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361.
Total Synthesis Establishes the Biosynthetic Pathway to the Naphterpin and Marinone Natural Products
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Lauren A. M. Murray Dr. Shaun M. K. McKinnie Dr. Henry P. Pepper Reto Erni Dr. Zachary D. Miles Michelle C. Cruickshank Dr. Borja López‐Pérez Prof. Bradley S. Moore Dr. Jonathan H. George 《Angewandte Chemie (International ed. in English)》2018,57(34):11009-11014
The naphterpins and marinones are naphthoquinone meroterpenoids with an unusual aromatic oxidation pattern that is biosynthesized from 1,3,6,8‐tetrahydroxynaphthalene (THN). We propose that cryptic halogenation of THN derivatives by vanadium‐dependent chloroperoxidase (VCPO) enzymes is key to this biosynthetic pathway, despite the absence of chlorine in these natural products. This speculation inspired a total synthesis to mimic the naphterpin/marinone biosynthetic pathway. In validation of this biogenetic hypothesis, two VCPOs were discovered that interconvert several of the proposed biosynthetic intermediates. 相似文献
362.
Stereochemical Definition of the Natural Product (6R,10R,13R, 14R,16R,17R,19S,20S,21R,24S,25S,28S,30S,32R,33R,34R,36S,37S,39R)‐Azaspiracid‐3 by Total Synthesis and Comparative Analyses
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Nathaniel T. Kenton Dr. Daniel Adu‐Ampratwum Dr. Antony A. Okumu Dr. Pearse McCarron Dr. Jane Kilcoyne Prof. Dr. Frode Rise Prof. Dr. Alistair L. Wilkins Dr. Christopher O. Miles Prof. Dr. Craig J. Forsyth 《Angewandte Chemie (International ed. in English)》2018,57(3):810-813
The previously accepted structure of the marine toxin azaspiracid‐3 is revised based upon an original convergent and stereoselective total synthesis of the natural product. The development of a structural revision hypothesis, its testing, and corroboration are reported. Synthetic (6R,10R,13R,14R,16R,17R,19S,20S,21R,24S,25S,28S,30S,32R, 33R,34R,36S,37S,39R)‐azaspiracid‐3 chromatographically and spectroscopically matched naturally occurring azaspiracid‐3, whereas the previously assigned 20R epimer did not. 相似文献
363.
O→S Relay Deprotection: A General Approach to Controllable Donors of Reactive Sulfur Species
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Jianming Kang Shi Xu Miles N. Radford Wenjia Zhang Shane S. Kelly Jacob J. Day Prof. Dr. Ming Xian 《Angewandte Chemie (International ed. in English)》2018,57(20):5893-5897
Reactive sulfur species (RSS) are biologically important molecules. Among them, H2S, hydrogen polysulfides (H2Sn, n>1), persulfides (RSSH), and HSNO are believed to play regulatory roles in sulfur‐related redox biology. However, these molecules are unstable and difficult to handle. Having access to their reliable and controllable precursors (or donors) is the prerequisite for the study of these sulfur species. Reported in this work is the preparation and evaluation of a series of O‐silyl‐mercaptan‐based sulfur‐containing molecules which undergo pH‐ or F?‐mediated desilylation to release the corresponding H2S, H2Sn, RSSH, and HSNO in a controlled fashion. This O→S relay deprotection serves as a general strategy for the design of pH‐ or F?‐triggered RSS donors. Moreover, we have demonstrated that the O‐silyl groups in the donors could be changed into other protecting groups like esters. This work should allow the development of RSS donors with other activation mechanisms (such as esterase‐activated donors). 相似文献
364.
Gerald R. Willey Miles T. Lakin Nathaniel W. Alcock Christopher J. Samuel 《Journal of inclusion phenomena and macrocyclic chemistry》1994,15(3):293-304
The X-ray crystal structure of 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane has been determined. The neutral ligand crystallises in the triclinic space groupP
with unit cell parametersa=8.467(4),b=10.057(5),c=10.637(5) Å, =67.68(3), =75.38(4), =76.34(4)°,V=800.75 Å3 andD
c=1.063 g cm–3 forZ=2.R=0.047 for 2140 unique observed (I/(I)2.0) reflections (R
w=0.052). Two crystallographically independent molecules are observed. Both are centrosymmetric and adopt a mesodentate conformation. Molecule (1) is identified as the (R, S, S, R)-[trans-IV] isomer and molecule (2) as the (R, R, S, S)-[trans-III] isomer. Molecular mechanics calculations provide a basis for understanding the structural and energetic relationships between the neutral and protonated forms of this tetraazamacrocyclic ligand.
Supplementary Data relating to this article have been deposited with the British Library at Boston Spa, Wetherby, West Yorkshire, U.K. as Supplementary Publication No. 82149 (13 pages). 相似文献
365.
