全文获取类型
收费全文 | 572篇 |
免费 | 29篇 |
国内免费 | 3篇 |
专业分类
化学 | 463篇 |
晶体学 | 4篇 |
力学 | 11篇 |
数学 | 80篇 |
物理学 | 46篇 |
出版年
2022年 | 9篇 |
2021年 | 12篇 |
2020年 | 8篇 |
2019年 | 10篇 |
2018年 | 10篇 |
2017年 | 2篇 |
2016年 | 14篇 |
2015年 | 22篇 |
2014年 | 15篇 |
2013年 | 25篇 |
2012年 | 42篇 |
2011年 | 57篇 |
2010年 | 29篇 |
2009年 | 32篇 |
2008年 | 40篇 |
2007年 | 32篇 |
2006年 | 30篇 |
2005年 | 27篇 |
2004年 | 24篇 |
2003年 | 27篇 |
2002年 | 20篇 |
2001年 | 9篇 |
2000年 | 4篇 |
1999年 | 6篇 |
1998年 | 5篇 |
1997年 | 6篇 |
1996年 | 4篇 |
1994年 | 3篇 |
1993年 | 5篇 |
1992年 | 3篇 |
1991年 | 3篇 |
1989年 | 4篇 |
1988年 | 5篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 6篇 |
1984年 | 5篇 |
1983年 | 3篇 |
1982年 | 2篇 |
1981年 | 5篇 |
1980年 | 5篇 |
1979年 | 3篇 |
1978年 | 3篇 |
1977年 | 2篇 |
1976年 | 4篇 |
1975年 | 2篇 |
1974年 | 4篇 |
1973年 | 2篇 |
1955年 | 2篇 |
1954年 | 1篇 |
排序方式: 共有604条查询结果,搜索用时 0 毫秒
41.
Feltham HL Klöwer F Cameron SA Larsen DS Lan Y Tropiano M Faulkner S Powell AK Brooker S 《Dalton transactions (Cambridge, England : 2003)》2011,40(43):11425-11432
A family of thirteen tetranuclear heterometallic zinc(II)-lanthanide(III) complexes of the hexa-imine macrocycle (L(Pr))(6-), with general formula Zn(II)(3)Ln(III)(L(Pr))(NO(3))(3)·xsolvents (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm or Yb), were prepared in a one-pot synthesis using a 3:1:3:3 reaction of zinc(II) acetate, the appropriate lanthanide(III) nitrate, the dialdehyde 1,4-diformyl-2,3-dihydroxybenzene (H(2)L(1)) and 1,3-diaminopropane. A hexanuclear homometallic zinc(II) macrocyclic complex [Zn(6)(L(Pr))(OAc)(5)(OH)(H(2)O)]·3H(2)O was obtained using a 2:0:1:1 ratio of the same reagents. A control experiment using a 1:0:1:1 ratio failed to generate the lanthanide-free [Zn(3)(L(Pr))] macrocyclic complex. The reaction of H(2)L(1) and zinc(II) acetate in a 1:1 ratio yielded the pentanuclear homometallic complex of the dialdehyde H(2)L(1), [Zn(5)(L(1))(5)(H(2)O)(6)]·3H(2)O. An X-ray crystal structure determination revealed [Zn(3)(II)Pr(III)(L(Pr))(NO(3))(2)(DMF)(3)](NO(3))·0.9DMF has the large ten-coordinate lanthanide(III) ion bound in the central O(6) site with two bidentate nitrate anions completing the O(10) coordination sphere. The three square pyramidal zinc(II) ions are in the outer N(2)O(2) sites with a fifth donor from DMF. Measurement of the magnetic properties of [Zn(II)(3)Dy(III)(L(Pr))(NO(3))(3)(MeOH)(3)]·4H(2)O with a weak external dc field showed that it has a frequency-dependent out-of-phase component of ac susceptibility, indicative of slow relaxation of the magnetization (SMM behaviour). Likewise, the Er and Yb analogues are field-induced SMMs; the latter is only the second example of a Yb-based SMM. The neodymium, ytterbium and erbium complexes are luminescent in the solid phase, but only the ytterbium and neodymium complexes show strong lanthanide-centred luminescence in DMF solution. 相似文献
42.
