全文获取类型
收费全文 | 83篇 |
免费 | 5篇 |
专业分类
化学 | 72篇 |
数学 | 10篇 |
物理学 | 6篇 |
出版年
2023年 | 4篇 |
2021年 | 2篇 |
2020年 | 4篇 |
2019年 | 5篇 |
2018年 | 2篇 |
2016年 | 2篇 |
2015年 | 1篇 |
2014年 | 1篇 |
2013年 | 1篇 |
2012年 | 8篇 |
2011年 | 4篇 |
2010年 | 10篇 |
2009年 | 8篇 |
2008年 | 5篇 |
2007年 | 9篇 |
2006年 | 1篇 |
2005年 | 3篇 |
2004年 | 2篇 |
2003年 | 2篇 |
2000年 | 1篇 |
1998年 | 1篇 |
1991年 | 1篇 |
1989年 | 1篇 |
1987年 | 1篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1979年 | 3篇 |
1978年 | 1篇 |
1972年 | 2篇 |
排序方式: 共有88条查询结果,搜索用时 281 毫秒
1.
Dr. Anna Notaro Marta Jakubaszek Severin Koch Dr. Riccardo Rubbiani Dr. Orsolya Dömötör Dr. Éva A. Enyedy Mazzarine Dotou Dr. Fethi Bedioui Mickaël Tharaud Dr. Bruno Goud PD Dr. Stefano Ferrari Prof. Dr. Enzo Alessio Dr. Gilles Gasser 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(22):4997-5009
Cancer is one of the main causes of death worldwide. Chemotherapy, despite its severe side effects, is to date one of the leading strategies against cancer. Metal-based drugs present several potential advantages when compared to organic compounds and they have gained trust from the scientific community after the approval on the market of the drug cisplatin. Recently, we reported the ruthenium complex ([Ru(DIP)2(sq)](PF6) (where DIP is 4,7-diphenyl-1,10-phenantroline and sq is semiquinonate) with a remarkable potential as chemotherapeutic agent against cancer, both in vitro and in vivo. In this work, we analyse a structurally similar compound, namely [Ru(DIP)2(mal)](PF6), carrying the flavour-enhancing agent approved by the FDA, maltol (mal). To possess an FDA approved ligand is crucial for a complex, whose mechanism of action might include ligand exchange. Herein, we describe the synthesis and characterisation of [Ru(DIP)2(mal)](PF6), its stability in solutions and under conditions that resemble the physiological ones, and its in-depth biological investigation. Cytotoxicity tests on different cell lines in 2D model and on HeLa MultiCellular Tumour Spheroids (MCTS) demonstrated that our compound has higher activity than cisplatin, inspiring further tests. [Ru(DIP)2(mal)](PF6) was efficiently internalised by HeLa cells through a passive transport mechanism and severely affected the mitochondrial metabolism. 相似文献
2.
3.
Dirk Schlüter Florian Kleemiss Dr. Malte Fugel Dr. Enno Lork Prof. Dr. Kunihisa Sugimoto PD Dr. Simon Grabowsky Prof. Dr. Jeffrey R. Harmer Dr. Matthias Vogt 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(6):1335-1343
Derivatives of 1,2-dithienylethene (DTE) have superb photochromic properties due to an efficient reversible photocyclization reaction of their hexatriene structure and, thus, have application potential in materials for optoelectronics and (multi-responsive) molecular switches. Transition-metal complexes bearing switchable DTE motifs commonly incorporate their coordination site rather distant from the hexatriene system. In this work the redox active ligand 1,2-bis(2,5-dimethylthiophen-3-yl)ethane-1,2-dione is described, which reacts with [V(TMEDA)2Cl2] to give a rare non-oxido vanadium(IV) species 3(M,M/P,P) . This blue complex has two bidentate en-diolato ligands which chelate the VIV center and give rise to two five-membered metallacycles with the adjacent hexatriene DTE backbone bearing axial chirality. Upon irradiation with UVA light or prolonged heating in solution, the blue compound 3(M,M/P,P) converts into the purple atropisomer 4(para,M/para,P) . Both complexes were isolated and structurally characterized by single-crystal X-ray diffraction analysis (using lab source and synchrotron radiation). The antiparallel configuration (M or P helicity) present in both 3(M,M/P,P) and 4(para,M/para,P) is a prerequisite for (reversible) 6π cyclization reactions. A CW EPR spectroscopic study reveals the metalloradical character for 3(M,M/P,P) and 4(para,M/para,P) and indicates dynamic reversible cyclization of the DTE backbone in complex 3(M,M/P,P) at ambient temperature in solution. 相似文献
4.
