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101.
Caterpillar Track Complexes in Template‐Directed Synthesis and Correlated Molecular Motion 下载免费PDF全文
Shiqi Liu Dr. Dmitry V. Kondratuk Dr. Sophie A. L. Rousseaux Dr. Guzmán Gil‐Ramírez Dr. Melanie C. O'Sullivan Jonathan Cremers Prof. Tim D. W. Claridge Prof. Harry L. Anderson 《Angewandte Chemie (International ed. in English)》2015,54(18):5355-5359
Small alterations to the structure of a star‐shaped template totally change its mode of operation. The hexapyridyl template directs the conversion of a porphyrin dimer to the cyclic hexamer, but deleting one pyridine site changes the product to the cyclic decamer, while deleting two binding sites changes the product to the cyclic octamer. This surprising switch in selectivity is explained by the formation of 2:1 caterpillar track complexes, in which two template wheels bind inside the nanoring. Caterpillar track complexes can also be prepared by binding the hexapyridyl template inside the 8‐ and 10‐porphyrin nanorings. NMR exchange spectroscopy (EXSY) experiments show that these complexes exhibit correlated motion, in which the conrotatory rotation of the two template wheels is coupled to rotation of the nanoring track. In the case of the 10‐porphyrin system, the correlated motion can be locked by binding palladium(II) dichloride between the two templates. 相似文献
102.
Electronic Olfactory Sensor Based on A. mellifera Odorant‐Binding Protein 14 on a Reduced Graphene Oxide Field‐Effect Transistor 下载免费PDF全文
Dr. Melanie Larisika Caroline Kotlowski Christoph Steininger Rosa Mastrogiacomo Prof. Paolo Pelosi Prof. Stefan Schütz Serban F. Peteu Prof. Christoph Kleber Ciril Reiner‐Rozman Dr. Christoph Nowak Prof. Wolfgang Knoll 《Angewandte Chemie (International ed. in English)》2015,54(45):13245-13248
An olfactory biosensor based on a reduced graphene oxide (rGO) field‐effect transistor (FET), functionalized by the odorant‐binding protein 14 (OBP14) from the honey bee (Apis mellifera) has been designed for the in situ and real‐time monitoring of a broad spectrum of odorants in aqueous solutions known to be attractants for bees. The electrical measurements of the binding of all tested odorants are shown to follow the Langmuir model for ligand–receptor interactions. The results demonstrate that OBP14 is able to bind odorants even after immobilization on rGO and can discriminate between ligands binding within a range of dissociation constants from Kd=4 μM to Kd=3.3 mM . The strongest ligands, such as homovanillic acid, eugenol, and methyl vanillate all contain a hydroxy group which is apparently important for the strong interaction with the protein. 相似文献
103.
Chaw-Keong Yong Patrick Parkinson Dmitry V. Kondratuk Wei-Hsin Chen Andrew Stannard Alex Summerfield Johannes K. Sprafke Melanie C. O'Sullivan Peter H. Beton Harry L. Anderson Laura M. Herz 《Chemical science》2015,6(1):181-189
Rings of chlorophyll molecules harvest sunlight remarkably efficiently during photosynthesis in purple bacteria. The key to their efficiency lies in their highly delocalized excited states that allow for ultrafast energy migration. Here we show that a family of synthetic nanorings mimic the ultrafast energy transfer and delocalization observed in nature. π-Conjugated nanorings with diameters of up to 10 nm, consisting of up to 24 porphyrin units, are found to exhibit excitation delocalization within the first 200 fs of light absorption. Transitions from the first singlet excited state of the circular nanorings are dipole-forbidden as a result of symmetry constraints, but these selection rules can be lifted through static and dynamic distortions of the rings. The increase in the radiative emission rate in the larger nanorings correlates with an increase in static disorder expected from Monte Carlo simulations. For highly symmetric rings, the radiative rate is found to increase with increasing temperature. Although this type of thermally activated superradiance has been theoretically predicted in circular chromophore arrays, it has not previously been observed in any natural or synthetic systems. As expected, the activation energy for emission increases when a nanoring is fixed in a circular conformation by coordination to a radial template. These nanorings offer extended chromophores with high excitation delocalization that is remarkably stable against thermally induced disorder. Such findings open new opportunities for exploring coherence effects in nanometer molecular rings and for implementing these biomimetic light-harvesters in man-made devices. 相似文献
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106.
