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71.
Ryan M. Rich Dorota L. Stankowska Badri P. Maliwal Thomas Just Sørensen Bo W. Laursen Raghu R. Krishnamoorthy Zygmunt Gryczynski Julian Borejdo Ignacy Gryczynski Rafal Fudala 《Analytical and bioanalytical chemistry》2013,405(6):2065-2075
Sample autofluorescence (fluorescence of inherent components of tissue and fixative-induced fluorescence) is a significant problem in direct imaging of molecular processes in biological samples. A large variety of naturally occurring fluorescent components in tissue results in broad emission that overlaps the emission of typical fluorescent dyes used for tissue labeling. In addition, autofluorescence is characterized by complex fluorescence intensity decay composed of multiple components whose lifetimes range from sub-nanoseconds to a few nanoseconds. For these reasons, the real fluorescence signal of the probe is difficult to separate from the unwanted autofluorescence. Here we present a method for reducing the autofluorescence problem by utilizing an azadioxatriangulenium (ADOTA) dye with a fluorescence lifetime of approximately 15 ns, much longer than those of most of the components of autofluorescence. A probe with such a long lifetime enables us to use time-gated intensity imaging to separate the signal of the targeting dye from the autofluorescence. We have shown experimentally that by discarding photons detected within the first 20 ns of the excitation pulse, the signal-to-background ratio is improved fivefold. This time-gating eliminates over 96 % of autofluorescence. Analysis using a variable time-gate may enable quantitative determination of the bound probe without the contributions from the background. 相似文献
72.
Dr. Daniel Brodbeck Dr. Sonia Álvarez-Barcia Dr. Jan Meisner Dr. Florian Broghammer Julian Klepp Dr. Delphine Garnier Dr. Wolfgang Frey Prof. Dr. Johannes Kästner Prof. Dr. René Peters 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(6):1515-1524
Asymmetric 1,2-additions of cyanide yield enantioenriched cyanohydrins as versatile chiral building blocks. Next to HCN, volatile organic cyanide sources are usually used. Among them, cyanoformates are more attractive on technical scale than TMSCN for cost reasons, but catalytic productivity is usually lower. Here, the development of a new strategy for cyanations is described, in which this activity disadvantage is overcome. A Lewis acidic Al center cooperates with an aprotic onium moiety within a remarkably robust bifunctional Al–F–salen complex. This allowed for unprecedented turnover numbers of up to 104. DFT studies suggest an unexpected unique trimolecular pathway in which the ammonium bound cyanide attacks the aldehyde, which itself is activated by the carbonyl group of the cyanoformate binding to the Al center. In addition, a novel practical carboxycyanation method was developed that makes use of KCN as the sole cyanide source. The use of a pyrocarbonate as carboxylating reagent provided the best results. 相似文献
73.
Dr. Tanya K. Ronson Chandan Giri Dr. N. Kodiah Beyeh Antti Minkkinen Filip Topić Dr. Julian J. Holstein Prof. Kari Rissanen Dr. Jonathan R. Nitschke 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(10):3374-3382
Subtle differences in metal–ligand bond lengths between a series of [M4L6]4? tetrahedral cages, where M=FeII, CoII, or NiII, were observed to result in substantial differences in affinity for hydrophobic guests in water. Changing the metal ion from iron(II) to cobalt(II) or nickel(II) increases the size of the interior cavity of the cage and allows encapsulation of larger guest molecules. NMR spectroscopy was used to study the recognition properties of the iron(II) and cobalt(II) cages towards small hydrophobic guests in water, and single‐crystal X‐ray diffraction was used to study the solid‐state complexes of the iron(II) and nickel(II) cages. 相似文献
74.
Dr. Luca Gabrielli Dr. Laura Russo Dr. Ana Poveda Dr. Julian R. Jones Prof. Francesco Nicotra Dr. Jesús Jiménez‐Barbero Prof. Laura Cipolla 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(24):7856-7864
Hybrid organic–inorganic solids represent an important class of engineering materials, usually prepared by sol–gel processes by cross‐reaction between organic and inorganic precursors. The choice of the two components and control of the reaction conditions (especially pH value) allow the synthesis of hybrid materials with novel properties and functionalities. 3‐Glycidoxypropyltrimethoxysilane (GPTMS) is one of the most commonly used organic silanes for hybrid‐material fabrication. Herein, the reactivity of GPTMS in water at different pH values (pH 2–11) was deeply investigated for the first time by solution‐state multinuclear NMR spectroscopic and mass spectrometric analysis. The extent of the different and competing reactions that take place as a function of the pH value was elucidated. The NMR spectroscopic and mass spectrometric data clearly indicate that the pH value determines the kinetics of epoxide hydrolysis versus silicon condensation. Under slighly acidic conditions, the epoxy‐ring hydrolysis is kinetically more favourable than the formation of the silica network. In contrast, under basic conditions, silicon condensation is the main reaction that takes place. Full characterisation of the formed intermediates was carried out by using NMR spectroscopic and mass spectrometric analysis. These results indicate that strict control of the pH values allows tuning of the reactivity of the organic and inorganic moities, thus laying the foundations for the design and synthesis of sol–gel hybrid biomaterials with tuneable properties. 相似文献
75.