Electrochemiluminescence Bioassays with a Water‐Soluble Luminol Derivative Can Outperform Fluorescence Assays 下载免费PDF全文
Michael Mayer Prof. Dr. Shigehiko Takegami Michael Neumeier Simone Rink Prof. Dr. Axel Jacobi von Wangelin Silja Schulte Moritz Vollmer Prof. Dr. Axel G. Griesbeck PD Dr. Axel Duerkop Prof. Dr. Antje J. Baeumner 《Angewandte Chemie (International ed. in English)》2018,57(2):408-411
The most efficient and commonly used electrochemiluminescence (ECL) emitters are luminol, [Ru(bpy)3]2+, and derivatives thereof. Luminol stands out due to its low excitation potential, but applications are limited by its insolubility under physiological conditions. The water‐soluble m‐carboxy luminol was synthesized in 15 % yield and exhibited high solubility under physiological conditions and afforded a four‐fold ECL signal increase (vs. luminol). Entrapment in DNA‐tagged liposomes enabled a DNA assay with a detection limit of 3.2 pmol L?1, which is 150 times lower than the corresponding fluorescence approach. This remarkable sensitivity gain and the low excitation potential establish m‐carboxy luminol as a superior ECL probe with direct relevance to chemiluminescence and enzymatic bioanalytical approaches. 相似文献
5.
H. Joseph Straight 《Journal of Graph Theory》1979,3(1):43-51
The cochromatic number of a graph G, denoted by z(G), is the minimum number of subsets into which the vertex set of G can be partitioned so that each sbuset induces an empty or a complete subgraph of G. In this paper we introduce the problem of determining for a surface S, z(S), which is the maximum cochromatic number among all graphs G that embed in S. Some general bounds are obtained; for example, it is shown that if S is orientable of genus at least one, or if S is nonorientable of genus at least four, then z(S) is nonorientable of genus at least four, then z(S)≤χ(S). Here χ(S) denotes the chromatic number S. Exact results are obtained for the sphere, the Klein bottle, and for S. It is conjectured that z(S) is equal to the maximum n for which the graph Gn = K1 ∪ K2 ∪ … ∪ Kn embeds in S. 相似文献
6.
H. Joseph Straight 《Journal of Graph Theory》1980,4(1):115-117
The cochromatic number of a graph G, denoted by z(G), is the minimum number of subsets into which the vertex set of G can be partitioned so that each subset induces an empty or a complete subgraph of G. In an earlier work, the author considered the problem of determining z(S), the maximum cochromatic number among all graphs that embed in a surface S. The value of z(S) was found for the sphere, the Klein bottle, and for the nonorientable surface of genus 4. In this note, some recent results of Albertson and Hutchinson are used to determine the cochromatic numbers of the projective plane and the nonorientable surface of genus 3. These results lend further evidence to support the conjecture that z(S) is equal to the maximum n for which the graph Gn = K1 U K2 U … U Kn embeds in S. 相似文献
7.