Brasch M de la Escosura A Ma Y Uetrecht C Heck AJ Torres T Cornelissen JJ 《Journal of the American Chemical Society》2011,133(18):6878-6881
We report herein the encapsulation of a water-soluble phthalocyanine (Pc) into virus-like particles (VLPs) of two different sizes, depending on the conditions. At neutral pH, the cooperative encapsulation/templated assembly of the particles induces the formation of Pc stacks instead of Pc dimers, due to an increased confinement concentration. The Pc-containing VLPs may potentially be used as photosensitizer/vehicle systems for biomedical applications such as photodynamic therapy. 相似文献
107.
Park TH Hickman AJ Koh K Martin S Wong-Foy AG Sanford MS Matzger AJ 《Journal of the American Chemical Society》2011,133(50):20138-20141
High reversibility during crystallization leads to relatively defect-free crystals through repair of nonperiodic inclusions, including those derived from impurities. Microporous coordination polymers (MCPs) can achieve a high level of crystallinity through a related mechanism whereby coordination defects are repaired, leading to single crystals. In this work, we discovered and exploited the fact that this process is far from perfect for MCPs and that a minority ligand that is coordinatively identical to but distinct in shape from the majority linker can be inserted into the framework, resulting in defects. The reaction of Zn(II) with 1,4-benzenedicarboxylic acid (H(2)BDC) in the presence of small amounts of 1,3,5-tris(4-carboxyphenyl)benzene (H(3)BTB) leads to a new crystalline material, MOF-5(O(h)), that is nearly identical to MOF-5 but has an octahedral morphology and a number of defect sites that are uniquely functionalized with dangling carboxylates. The reaction with Pd(OAc)(2) impregnates the metal ions, creating a heterogeneous catalyst with ultrahigh surface area. The Pd(II)-catalyzed phenylation of naphthalene within Pd-impregnated MOF-5(O(h)) demonstrates the potential utility of an MCP framework for modulating the reactivity and selectivity of such transformations. Furthermore, this novel synthetic approach can be applied to different MCPs and will provide scaffolds functionalized with catalytically active metal species. 相似文献
108.
Li Y Al-Eryani R Yarbrough ML Orth K Ball HL 《Journal of the American Society for Mass Spectrometry》2011,22(4):752-761
Recent studies have suggested that adenosine 5'-monophosphate (AMP) post-translational modification of proteins could represent
a novel molecular signaling pathway. Mass spectrometric fragmentation characteristics of this modification have not previously
been described and studied systematically. In this work, we therefore examined the fragmentation pattern of chemically synthesized
peptides containing AMPylated Thr, Ser, and Tyr. The formation of characteristic ions and the influence of collision energy
(CE) on the detection of characteristic ions and their relative peak intensity are reported. When peptide with AMPylated Ser/Thr
underwent collision induced dissociation (CID), peaks at m/z 348.1, 136.1, and 250.1, fragments with AMP group attached, and fragments consistent with neutral loss of 347 Da were major
characteristic ions; fragments consistent with neutral loss of 135 Da or 249 Da were weaker and not always detectable. The
observations for Tyr AMPylation followed the same general patterns as those for Ser/Thr modification, with the exception that
the ions detected for Tyr AMPylation did not include either the peak at m/z 348.1, or fragments with a mass shift of –347 Da. The results described in this paper highlight a series of diagnostic ions,
which can be used not only to confidently identify the AMPylation site based on MS and MS/MS data, but also to selectively
scan AMPylated peptides in complex protein mixtures. 相似文献
109.
This paper describes the 1,1-arylacetoxylation of diverse α-olefins using organostannanes and hypervalent iodine oxidants. The reaction provides a convergent approach for generating a C-C and a C-O bond as well as a new stereocenter in a single catalytic transformation. 相似文献
110.