Thermotropic liquid crystals offer uniquely ordered media for intermolecular reactions such as polymerization. Unlike the recently investigated topochemical polymerizations where molecules are rigidly constrained on lattice points [l], the liquid crystalline state permits full two-dimensional (nematic and cholesteric) and one-dimensional (smectic) movement. In addition, various degrees of translational freedom are attainable depending on the class of mesogen. Such freedom of choice, plus the ability to orient nematic and cholesteric mesogens on a molecular scale in an electric or magnetic field or on certain surfaces, makes the liquid crystal state an attractive polymerization medium. 相似文献
76.
Till J. B. Zähringer Julian A. Moghtader Maria-Sophie Bertrams Dr. Bibhisan Roy Masanori Uji Prof. Dr. Nobuhiro Yanai Prof. Dr. Christoph Kerzig 《Angewandte Chemie (International ed. in English)》2023,62(8):e202215340
Several energy-demanding photoreactions require harsh UV light from inefficient light sources. The conversion of low-energy visible light to high-energy singlet states via triplet-triplet annihilation upconversion (TTA-UC) could offer a solution for driving such reactions under mild conditions. We present the first annihilator with an emission maximum in the UVB region that, combined with an organic sensitizer, is suitable for blue-to-UVB upconversion. The annihilator singlet was successfully employed as an energy donor in subsequent FRET activations of aliphatic carbonyls. This hitherto unreported UC-FRET reaction sequence was directly monitored using laser spectroscopy and applied to mechanistic irradiation experiments demonstrating the feasibility of Norrish chemistry. Our results provide clear evidence for a novel blue light-driven substrate or solvent activation strategy, which is important in the context of developing more sustainable light-to-chemical energy conversion systems. 相似文献
77.
Dr. Eduard O. Bobylev Julian Ruijter Dr. David A. Poole III Dr. Simon Mathew Prof. Dr. Bas de Bruin Prof. Dr. Joost N. H. Reek 《Angewandte Chemie (International ed. in English)》2023,62(16):e202218162
Metabolic pathways are highly regulated by effector molecules that influences the rate of enzymatic reactions. Inspired by the catalytic regulation found in living cells, we report a Pt2L4 cage of which the activity can be controlled by effectors that bind inside the cage. The cage shows catalytic activity in the lactonization of alkynoic acids, with the reaction rates dependent on the effector guest bound in the cage. Some effector guests enhance the rate of the lactonization by up to 19-fold, whereas one decreases it by 5-fold. When mixtures of specific substrates are used, both starting materials and products act as guests for the Pt2L4 cage, enhancing its catalytic activity for one substrate while reducing its activity for the other. The reported regulatory behavior obtained by the addition of effector molecules paves the way to the development of more complex, metabolic-like catalyst systems. 相似文献
78.
Dr. Sunewang R. Wang Dr. Merle Arrowsmith Julian Böhnke Prof. Dr. Holger Braunschweig Dr. Theresa Dellermann Dr. Rian D. Dewhurst Hauke Kelch Dr. Ivo Krummenacher James D. Mattock Jonas H. Müssig Torsten Thiess Dr. Alfredo Vargas Dr. Jiji Zhang 《Angewandte Chemie (International ed. in English)》2017,56(27):8009-8013
The diborene 1 was synthesized by reduction of a mixture of 1,2-di-9-anthryl-1,2-dibromodiborane(4) ( 6 ) and trimethylphosphine with potassium graphite. The X-ray structure of 1 shows the two anthryl rings to be parallel and their π(C14) systems perpendicular to the diborene π(B=B) system. This twisted conformation allows for intercalation of the relatively high-lying π(B=B) orbital and the low-lying π* orbital of the anthryl moiety with no significant conjugation, resulting in a small HOMO–LUMO gap (HLG) and ultimately a C−H borylation of the anthryl unit. The HLG of 1 was estimated to be 1.57 eV from the onset of the long wavelength band in its UV/Vis absorption spectrum (THF, λonset=788 nm). The oxidation of 1 with elemental selenium afforded diboraselenirane 8 in quantitative yield. By oxidative abstraction of one phosphine ligand by another equivalent of elemental selenium, the B−B and C1−H bonds of 8 were cleaved to give the cyclic 1,9-diborylanthracene 9 . 相似文献
79.
80.
Sergey Miltsov Vladimir Karavan Alexandr Misharev Galina Starova Julian Alonso-Chamarro Mar Puyol 《Tetrahedron letters》2017,58(34):3353-3357
meso-Bromosubstituted indodicarbocyanine dyes produce dimeric molecules, together with the debrominated species, under acid catalysis. The relationship between the dimerization and hydrodebromination routes depends on the aryl substitution of the dyes. A possible reaction mechanism is also proposed. 相似文献