全文获取类型
收费全文 | 144篇 |
免费 | 5篇 |
专业分类
化学 | 116篇 |
力学 | 4篇 |
数学 | 13篇 |
物理学 | 16篇 |
出版年
2023年 | 5篇 |
2021年 | 4篇 |
2020年 | 5篇 |
2019年 | 6篇 |
2018年 | 2篇 |
2016年 | 3篇 |
2015年 | 2篇 |
2014年 | 2篇 |
2013年 | 2篇 |
2012年 | 16篇 |
2011年 | 11篇 |
2010年 | 12篇 |
2009年 | 11篇 |
2008年 | 8篇 |
2007年 | 8篇 |
2006年 | 4篇 |
2005年 | 1篇 |
2004年 | 1篇 |
2003年 | 3篇 |
2002年 | 1篇 |
2001年 | 1篇 |
2000年 | 3篇 |
1998年 | 3篇 |
1997年 | 1篇 |
1996年 | 1篇 |
1995年 | 2篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1987年 | 2篇 |
1986年 | 1篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1979年 | 2篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1972年 | 2篇 |
1970年 | 1篇 |
1942年 | 3篇 |
1941年 | 1篇 |
1935年 | 2篇 |
排序方式: 共有149条查询结果,搜索用时 15 毫秒
1.
R. P. Hallett K. G. McKay S. P. Balm A. W. Allaf H. W. Kroto A. J. Stace 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1995,34(1):65-70
Reaction studies of carbon clustersC
n
in the rangen=8–37, produced by laser vaporisation in a supersonic nozzle, have been investigated using time-of-flight mass spectrometry. Clear differences in reaction products formed on hydrogenation are detected which show that even and odd clusters behave quite differently and furthermore thatat least two different types of even cluster appear to exist. The reactivity patterns for clusters C
n
withn=16, 18 and 22 are in a different class from those withn=20, 24, 26 ..., a behaviour consistent with the existence of closed cage fullerene structures for even clusters with 20 or more carbon atoms (other thann=22). 相似文献
2.
Handley LL Johnston AM Hallett PD Scrimgeour CM Wheatley RE 《Rapid communications in mass spectrometry : RCM》2001,15(15):1274-1278
New evidence, obtained using a robust method for measuring the delta(15)N of NO(3)(-)-N in soil, is consistent with denitrification being the major determinant in the vertical distribution of NO(3)(-)-delta(15)N in soil profiles. These data also suggest that varying moisture regimes result in different effects of soil NO(3)(-)-N leaching on residual whole soil delta(15)N. 相似文献
3.
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
4.
5.
The assembly of colloidal particles in a nematic liquid crystal has been investigated using small-angle X-ray scattering. The structure and orientation of nanoparticle assemblies in bulk samples of aligned nematic liquid crystal have been determined. The method offers some advantages over optical microscopy, which is usually restricted to investigations of thin cells and micron-sized particles. The scattering from chains of particles has been calculated, and comparison with experimental results has shown that suspensions of 48 and 105 nm diameter silica nanoparticles formed highly ordered structures perpendicular to the liquid crystal director, consistent with quadrupolar defect-induced assembly. 相似文献
6.
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
7.
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
8.
Chung MK Orlova G Goddard JD Schlaf M Harris R Beveridge TJ White G Hallett FR 《Journal of the American Chemical Society》2002,124(35):10508-10518
Palladium(0)-catalyzed silane alcoholysis was applied to sugars for the first time using tert-butyldimethylsilane (TBDMS-H) and Ph(3)SiH as the silanes. The catalyst is a colloidal solution of Pd(0) generated in situ from PdX(2) (X = Cl(-), OAc(-)) and TBDMS-H in N,N-dimethylacetamide. The colloid has been characterized by dynamic light scattering and transmission electron microscopy and consists of catalytically highly active nanoparticles of approximately 2 nm diameter. The silane alcoholysis reaction is an effective method for the regioselective silylation of methyl and phenyl glycosides and generates hydrogen gas as the only side product. For many of the sugar substrates investigated, the distribution of regioisomers obtained is complementary to that of the traditional R(3)SiCl/base (base = pyridine, imidazole) methodology and gives convenient access to the 3,6- rather than the 2,6-silylated pyranosides, obtained as the main product by the silyl chloride method. The method also allows a selective axial silylation of levoglucosan and 1,3,5-O-methylidene-myo-inositol. In an attempt to rationalize the observed regioselectivities, ab initio predictions (HF/3-21G) have been made on the relative energies of some of the silylated products. They suggest that the observed regioselectivities do not reflect a kinetic vs thermodynamic product distribution but are induced by the silylation agent employed. Models for the possible origin of the observed regioselectivity in both silylation methods (silane- and silyl chloride-based) are discussed. 相似文献
9.
10.
Stephen A. Eastham Michael R. Hallett Andrea Modi James E. Painter Peter Quayle Dean C. Ricketts 《Tetrahedron》2008,64(5):936-948
The development of a formal synthesis of aflatoxin B2 is described, which utilizes a Dötz benzannulation reaction as a key step. 相似文献