Amily Fang-ju Jou Chun-Hua Lu Yen-Chuan Ou Shian-Shiang Wang Shih-Lan Hsu Itamar Willner Ja-an Annie Ho 《Chemical science》2015,6(1):659-665
The microRNA, miR-141, is a promising biomarker for prostate cancer. We implement here a two-step sensing platform for the sensitive detection of miR-141. The first step involves the use of semiconductor CdSe/ZnS quantum dots (QDs) modified by FRET quencher-functionalized nucleic acids, that include the recognition sequence for miR-141 and a telomerase primer sequence for the second step of the analytical platform. Subjecting the probe-modified QDs to miR-141, in the presence of duplex specific nuclease, DSN, leads to the formation of a miR-141/probe duplex and to its DSN-mediated cleavage, while regenerating the miR-141. The DSN-induced cleavage of the quencher units leads to the activation of the fluorescence of the QDs, thus allowing the optical detection of miR-141 with a sensitivity corresponding to 1.0 × 10–12 M. The nucleic acid residues associated with the QDs after cleavage of the probe nucleic acids by DSN act as primers for telomerase. The subsequent telomerase/dNTPs-stimulated elongation of the primer units forms G-quadruplex telomer chains. Incorporation of hemin in the resulting G-quadruplex telomer chains yields horseradish peroxidase-mimicking DNAzyme units, that catalyze the generation of chemiluminescence in the presence of luminol/H2O2. The resulting chemiluminescence intensities provide a readout signal for miR-141, DL = 2.8 × 10–13 M. The first step of the sensing platform is non-selective toward miR-141 and the resulting fluorescence may be considered only as an indicator for the existence of miR-141. The second step in the sensing protocol, involving telomerase, provides a selective chemiluminescence signal for the existence of miR-141. The two-step sensing platform is implemented for the analysis of miR-141 in serum samples from healthy individuals and prostate cancer carriers. Impressive discrimination between healthy individuals and prostate cancer carriers is demonstrated. 相似文献
43.
Dr. Guo Peng Dr. Valeriu Mereacre Dr. George E. Kostakis Dr. Juliusz A. Wolny Prof.Dr. Volker Schünemann Prof. Dr. Annie K. Powell 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(39):12381-12384
Two [FeLn2Fe(μ3‐OH)2(teg)2(N3)2(C6H5COO)4] compounds (where Ln=YIII and DyIII; teg=triethylene glycol anion) have been synthesized and studied using SQUID and Mössbauer spectroscopy. The magnetic measurements on both compounds indicate dominant antiferromagnetic interactions between the metal centers. Analysis of the 57Fe Mössbauer spectra complement the ac magnetic susceptibility measurements, which show how a static magnetic field can quench the slow relaxation of magnetization generated by the anisotropic DyIII ions. 相似文献
44.
45.
Annie Praud-Tabaries 《Tetrahedron letters》2009,50(14):1645-6755
A terpenoid-like library containing 1,4-disubstituted-(1H)-1,2,3-triazoles was prepared by means of 1,3-dipolar cycloaddition of geranyl and farnesyl azides with a set of terminal alkynes, in order to design a new class of potentially active anti-biofilm compounds. Reactions were optimized to proceed under mild conditions and in high yields. Two compounds were found to possess interesting activity against Pseudoalteromonas sp. biofilm. This process is suitable for combinatorial chemistry of marine natural product-like compounds. 相似文献
46.
