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111.
Justin Lange Balkis Eddhif Mehrad Tarighi Tha Garandeau Elodie Praudeau Jonathan Clarhaut Brigitte Renoux Sbastien Papot Pauline Poinot 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(49):17727-17730
The development of efficient protocols for cancer diagnosis remains highly challenging. An emerging approach relies on the detection in exhaled breath of volatile organic compounds (VOC) produced by tumours. In this context, described here is a novel strategy in which a VOC‐based probe is converted selectively in malignant tissues, by a tumour‐associated enzyme, for releasing the corresponding VOC. The latter is then detected in the exhaled breath as a tumour marker for cancer diagnosis. This approach allows the detection of several different tumours in mice, the monitoring of tumour growth and tumour response to chemotherapy. Thus, the concept of “induced volatolomics” provides a new way to explore biological processes using VOC‐based probes that could be adapted to many biomedical applications. 相似文献
112.
Kinetic Resolution in the [2+2] Cycloaddition of Ketenes: An Experimental and Theoretical Study 下载免费PDF全文
Pauline Rullière Dr. Sébastien Carret Prof. Anne Milet Prof. Jean‐François Poisson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(10):3876-3881
The kinetic resolution of Z and E olefins by [2+2] cycloaddition with ketenes allows the isolation of pure E olefin, as well as the synthesis of pure cis‐cyclobutanones, starting from Z/E mixtures. A computational rationale for this kinetic difference is reported. The obtained difference of energy of activation matches with the experimental results. 相似文献
113.
The hydroazulene core of guanacastepene A has been synthesized in five steps from commercially available starting materials using a classical Nazarov cyclization to install the stereochemistry in the cyclopentanone diastereoselectively. In the presence or absence of Lewis bases, a hydroazulenone or a spirocyclic ketone generated via a novel Wagner-Meerwein rearrangement is obtained with excellent selectivity and yield. 相似文献
114.
Tumanskii B Pine P Apeloig Y Hill NJ West R 《Journal of the American Chemical Society》2004,126(25):7786-7787
Reaction of the stable silylene, 1,3-di-tert-butyl-1,3,2-diazasilol-2-ylidene, with the free radical sources TEMPO, Hg[P(O)(OPri)2]2, (CO)3CpM-MCp(CO)3 (M = W, Mo), (CO)5Re-Re(CO)5, and toluene leads to radical adducts. The EPR spectra of these radicals indicate that the unpaired electron is delocalized over the silicon-containing five-membered ring. 相似文献
115.
Soluble and insoluble polystyrene-bound triphenylarsine reagents have been prepared from 4-styryldiphenylarsine. The utility of these reagents as ligands for palladium in Suzuki cross-coupling reactions is demonstrated. In these applications, the use of polymeric triphenylarsine simplifies the purification of the coupled product and allows for the ligand to be recycled. Furthermore, the soluble polymeric arsine reagent permits the palladium catalyst to be recovered and reused. 相似文献
116.
A sheath-flow capillary electrophoresis-mass spectrometry (CE-MS) system utilizing a fully integrated large-bore stainless-steel emitter electrode tapered at the end for micro-ionspray operation has been developed and evaluated. A separation capillary with an outer diameter of up to 360 microm was inserted into the electrode thus forming a void volume of less than 15 nL between the capillary end and the electrospray ionisation (ESI) tip. The sheath liquid, usually methanol-water (80:20) with 0.1% formic acid for positive ion mode or methanol for negative ion mode, was delivered at 0.5-1.0 microL/min. Unlike previously reported CE-MS interfaces, the CE-MS probe was incorporated directly onto an Applied Biosystems/MDS SCIEX orthogonal-spray Turbo "V" ion source for ease of use and automatic operation. This integration enables fast and facile coupling and replacement of the separation capillary without interrupting the ion source configuration, and the sheath liquid supply. The reusable electrospray electrode was precisely fabricated and aligned with the length of the nebulizing gas tube for improved reproducibility. Automation was achieved through software control of both CE and tandem MS (MS/MS) for unattended batch sample analysis. The system was evaluated for attomole- to low femtomole-level profiling of model peptides and protein mixtures, bisphosphates, as well as antiviral nucleosidic drugs in cellular extracts. 相似文献
117.
