecules is mainly responsible for differences in the abundances of the derivatives obtained. The use of catalysts produces an increase in the derivatization yield, especially for compounds with low steric hindrance (substituents with primary and secondary carbon atoms). The formation of trimethylsilyl (TMS) ethers is not influenced by structural molecular differences when only hydroxy groups are involved in derivatization. Combined trimethylsilylation and acylation showed that compounds with a secondary carbon atom linked to the nitrogen atom form mainly N-TFA-O-TMS derivatives, with a small amount of N-TMS-O-TMS derivatives. Compounds with tert-butyl substituents at the amino group (bambuterol, salbutamol and terbutaline) formed O-TMS derivatives as the main products, although a limited amount of trifluoroacylation at the nitrogen atom also occurred. Cyclic methylboronates were formed with bambuterol, clenbuterol, formoterol, salbutamol and salmeterol. Owing to hydroxy substituents in unsuitable positions for ring formation, this procedure was not effective for fenoterol and terbutaline. Mass spectra of different derivatives and tentative fragmentation profiles are also shown. For screening purpose (e.g. sports drug testing), derivatization with MSTFA or BSTFA alone is recommended as a comprehensive derivatization technique for beta(2)-agonists owing to minimal by-product formation; formation of cyclic methylboronates can be useful for confirmation purposes. Detection limits were obtained for the TMS and cyclic methylboronate derivatives using the derivatizing reagents MSTFA and trimethylboroxine, respectively. For most of the compounds, lower detection limits were found for the TMS derivatives. 相似文献
168.
Marlin Opałło Nagao Kobayashi Tetsuo Osa 《Journal of inclusion phenomena and macrocyclic chemistry》1989,7(4):413-422
The complexation of 2,3-anthracenedicarboxylate (ADC) by- and-cyclodextrins in water containing an organic solvent has been studied by induced circular dichroism. It has been shown that an increase of organic solvent ratio causes the degradation of the 1:1 ADC:-CD complex and the liberation of one guest molecule from the 2:1 ADC:-CD complex in water. The higher the hydrophobicity of the cosolvent, the weaker the complexation of ADC by-CD. 相似文献
169.
The influence of different modes of preparation on the stoichiometry of thermal decomposition of isothiocyanatonickel(II) complexes with ammonia was studied. It was found that the complex Ni(NCS)2(NH3)4 (I) prepared by heterogeneous reaction undergoes decomposition in two steps (–2 NH3, –2 NH3), while for complex II, of the same composition but prepared by homogeneous reaction from solution, the decomposition proceeds in three steps (–1 NH3, –1 NH3, –2NH3). Electronic and infrared absorption spectra were used for the study of the spectral properties of the starting complex. It was found that the different stoichiometries of thermal decompositions of complexes I and II do not cause differences in the bonding strength of the ammonia molecules (chemical factor); this effect is rather brought about by physical factors such as different imperfections of the crystal lattice.
Zusammenfassung Der Einfluß der Herstellung auf die Stöchiometrie der thermischen Zersetzung von Amin-Komplexen des Isothiocyanatonickels wurde studiert. Der Zerfall des Komplexes Ni(NCS)2(NH3)4 (I), hergestellt durch heterogene Reaktion, verlief in zwei Etappen (–2 NH3, –2 NH3). Beim selben Komplex (II), hergestellt durch homogene Reaktion in Lösung, wurden jedoch drei Etappen beobachtet (–1 NH3, –1 NH3, –2 NH3). Die Eigenschaften des Ausgangsproduktes wurden durch Elektronen- und IR-Spektroskopie untersucht. Das unterschiedliche thermische Verhalten ist nicht auf eine verschiedene Bindungsstärke der NH3 Moleküle, sondern auf physikalische Ursachen, wie z. B. Unregelmässigkeiten im Kristallgitter zurückzuführen.
Résumé On a étudié l'influence des diverses méthodes de préparation sur la stoechiométrie de la réaction de décomposition thermique des complexes de l'isothiocyanate de nickel(II) avec l'ammoniac. On a établi que le complexe Ni(SCN)2(NH3)4, (I), préparé rar réaction hétérogène, subit une décomposition en deux étapes (–2NH3, –2NH3), tandis que le complexe (II), de même composition, mais préparé par réaction homogène, à partir de solutions, se décompose en trois étapes (–1NH3,–1NH3, –2NH3). Les propriétés spectrales du complexe initial ont été étudiées par absorption électronique et infrarouge. On a trouvé que les différences de stoechiométrie des réactions de décomposition thermique des complexes (I) et (II) n'apportaient pas de différences entre les énergies de liaison des molécules d'ammoniac (facteur chimique). C'est plutôt à des facteurs physiques, comme les différentes imperfections du réseau cristallin, que cet effet serait dû.
(II) . , Ni(NCS)2(NH3)4 (I), , (–2NH3,–2NH3). , II , , (–1 NH3,–1 NH3 –2NH3). . , I II ( ), , .相似文献
170.
Hassan Acherki Carlos Alvarez-Ibarra Juan F. Collados Lujn María L. Quiroga-Feijo 《Tetrahedron: Asymmetry》2005,16(24):4034-4044
The base-mediated reaction of enantiomerically pure -sulfinylketimine (+)-1 with (E)-,β-disubstituted propenoate esters afforded 3,4-disubstituted-5-(p-tolylsulfinyl)-5,6-dehydropiperidin-2-ones 9-13 and 14 with high or complete diastereoselectivity. A sole diastereomer of the four possible ones, with regard to the nature of ester, was isolated, which revealed the stereocontrol of the chiral sulfinyl group in the Michael reaction and transenolization steps. In addition, the enantioselective synthesis of ethyl (+)-(3S,4aS,7aS)-1-oxo-octahydro-1H-cyclopenta[c]pyridine-3-carboxylates (+)-17 is described (five steps; 47% yield; ee 97%). The absolute configuration of stereocentres introduced in (+)-17 was assigned on the basis of 1H NMR data. 相似文献