We present a combined Monte‐Carlo/molecular dynamics study of a Cu0.327Ni0.673 alloy system. On the basis of nearest‐neighbor coordination number analyses atomic clustering and phase segregation is explored. Along this line, free energy profiles are calculated and separated into entropic and energetic contributions. The competition of both terms was found in accordance to the experimental phase diagrams (phase separation of the solid solution below about 600 Kelvin). Two independent simulation runs were performed. At 1000 Kelvin the observed configurations correspond to solid solutions exhibiting a weak tendency to cluster atoms of identical species. At room temperature the energetic favoring of atomic separation is clearly dominant and leads to the formation of Ni‐rich and Cu‐rich domains. The latter are separated by interfacial regions whose width ranges from 0.5 to 1 nanometers. 相似文献
8.
Reaction of iron(II) thiocyanate with 4,4‐bipyridine (bipy) in methanol leads to the formation of three new solvates of different composition depending on the reaction conditions: At room temperature two new ligand‐rich 1:2 (1:2 = ratio between metal and N‐donor ligand) polymorphic forms [Fe(NCS)2(bipy)2 · 2MeOH]n ( 1I ) and [Fe(NCS)2(bipy)(MeOH)2 · (bipy)]n ( 1II ) are obtained, whereas solvothermal conditions leads to the formation of the new ligand‐deficient 1:1 compound [{Fe(NCS)2(bipy)(MeOH)}2]n ( 2 ). All crystal structures were determined by X‐ray single crystal structure analysis. In the crystal structure of modification 1I the metal atoms are coordinated by four bridging bipy ligands, which connect them into layers. The methanol molecules occupy voids in the structure. Compared to 1I in modification 1II the crystal structure contains of linear Fe–bipy–Fe chains, which are further connected by hydrogen bonds between coordinating MeOH and noncoordinated bipy ligands into layers. The ligand‐deficient 1:1 compound 2 shows a completely different coordination topology with linear Fe–bipy–Fe chains, which are connected by coordinating methanol molecules into double‐chains. In all compounds the thiocyanato anions are terminal N‐bonded to the metal atoms. Investigation of the thermal behavior of compound 1I shows a two‐step decomposition, in which ligand‐deficient intermediates are formed. Magnetic measurements on 1I reveal Curie–Weiss paramagnetism with increasing antiferromagnetic interactions on cooling. 相似文献
9.
10.
C.D. Lytle P.G. Carney R.P. Felten H.F. Bushar R.C. Straight 《Photochemistry and photobiology》1989,50(3):367-371
Dyes which photosensitize membranes may be clinically useful for photodynamic treatment (PDT) of Herpes simplex virus (HSV) infections. It is important to determine whether the enveloped HSV can be inactivated via membrane damage without affecting the genetic material. Selection of appropriate PDT conditions, including the choice of dye, could minimize viral mutagenesis. We determined the mutagenesis caused by PDT employing three membrane-photosensitizing dyes of potential use in cancer photochemotherapy (Photofrin II, polyhematoporphyrin esters, zinc phthalocyanine tetrasulfonates) and a DNA-photosensitizing dye (proflavine sulfate). The effects were compared to those caused by exposure of HSV to ultraviolet radiation (UV). The procedure consisted of incubating HSV with microgram/ml (microM) concentrations of the dye, irradiating the samples with broad spectrum visible/near-UV radiation (Daylight fluorescent lamps) and assaying the survival of the treated HSV. Zinc phthalocyanine was the most potent dye per absorbed photon for inactivating HSV. In parallel with determination of survival, progeny of the surviving virus were grown for determination of mutagenesis. The progeny virus was harvested and subsequently assayed in the presence and absence of 40 micrograms/ml iododeoxycytidine (ICrd) to determine the frequency of mutation to ICrd resistance. Mutation frequencies were determined for progeny from the 1-4% survival level. For PDT with each membrane-photosensitizing dye, only zinc phthalocyanine increased the mutation frequency over the untreated control. This increase was less than 2-fold. Proflavine increased the mutation frequency 2-3 fold over the untreated control. Ultraviolet produced a 15-20 fold increase over the untreated control.(ABSTRACT TRUNCATED AT 250 WORDS) 相似文献