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排序方式: 共有196条查询结果,搜索用时 156 毫秒
41.
A.F. Maarten Altelaar Ioana M. Taban Liam A. McDonnell Peter D.E.M. Verhaert Robert P.J. de Lange Roger A.H. Adan Wolter J. Mooi Ron M.A. Heeren Sander R. Piersma 《International journal of mass spectrometry》2007,260(2-3):203
Matrix assisted laser desorption/ionization (MALDI) imaging mass spectrometry (IMS) has been used to determine peptide distributions directly from rat, mouse and human pituitary tissue sections. Since these organs are small (102–103 μm) the spatial resolution of IMS is a key issue in molecular imaging of pituitary tissue sections. Here we show that high-resolution IMS allows localization of neuropeptide distributions within different cell clusters of a single organ of a pituitary tissue section. The sample preparation protocol does not result in analyte redistribution and is therefore applicable to IMS experiments at cellular length scales. The stigmatic imaging mass spectrometer used in this study produces selected-ion-count images with pixel sizes of 500 nm and a resolving power of 4 μm, yielding superior spatial detail compared to images obtained in microprobe imaging experiments. Furthermore, we show that with imaging mass spectrometry a distinction can be made between different mammalian tissue sections based on differences in the amino acid sequence of neuropeptides with the same function. This example demonstrates the power of IMS for label-free molecular imaging at relevant biological length scales. 相似文献
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43.
Dr. Valentin Magné Dr. Liam T. Ball 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(37):8903-8910
Thiophenols are versatile synthetic intermediates whose practical appeal is marred by their air sensitivity, toxicity and extreme malodor. Herein we report an efficient catalytic method for the preparation of S-aryl isothiouronium salts, and demonstrate that these air-stable, odorless solids serve as user-friendly sources of thiophenols in synthesis. Diverse isothiouronium salts featuring synthetically useful functionality are readily accessible by nickel-catalyzed C−S cross-coupling of (hetero)aryl iodides and thiourea. Convenient, chromatography-free isolation of these salts is achieved by precipitation, allowing the methodology to be applied directly to large scales. Thiophenols are liberated from the corresponding isothiouronium salts upon treatment with a weak base, enabling an in situ release/S-functionalization strategy that entirely negates the need to isolate, purify or manipulate these noxious reagents. 相似文献
44.
45.
Russell MT Pingree LS Hersam MC Marks TJ 《Langmuir : the ACS journal of surfaces and colloids》2006,22(15):6712-6718
Poly(dimethylsiloxane) (PDMS) has become a ubiquitous material for microcontact printing, yet there are few methods available to pattern a completed PDMS stamp in a single step. It is shown here that electron beam lithography (EBL) is effective in writing patterns directly onto cured PDMS stamps, thus overcoming the need for multiple patterning steps. Not only does this method allow the modification of an existing lithographic pattern, but new 3D features such as cones, pits, and channels can also be fabricated. EBL can also be used to fabricate PDMS masks for photolithography whereby 1:1 pattern transfer into a photoresist is achieved. Additionally, direct EBL writing of surface chemical features has been achieved using a PDMS stamp coated with a self-assembled monolayer. An electrostatic mechanism appears to be operative in the EBL patterning process, as supported by calculations, thermogravimetric analysis, time-of-flight secondary ion mass spectroscopy, optical and atomic force microscopy, and chemical functionalization assays. 相似文献
46.
Spencer LP Beddie C Hall MB Fryzuk MD 《Journal of the American Chemical Society》2006,128(38):12531-12543
The syntheses of tantalum derivatives with the potentially tridentate diamido-N-heterocyclic carbene (NHC) ligand are described. Aminolysis and alkane elimination reactions with the diamine-NHC ligands, (Ar)[NCN]H(2) (where (Ar)[NCN]H(2) = (ArNHCH(2)CH(2))(2)(C(3)N(2)); Ar = Mes, p-Tol), provided complexes with a bidentate amide-amine donor configuration. Attempts to promote coordination of the remaining pendent amine donor were unsuccessful. Metathesis reactions with the dilithiated diamido-NHC ligand ((Ar)[NCN]Li(2)) and various Cl(x)Ta(NR'(2))(5-)(x) precursors were successful and generated the desired octahedral (Ar)[NCN]TaCl(x)(NR'(2))(3-)(x) complexes. Attempts to prepare trialkyl tantalum complexes by this methodology resulted in the formation of an unusual metallaaziridine derivative. DFT calculations on model complexes show that the strained metallaaziridine ring forms because it allows the remaining substituents to adopt preferable bonding positions. The calculations predict that the lowest energy pathway involves a tantalum alkylidene intermediate, which undergoes C-H bond activation alpha to the amido to form the metallaaziridine moiety. This mechanism was confirmed by examining the distribution of deuterium atoms in an experiment between (Mes)[NCN]Li(2) and Cl(2)Ta(CD(2)Ph)(3). The single-crystal X-ray structures of (p)(-Tol)[NCNH]Ta(NMe(2))(4) (3), (Mes)[NCNH]Ta=CHPh(CH(2)Ph)(2) (4), (p)(-Tol)[NCN]Ta(NMe(2))(3) (7), (Mes)[NCCN]Ta(CH(2)(t)Bu)(2) (11), and (Mes)[NCCN]TaCl(CH(2)(t)Bu) (14) are included. 相似文献
47.
