全文获取类型
收费全文 | 1636篇 |
免费 | 87篇 |
国内免费 | 126篇 |
专业分类
化学 | 1592篇 |
晶体学 | 18篇 |
力学 | 1篇 |
综合类 | 1篇 |
物理学 | 237篇 |
出版年
2023年 | 20篇 |
2022年 | 23篇 |
2021年 | 19篇 |
2020年 | 34篇 |
2019年 | 42篇 |
2018年 | 34篇 |
2017年 | 29篇 |
2016年 | 41篇 |
2015年 | 36篇 |
2014年 | 47篇 |
2013年 | 165篇 |
2012年 | 151篇 |
2011年 | 83篇 |
2010年 | 69篇 |
2009年 | 99篇 |
2008年 | 91篇 |
2007年 | 84篇 |
2006年 | 70篇 |
2005年 | 88篇 |
2004年 | 109篇 |
2003年 | 71篇 |
2002年 | 44篇 |
2001年 | 29篇 |
2000年 | 32篇 |
1999年 | 33篇 |
1998年 | 23篇 |
1997年 | 24篇 |
1996年 | 33篇 |
1995年 | 25篇 |
1994年 | 25篇 |
1993年 | 17篇 |
1992年 | 34篇 |
1991年 | 15篇 |
1990年 | 10篇 |
1989年 | 7篇 |
1988年 | 14篇 |
1987年 | 9篇 |
1986年 | 9篇 |
1985年 | 10篇 |
1984年 | 4篇 |
1982年 | 4篇 |
1981年 | 2篇 |
1980年 | 8篇 |
1979年 | 9篇 |
1978年 | 5篇 |
1977年 | 2篇 |
1976年 | 4篇 |
1974年 | 3篇 |
1973年 | 2篇 |
1972年 | 2篇 |
排序方式: 共有1849条查询结果,搜索用时 31 毫秒
1.
Jong Chan Lee Jin Young Park So Young Yoon Yong Hun Bae Seung Jun Lee 《Tetrahedron letters》2004,45(1):191-193
A novel and direct method for the synthesis of α-halocarbonyl compounds using sequential treatment of carbonyl compounds with [hydroxy(tosyloxy)iodo]benzene followed by magnesium halides under solvent-free microwave irradiation conditions is described. 相似文献
2.
We show that using ionic liquids as reagents in conjunction with microwave heating it is possible to prepare primary alkyl halides from the corresponding alcohols rapidly. Using ionic liquids as solvents in conjunction with microwave heating it is possible to prepare aryl nitriles from the corresponding aryl bromides or iodides. The scope and limitations of using microwave-promotion as a tool in these reactions is discussed. 相似文献
3.
A variety of aryl nitriles were prepared in excellent yields from the palladium acetate catalyzed coupling of aryl halides with Zn(CN)2 using polymer-supported triphenyl phosphine as the ligand and dimethylformamide as solvent under microwave irradiation conditions. 相似文献
4.
In the present paper, a new two-parameter inverted equation of state (EOS) is developed which is found to be working very
well in the high-pressure region. To check its success and validity, this EOS has been applied in a number of solids. The
computed volume compression is found to be in very good agreement with the experimental data in the whole range of pressure
in all the solids. The minimum and the maximum pressure range used in the present study is 0–320 kbar and 0–3000 kbar, respectively. 相似文献
5.
Adriana Tudose 《Tetrahedron letters》2006,47(48):8529-8533
Simple catalysts formed in situ from palladium acetate and a variety of imidazolium and imidazolinium carboxylates and dithiocarboxylates have been screened in the coupling of aryl halides with trans-2-phenylvinylboronic acid. Imidazol(in)ium carboxylates show an excellent activity, which compares to that displayed by the parent imidazol(in)ium chlorides, whereas imidazol(in)ium dithiocarboxylates are poorly efficient. Interestingly, the base employed exerts a profound influence on the trans/cis stereochemistry of the coupling product. 相似文献
6.
Historical perspectives for the chemistry of diene complexes of early transition metals developed at Osaka University in the period after 1970s were reviewed briefly and personally. Preparative chemistry of this field commenced from the magnesium-diene 1:1 compounds and quickly extended to almost all the early transition metals. By the studies operated together with other researchers, unique features of these diene complexes, especially their bonding and structure, selective reactions, and catalysis performances are described. 相似文献
7.
