全文获取类型
收费全文 | 6249篇 |
免费 | 98篇 |
国内免费 | 40篇 |
专业分类
化学 | 4255篇 |
晶体学 | 48篇 |
力学 | 141篇 |
数学 | 1077篇 |
物理学 | 866篇 |
出版年
2024年 | 33篇 |
2023年 | 47篇 |
2022年 | 140篇 |
2021年 | 195篇 |
2020年 | 138篇 |
2019年 | 176篇 |
2018年 | 123篇 |
2017年 | 92篇 |
2016年 | 207篇 |
2015年 | 186篇 |
2014年 | 213篇 |
2013年 | 367篇 |
2012年 | 408篇 |
2011年 | 454篇 |
2010年 | 293篇 |
2009年 | 293篇 |
2008年 | 364篇 |
2007年 | 376篇 |
2006年 | 357篇 |
2005年 | 339篇 |
2004年 | 253篇 |
2003年 | 187篇 |
2002年 | 193篇 |
2001年 | 86篇 |
2000年 | 69篇 |
1999年 | 64篇 |
1998年 | 46篇 |
1997年 | 46篇 |
1996年 | 75篇 |
1995年 | 40篇 |
1994年 | 39篇 |
1993年 | 37篇 |
1992年 | 46篇 |
1991年 | 33篇 |
1990年 | 21篇 |
1989年 | 28篇 |
1988年 | 22篇 |
1987年 | 21篇 |
1986年 | 25篇 |
1985年 | 44篇 |
1984年 | 30篇 |
1983年 | 22篇 |
1982年 | 29篇 |
1981年 | 18篇 |
1980年 | 20篇 |
1979年 | 15篇 |
1978年 | 12篇 |
1977年 | 7篇 |
1975年 | 8篇 |
1974年 | 7篇 |
排序方式: 共有6387条查询结果,搜索用时 0 毫秒
61.
62.
Alexander Classen's Martin Kiliani Edgar F. Smith W. S. Hoskinson Luis de la Escosura Horacio Bentabol und Alexander Classen 《Fresenius' Journal of Analytical Chemistry》1886,25(1):403-406
Ohne Zusammenfassung 相似文献
63.
Synthesis of an N-protected derivative of 2-amino-2'-deoxyadenosine (dA') from 2'-deoxyguanosine is reported. The syntheses of several oligodeoxynucleotides containing this modified nucleoside are described, together with physical characterization via melting studies and CD conformational analysis. As expected, the 2-amino group is seen to add to the duplex stability. Although the sequence d(TA')3 was found to undergo a salt-induced conformational transition, mixed sequences such as d(CGTA'CG) did not display this behavior. All guanine residues present in these sequences were O6 protected, either with the cyanoethyl group or the 4-nitrophenylethyl group, to eliminate guanine degradation during phosphorylation and condensation reactions. Procedures for the introduction and removal of these O6 protecting groups are described. 相似文献
64.
Superoxide generated in DMF readily converts the dihalovinyl group of permethrin and related compounds to a haloethynyl moiety and yields major products from elimination reactions of DDT, -chlordane, and 1,2-dibromo-3-chloropropane (DBCP). 相似文献
65.
María Del Carmen Chacn María Del Carmen Pardot Jos Luis Soto Antonio Lorente Luis Fuentes 《Journal of heterocyclic chemistry》1982,19(2):421-423
Reaction of cinnamonitriles with malononitrile, in methanolmethoxide, yield dihydropyridines, which by aromatisation give pyridines. Pyridine is directly obtained when p-nitrocinnamonitrile is used 相似文献
66.
Dr. Thais F. Abelha Dr. Graeme Morris Dr. Sandro M. Lima Dr. Luis H. C. Andrade Dr. Andrew J. McLean Prof. Cameron Alexander Dr. Jesus Calvo-Castro Dr. Callum J. McHugh 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(14):3173-3180
Development of novel bioimaging materials that exhibit organelle specific accumulation continues to be at the forefront of research interests and efforts. Among the various subcellular organelles, mitochondria, which are found in the cytoplasm of eukaryotic cells, are of particular interest in relation to their vital function. To date, most molecular probes that target mitochondria utilise delocalised lipophilic cations such as triphenylphosphonium and pyridinium. However, the use of such charged motifs is known to be detrimental to the working function of the mitochondrial transmembrane potential and there remains a strong case for development of neutral mitochondrial fluorescent probes. Herein, we demonstrate for the first time the exploitation of diketopyrrolopyrrole-based chemistries for the realisation of a neutral fluorescent probe that exhibits organelle specific accumulation within the mitochondria at the nanomolar level. The synthesised probe, which bears a neutral triphenylphosphine oxide moiety, exhibits a large Stokes shift and high fluorescence quantum yield in water, both highly sought-after properties in the development of bioimaging agents. In vitro studies reveal no interference with cell metabolism when tested for the human MCF7 breast cancer cell and nanomolar subcellular organelle colocalisation with commercially available mitochondrial staining agent Mitotracker Red. In light of its novelty, neutral structure and the preferential accumulation at nanomolar concentrations we anticipate this work to be of significant interest for the increasingly larger community devoted to the realisation of neutral mitochondrial selective systems and more widely to those engaged in the rational development of superior organic architectures in the biological field. 相似文献
67.