A new mesoscopic membrane model is developed in order to examine long-wavelength structural and dynamical membrane phenomena. Two different explicit mesoscopic solvent models are employed. The first mesoscopic solvent is denoted the big liquid oscillating blob system, which is parametrized to model water at a coarse-grained level and is motivated by a Langevin-like approach; the resulting membrane dynamics predict a solvent viscosity dependence consistent with the known viscosity of water. The second mesoscopic solvent is a Weeks-Chandler-Anderson model. Here, it is found that the correct mesoscopic hydrodynamic scaling of the membrane undulation dynamics is still preserved, although accelerated. When the behavior of the two membranes in close proximity to one another is examined, very little correlated motion is observed. However, the theoretically predicted scaling of the entropic undulation energy is confirmed, demonstrating that the entropic interaction between two membranes becomes increasingly repulsive with decreasing separation. 相似文献
48.
Primary amines react with keto-aldehyde functionality located in the side-chain of an eta4-dienetricarbonyliron complex to provide the corresponding pyrrolidines in excellent diastereoselectivity. Two of the pyrrolidine products, 1i and 1k, have been elaborated into pyrrolizidines using a 1,5-C-H insertion and radical cyclization strategy, respectively. 相似文献
49.
Liam A. McDonnell Alexandra van Remoortere Nico de Velde René J. M. van Zeijl André M. Deeldera 《Journal of the American Society for Mass Spectrometry》2010,21(12):1969-1978
Imaging MS now enables the parallel analysis of hundreds of biomolecules, spanning multiple molecular classes, which allows
tissues to be described by their molecular content and distribution. When combined with advanced data analysis routines, tissues
can be analyzed and classified based solely on their molecular content. Such molecular histology techniques have been used
to distinguish regions with differential molecular signatures that could not be distinguished using established histologic
tools. However, its potential to provide an independent, complementary analysis of clinical tissues has been limited by the
very large file sizes and large number of discrete variables associated with imaging MS experiments. Here we demonstrate data
reduction tools, based on automated feature identification and extraction, for peptide, protein, and lipid imaging MS, using
multiple imaging MS technologies, that reduce data loads and the number of variables by >100×, and that highlight highly-localized
features that can be missed using standard data analysis strategies. It is then demonstrated how these capabilities enable
multivariate analysis on large imaging MS datasets spanning multiple tissues. 相似文献
50.
Michal Friesl Liam J. A. Lenten Jan Libich Petr Stehlík 《The Journal of the Operational Research Society》2017,68(9):1006-1018
The popularity and business impact of major sports have been growing globally over time. This paper focuses on ice hockey, specifically the National Hockey League in North America. It reports a striking irregularity in ice hockey’s scoring dynamics relative to comparable sports such as soccer and rugby, namely a scoring surge in the middle section of the game. We explore an explanation for this irregularity related to the convention on the spatial location of the teams’ benches (which are fixed throughout the game) and on-ice sides (which are switched every period). Because a large number of the players’ substitutions occur while the play is in progress, this convention determines the distance forwards and defenders need to travel to make a substitution, and thus indirectly substitution strategies and scoring. We consider two simple operational changes that could increase the number of goals in the NHL by approximately 5 and 10%, respectively, corresponding to roughly 350 and 700 additional goals each season. This would partly offset the current downward scoring trend and thus enhance the game’s attractiveness. The estimated impact of the proposed reforms, one of which is largely costless, is robust across several specifications—using per-minute and per-second scoring data and controlling for various factors, such as bookmakers’ odds. 相似文献