Decomposition of dinuclear manganese complexes for the preparation of nanostructured oxide materials
Hill JP Palza H Alam S Ariga K Schumacher AL D'Souza F Anson CE Powell AK 《Inorganic chemistry》2008,47(18):8306-8314
The crystal structures of several dinuclear complexes of manganese are reported, and the decomposition and analysis of the nanostructured products derived from them are presented. 1,4,7,10-Tetraazacyclododecane (cyclen) forms dinuclear complexes 1-4 containing doubly oxo-bridged or oxo-acetato bridging ligands depending on the manganese salt used for the reaction. Doubly oxo-bridged 1 crystallizes in the orthorhombic space group Pnma, a = 22.3850(14) A, b = 9.1934(5) A, c = 13.2424(10) A, V = 2725.2(3) A(3). 2, containing [Mn(SCN)5](3-) conteranions, crystallizes in monoclinic space group I2/a with a = 18.2699(10) A, b = 11.2384(6) A, c = 18.6432(9) A, alpha = 90.00 degrees, beta = 114.510(6) degrees, gamma = 90.00 degrees, V = 3483.0(3) A(3). Oxo-acetato-bridged 3 crystallizes in orthorhombic space group Pca21, a = 13.9322(11) A, b = 16.2332(13) A, c = 14.6794(8) A, V = 3320.0(4) A(3). Compound 4 consists of a templated quasi-one-dimensional manganese oxalate crystallized in the triclinic space group P1, a = 9.5442(11) A, b = 10.3758(10) A, c = 21.851(2) A, alpha = 83.720(12) degrees, beta = 80.106(13) degrees, gamma = 85.457(13) degrees, V = 2114.9(4) A(3). Compounds 1, 3, and 4 decompose to nanostructured oxide materials, which may be isolated in bulk as lamellar-structured particles or microspheres or deposited on substrates. 相似文献
47.
Philippini V Vercouter T Aupiais J Topin S Ambard C Chaussé A Vitorge P 《Electrophoresis》2008,29(10):2041-2050
The electrophoretic mobilities (mu ep,Ln) of twelve lanthanides (not Ce, Pr and Yb) were measured by CE-ICP-MS in 0.15 and 0.5 mol L(-1) Alk2 CO3 aqueous solutions for Alk+ = Li+, Na+, K+ and Cs+. In 0.5 mol L(-1) solutions, two different mu ep,Ln values were found for the light (La to Nd) and the heavy (Dy to Tm) lanthanides, which suggests two different stoichiometries for the carbonate limiting complexes. These results are consistent with a solubility study that attests the Ln(CO3)3(3-) and Ln(CO3)4(5-) stoichiometries for the heavy (small) and the light (big) lanthanides, respectively. The Alk+ counterions influence the mu ep,Ln Alk2 CO3 values, but not the overall shape of the mu ep,Ln Alk2 CO3 plots as a function of the lanthanide atomic numbers: the counterions do not modify the stoichiometries of the inner sphere complexes. The influence of the Alk+ counterions decreases in the Li+ > Na+ > K+ > Cs+ series. The K3,Ln stepwise formation constants of the Ln(CO3)3(3-) complexes slightly increase with the atomic numbers of the lanthanides while K4,Ln, the stepwise formation constants of Ln(CO3)4(5-) complexes, slightly decrease from La to Tb, and is no longer measurable for heavier lanthanides. 相似文献
48.
5-Aroyl-6-(methylsulfanyl)-2-oxo-1,2-dihydro-3-pyridinecarbonitriles and 5-aroyl-4-(methylsulfanyl)-2-oxo-1,2-dihydro-3-pyridinecarbonitriles are synthesized effectively by the reaction of 2-aroyl-3,3-bis(alkylsulfanyl)acrylaldehydes and cyanoacetamide under two different conditions. 相似文献
49.
Two planar tetranuclear dysprosium(III) complexes, [Dy(4)(mu(3)-OH)(2)(hmmpH)(2)(hmmp)(2)(Cl)(4)].3MeCN.MeOH (1) and [Dy(4)(mu(3)-OH)(2)(hmmpH)(2)(hmmp)(2)(N(3))(4)].4MeOH (2) {hmmpH(2) = 2-[(2-hydroxyethylimino)methyl]-6-methoxyphenol}, which exhibit an anion-dependent magnetic slow relaxation behavior, have been synthesized by in situ condensation of o-vanillin and 2-aminoethanol. The higher energy barrier observed in 2 could be the result of a more favorable crystal field and/or orientations of single-ion easy axes of magnetization of the Dy(III) ions. 相似文献
50.