Dr. Boris Schade Dr. Abhishek Kumar Singh Dr. Virginia Wycisk Dr. Jose Luis Cuellar-Camacho Dr. Hans von Berlepsch Prof. Rainer Haag Dr. Christoph Böttcher 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(30):6919-6934
The syntheses of novel amphiphilic 5,5′,6,6′-tetrachlorobenzimidacarbocyanine (TBC) dye derivatives with aminopropanediol head groups, which only differ in stereochemistry (chiral enantiomers, meso form and conformer), are reported. For the achiral meso form, a new synthetic route towards asymmetric cyanine dyes was established. All compounds form J aggregates in water, the optical properties of which were characterised by means of spectroscopic methods. The supramolecular structure of the aggregates is investigated by means of cryo-transmission electron microscopy, cryo-electron tomography and AFM, revealing extended sheet-like aggregates for chiral enantiomers and nanotubes for the mesomer, respectively, whereas the conformer forms predominately needle-like crystals. The experiments demonstrate that the aggregation behaviour of compounds can be controlled solely by head group stereochemistry, which in the case of enantiomers enables the formation of extended hydrogen-bond chains by the hydroxyl functionalities. In case of the achiral meso form, however, such chains turned out to be sterically excluded. 相似文献
68.
Yeray Dorca Roberto Sánchez-Naya Jesús Cerdá Dr. Joaquín Calbo Dr. Juan Aragó Dr. Rafael Gómez Prof. Dr. Enrique Ortí Prof. Dr. Luis Sánchez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(64):14700-14707
A comparative investigation of the chiral amplification features of a series of three families of C3-symmetric tricarboxamides, 1,3,5-triphenylbenzenetricarboxamides (TPBAs), benzenetricarboxamides (BTAs) and oligo(phenylene ethynylene) tricarboxamides (OPE-TAs), is here reported. As previously observed for BTAs and OPE-TAs, a similar dichroic response is obtained for TPBAs decorated with one, two or three chiral side chains bearing stereogenic centers, thus confirming the efficient transfer of point chirality to the supramolecular helical aggregates. Unlike BTAs and OPE-TAs, the chiral amplification ability of TPBAs in majority rules experiments shows a negligible dependence on the number of chiral centers per monomeric unit, and stands the largest among the series of tricarboxamides. Detailed experimental and theoretical studies demonstrate that the rotation angle between the TPBA units in the helical stack is intermediate to that observed for BTAs and OPE-TAs. This feature strongly conditions the steric interactions between vicinal molecules in the stack and the final chiral amplification outcome. Furthermore, theoretical calculations show that achiral side chains favor the interdigitation of the helical aggregates and thereby the formation of bundle superstructures. 相似文献
69.
Dr. Luis Martín-Gomis Sairaman Seetharaman David Herrero Prof. Dr. Paul A. Karr Prof. Dr. Fernando Fernández-Lázaro Prof. Dr. Francis D'Souza Prof. Dr. Ángela Sastre-Santos 《Chemphyschem》2020,21(20):2254-2262
The effect of donor-acceptor distance in controlling the rate of electron transfer in axially linked silicon phthalocyanine-C60 dyads has been investigated. For this, two C60-SiPc-C60 dyads, 1 and 2 , varying in their donor-acceptor distance, have been newly synthesized and characterized. In the case of C60-SiPc-C60 1 where the SiPc and C60 are separated by a phenyl spacer, faster electron transfer was observed with kcs equal to 2.7×109 s−1 in benzonitrile. However, in the case of C60-SiPc-C60 2 , where SiPc and C60 are separated by a biphenyl spacer, a slower electron transfer rate constant, kcs=9.1×108 s−1, was recorded. The addition of an extra phenyl spacer in 2 increased the donor-acceptor distance by ∼4.3 Å, and consequently, slowed down the electron transfer rate constant by a factor of ∼3.7. The charge separated state lasted over 3 ns, monitoring time window of our femtosecond transient spectrometer. Complimentary nanosecond transient absorption studies revealed formation of 3SiPc* as the end product and suggested the final lifetime of the charge separated state to be in the 3–20 ns range. Energy level diagrams established to comprehend these mechanistic details indicated that the comparatively high-energy SiPc.+-C60.− charge separated states (1.57 eV) populated the low-lying 3SiPc* (1.26 eV) prior returning to the ground state. 相似文献
70.