V. K. Rastogi K. V. R. Chary G. Govil F. B. Howard H. T. Miles 《Applied magnetic resonance》1994,7(1):1-19
An oligonucleotide dodecamer d-GGTACIAGTACC containing two inosine-adenosine mismatched base-pairs has been studied by1H and31P NMR spectroscopy. Unique assignments of1H and31P spins have been achieved by using a recently proposed two-dimensionalheteronuclearlong rangecorrelation (2D-HELCO) technique. The 2D nuclear Overhauser enhancement spectroscopy (NOESY) spectrum recorded in a mixed solvent of 90% H2O+10%2H2O has been used to assign all the exchangeable imino and amino proton resonances. NMR results indicate that at concentrations above 5 mM, the molecule adopts a duplex structure where the inosine imino protons are hydrogen bonded. Cross-strand NOEs between the imino proton of I6 and H2 proton of A7 and that between H2 of I6 and H2 of A7 provide evidence for inosine-adenosine base-pairing, with both bases I6 and A7 inanti conformation. The observed NOE connectivitiesd1,d2 andd3 from almost the middle of the molecule to the two ends are consistent with a right handed B-DNA conformation. However, the molecule adopts a more extended conformation in the mismatch region to accomodate the bulky purine-purine (IA) base pairs. NMR experiments at lower concentrations indicate the coexistence of a monomeric hairpin with a two base loop, consisting of I6 and A7 units, in equilibrium with the duplex. 2D-ROESY experiment at such a concentration shows that the conformation of the stem of the hairpin does not deviate much from the corresponding region of the duplex and four nucleotides C5, I6, A7 and G8 undergo significant structural changes during the formation of hairpin loop. 相似文献
366.
Several Polarization control transducers have appeared on the market, and now automated, endless polarization control systems using these transducers are becoming available. Unfortunately it is not entirely clear what benchmark performance tests a polarization control system must pass, and the polarization disturbances a system must handle are open to some debate. We present quantitative measurements of realistic polarization disturbances and two benchmark tests we have successfully used to evaluate the performance of an automated, endless polarization control system. We use these tests to compare the performance of a system using piezoelectric transducers to that of a system using LiNbO3 transducers. 相似文献
367.
368.
We report a simplified version of a mm-wave generator employing the sideband filtering technique which uses a single optical sideband filter. Instead of using a Mach-Zehnder-like fiber network to select a pair of sidebands, we employ a single Fabry-Perot fiber Bragg grating with a pair of passbands separated by the mm-wave frequency. Using a single filter eliminated the need for polarization control and pathlength matching that was required by the former interferometer-like arrangement. We describe a 30 GHz generator design and present its mm-wave signal spectrum showing an instrument-limited linewidth of ~20 Hz. The generation of such an extremely narrow signal spectrum from a laser with a 1 MHz linewidth demonstrates the remarkable laser frequency noise cancellation property of the sideband filtering technique. 相似文献
369.
The hetero-Diels-Alder reaction between 1-aza-3-siloxy-1,3-butadienes and electron deficient acetylenes is described. The reactivity of a range of α,β-unsaturated oximes and hydrazones is assessed in the synthesis of tri- and tetra-substituted pyridines bearing an oxygen functionality at C-3. Microwave irradiation has been employed to decrease the extended reaction times and increase the poor yields often associated with this reaction. 相似文献
370.
A Pd/C‐CeO2 Anode Catalyst for High‐Performance Platinum‐Free Anion Exchange Membrane Fuel Cells
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Dr. Hamish A. Miller Dr. Alessandro Lavacchi Dr. Francesco Vizza Dr. Marcello Marelli Dr. Francesco Di Benedetto Dr. Francesco D'Acapito Yair Paska Miles Page Dr. Dario R. Dekel 《Angewandte Chemie (International ed. in English)》2016,55(20):6004-6007
One of the biggest obstacles to the dissemination of fuel cells is their cost, a large part of which is due to platinum (Pt) electrocatalysts. Complete removal of Pt is a difficult if not impossible task for proton exchange membrane fuel cells (PEM‐FCs). The anion exchange membrane fuel cell (AEM‐FC) has long been proposed as a solution as non‐Pt metals may be employed. Despite this, few examples of Pt‐free AEM‐FCs have been demonstrated with modest power output. The main obstacle preventing the realization of a high power density Pt‐free AEM‐FC is sluggish hydrogen oxidation (HOR) kinetics of the anode catalyst. Here we describe a Pt‐free AEM‐FC that employs a mixed carbon‐CeO2 supported palladium (Pd) anode catalyst that exhibits enhanced kinetics for the HOR. AEM‐FC tests run on dry H2 and pure air show peak power densities of more than 500 mW cm?2. 相似文献