Two new polyacid derivative ligands of thienyl-substituted terpyridine analogues, N,N,N1,N1-[4′-(2?-thienyl)-2,2′:6′,2″-terpyridine-6,6″-diyl]bis(methylenenitrilo) tetrakis(acetic acid) (TTTA) and N,N,N1,N1-[2,6-bis(3′-aminomethyl-1′-pyrazolyl)-4-(2″-thienyl)pyridine] tetrakis(acetic acid) (BTTA), were synthesized, and the luminescence properties of their Eu3+ and Tb3+ chelates were investigated. The Eu3+chelates of the two ligands are strongly luminescent having luminescence quantum yields of 0.150 (TTTA-Eu3+) and 0.114 (BTTA-Eu3+), and lifetimes of 1.284 ms (TTTA-Eu3+) and 1.352 ms (BTTA-Eu3+), whereas their Tb3+ chelates are weakly luminescent. The TTTA-Eu3+ chelate was used for streptavidin (SA) labeling, and the labeled SA was used for time-resolved fluoroimmunoassay of insulin in human sera. The method gives the detection limits of 33 pg ml−1. 相似文献
8.
Sahadev R. K. Sharma S. K. Sindhwani 《Monatshefte für Chemie / Chemical Monthly》1992,123(10):883-889
Summary The chelation behaviour of some trivalent lanthanide and yttrium metal ion with biologically active 2-hydroxy-1-naphthaldehyde thiosemicarbazone (HNATS) has been investigated by potentiomotric measurements at 20±0.5°C in 75% (v/v) dioxane-water medium at various ionic strengths of sodium perchlorate. The method of Bjerrum and Calvin, as modified by Irving and Rossotti has been used to find out the values of
(average number of ligand bound per metal ion) andpL (free ligand exponent). The formation constants of metal chelates have been computed on a PC-XT computer, using a program patterned after that of Sullivan et al. to give
n
values using weighted least squares method. TheS
min
values (S
min
=2) have been calculated. The order of formation constants of chelates was found to be: La3+3+3+3+3+3+3+3+3+3+. The formation constants of the chelates formed have been correlated to size and ionization potentials of the metal ions.
Potentiometrische Untersuchungen der Komplexierungsgleichgewichte zwischen einigen trivalenten Metallionen und biologisch aktivem 2-Hydroxy-1-naphthaldehyd-thiosemicarbazon (HNATS)
Zusammenfassung Es wurde das Chelierungsverhalten einiger trivalenter Lanthanidenionen mit biologisch aktivem 2-Hydroxy-1-naphthaldehyd-thiosemicarbazon (HNATS) mittels potentiometrischer Messungen bei 20±0.5°C in 75% (v/v) Dioxan-Wasser bei verschiedener Ionenstärke an Natriumperchlorat untersucht. Die Methode nach Bjerrum und Calvin in der Modifikation nach Irving und Rossotti wurde zur Ermittlung der Werte (mittlere Anzahl an Liganden pro Metallion) undpL (Exponent an freiem Liganden) verwendet. Die Komplexbildungskonstanten wurden in Anlehnung an Sullivan et al. an einem PC-XT Computer errechnet. DieS min-Werte (S min=2) wurden ebenfalls bestimmt. Die Reihung der Chelatbildungskonstanten war: La3+相似文献3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+. Die Bildungskonstanten sind mit der Größe und dem Ionisierungspotential der Metallionen zu korrelieren.
9.
Bobonich F. M. Yaroshenko N. A. Solomakha V. N. Strelko V. V. Il'in V. G. 《Theoretical and Experimental Chemistry》2004,40(4):254-259
Under the conditions studied for the synthesis of mesophase materials with alkylpyridinium halides an increase in the density of packing of these molecules in the encapsulated micelles was observed with an increase in the length of the alkyl radicals. The difference in the density of packing of these surface active reagents (SAR) depended to a considerable extent on the perfection of the hexagonal structure and the characteristic absorption properties of the mesophase materials of MCM-41 type. 相似文献
10.
镧系离子与L-羟脯氨酸、DL-瓜氨酸配位作用研究 总被引:2,自引:0,他引:2
稀土与体内广泛存在的生物配体氨基酸的配位作用,尤其是三元体系的研究对于阐明稀土元素在体内的存在形态及探索稀土生物效应具有重要意义.羟脯氨酸和瓜氨酸均是人体中存在的重要氨基酸,它们在人体血浆中的浓度与必需的氨基酸相近[‘j.稀土与氨基酸配位作用的研究已有较多报道「’‘,但模拟生理条件下稀土离子与羟脯氨酸、瓜氨酸的二元、三元配合物的PH电位法研究尚未见报道.本文报道在模拟生理条件下(37C,0·15mol/LNaCI)湖系离子(Pm和Lu除外)与上述2种氨基酸的二元及三元配合物PH电位法研究结果.1实验部分1.1试剂和仪… 相似文献