ent‐Erythramine ((?)‐ 1 ), the enantiomer of the alkaloid erythramine, was prepared in 15 steps from known compounds. The first of three pivotal bond‐forming steps in the synthesis was a Suzuki–Miyaura cross‐coupling reaction of the starting materials to give a bis‐silyl ether. The second involved silver(I)‐induced electrocyclic ring opening of the gem‐dichlorocyclopropane formed in the next step and trapping of the ensuing π‐allyl cation by the tethered nitrogen atom to give, following cleavage of the allyloxycarbonyl protecting group, an approximately 5:6 mixture of the chromatographically separable diastereoisomeric spirocyclic products. In the third critical bond‐forming reaction, the iodide formed from one of the diastereoisomers underwent a radical‐addition/elimination reaction sequence that led to (?)‐ 1 in 89 % yield. The application of the same sequence of transformations to the other diastereoisomer afforded 3‐epi‐(+)‐erythramine (3‐epi‐(+)‐ 1 ). 相似文献
118.
The reactivity of SiO produced in a SiCl4/O2 plasma with the surface of a depositing silicon oxide film has been measured to be near zero for surface temperatures of 25–500 °C using the IRIS technique (imaging of radicals interacting with surfaces). This method combines spatially resolved laser-induced fluorescence with molecular beam techniques. The SiO desorbs from the surface with a spatial distribution consistent with a cosine angular distribution. 相似文献
119.
Reactions of oxygenated cobalt(II) complexes. IX. Oxidative properties of tetrakis(ethylenediamine)-μ-peroxo-μ-hydroxo-dicobalt(III) 1 VIII s. [1]. [(en)2Co(O2, OH)Co(en)2]3+ ( a ) reacts with I? in acidic aqueous solution according to: CoIII(O2, OH)CoIII + 21? + 5H+ ? 2CoIII + 3H2O + I2. Using I? in excess first order rate constants are obtained which, to a first approximation, are independent of [I?]. Comparison with kinetic data of deoxygenation of [(en)2Co(O2, OH)Co(en)2]3+ under analogous conditions suggests that both reactions have the same rate determining step. The singly bridged species [(en)2(H2O)CoO2Co(H2O) (en)2]4+ is shown to be the reactive intermediate in the iodide oxidation (Schema 2). 相似文献
120.
C−N Bond Formation from a Masked High‐Valent Copper Complex Stabilized by Redox Non‐Innocent Ligands 下载免费PDF全文
Jérémy Jacquet Pauline Chaumont Geoffrey Gontard Dr. Maylis Orio Dr. Hervé Vezin Dr. Sébastien Blanchard Dr. Marine Desage‐El Murr Prof. Louis Fensterbank 《Angewandte Chemie (International ed. in English)》2016,55(36):10712-10716
The reactivity of a stable copper(II) complex bearing fully oxidized iminobenzoquinone redox ligands towards nucleophiles is described. In sharp contrast with its genuine low‐valent counterpart bearing reduced ligands, this complex performs high‐yielding C?N bond formations. Mechanistic studies suggest that this behavior could stem from a mechanism akin to reductive elimination occurring at the metal center but facilitated by the ligand: it is proposed that a masked high oxidation state of the metal can be stabilized as a lower copper(II) oxidation state by the redox ligands without forfeiting its ability to behave as a high‐valent copper(III) center. These observations are substantiated by a combination of advanced EPR spectroscopy techniques with DFT studies. This work sheds light on the potential of redox ligands as promoters of unusual reactivities at metal centers and illustrates the concept of masked high‐valent metallic species. 相似文献