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181.
182.
Michael H. Palmer 《Journal of Molecular Spectroscopy》2006,237(1):123-125
Early assignments of the vacuum UV photoabsorption spectrum of allene (1951-1972) gave a number of Rydberg series, but these series had limiting values for the ionization potential, which are incompatible (by up to 0.4 eV) with more recent adiabatic IPs from molecular beam and high resolution photoelectron spectra (UV-PES). We have performed a re-analysis of the VUV spectrum of allene by a combination of overlay of the VUV and UV-PES spectra which leads to new experimental assignments. Major differences in assignment to the early studies are reported, and these include the lowlying Rydberg states, which are now assigned as follows: 6.55 (3s), 7.2 (3p), 8.15 (3d), and 8.25 eV (4s), respectively, with further assignments up to 6s, 6p, and 6d. 相似文献
183.
F. Hegelund R. Wugt Larsen R.A. Aitken K.M. Aitken M.H. Palmer 《Journal of Molecular Spectroscopy》2007,246(2):198-212
The Fourier transform infrared spectrum of gaseous 1,3,4-oxadiazole, C2H2N2O, has been recorded in the 800–1600 cm−1 wavenumber region with a resolution around 0.0030 cm−1. The four fundamental bands ν9(B1; 852.5 cm−1), ν14(B2; 1078.5 cm−1), ν4(A1; 1092.6 cm−1), and ν2(A1; 1534.9 cm−1) are analyzed by the standard Watson model. Ground state rotational and quartic centrifugal distortion constants are obtained from a simultaneous fit of ground state combination differences from three of these bands and previous microwave transitions. Upper state spectroscopic constants are obtained for all four bands from single band fits using the Watson model. The ν4 and ν14 bands form a c-Coriolis interacting dyad, and the two bands are analyzed simultaneously by a model including first and second order Coriolis resonance using the ab initio predicted Coriolis coupling constant . An extended local resonance in ν2 is explained as higher order b-Coriolis type resonance with ν6 + ν10, which is further perturbed globally by the ν15 + ν10 level. A fit of selected low-J transitions to a triad model including ν2(A1), ν6 + ν10(B1), and ν15 + ν10(A2) using an ab initio calculated Coriolis coupling constant is performed.The rotational constants, ground state quartic centrifugal distortion constants, anharmonic frequencies, and vibration–rotational constants (α-constants) predicted by quantum chemical calculations using a cc-pVTZ and TZ2P basis with B3LYP methodology, are compared with the present experimental data, where there is generally good agreement. A complete set of anharmonic frequencies and α-constants for all fundamental levels of the molecule is given. 相似文献
184.
Far‐Red and Near‐IR AIE‐Active Fluorescent Organic Nanoprobes with Enhanced Tumor‐Targeting Efficacy: Shape‐Specific Effects 下载免费PDF全文
Andong Shao Prof. Dr. Yongshu Xie Shaojia Zhu Dr. Zhiqian Guo Shiqin Zhu Dr. Jin Guo Prof. Dr. Ping Shi Prof. Dr. Tony D. James Prof. Dr. He Tian Prof. Dr. Wei‐Hong Zhu 《Angewandte Chemie (International ed. in English)》2015,54(25):7275-7280
The rational design of high‐performance fluorescent materials for cancer targeting in vivo is still challenging. A unique molecular design strategy is presented that involves tailoring aggregation‐induced emission (AIE)‐active organic molecules to realize preferable far‐red and NIR fluorescence, well‐controlled morphology (from rod‐like to spherical), and also tumor‐targeted bioimaging. The shape‐tailored organic quinoline–malononitrile (QM) nanoprobes are biocompatible and highly desirable for cell‐tracking applications. Impressively, the spherical shape of QM‐5 nanoaggregates exhibits excellent tumor‐targeted bioimaging performance after intravenously injection into mice, but not the rod‐like aggregates of QM‐2. 相似文献
185.
Dr. George N. Khairallah Dr. Alan T. Maccarone Dr. Huong T. Pham Timothy M. Benton Dr. Tony Ly Dr. Gabriel da Silva Prof. Stephen J. Blanksby Prof. Richard A. J. O'Hair 《Angewandte Chemie (International ed. in English)》2015,54(44):12947-12951
Although the deleterious effects of ozone on the human respiratory system are well‐known, many of the precise chemical mechanisms that both cause damage and afford protection in the pulmonary epithelial lining fluid are poorly understood. As a key first step to elucidating the intrinsic reactivity of ozone with proteins, its reactions with deprotonated cysteine [Cys?H]? are examined in the gas phase. Reaction proceeds at near the collision limit to give a rich set of products including 1) sequential oxygen atom abstraction reactions to yield cysteine sulfenate, sulfinate and sulfonate anions, and significantly 2) sulfenate radical anions formed by ejection of a hydroperoxy radical. The free‐radical pathway occurs only when both thiol and carboxylate moieties are available, implicating electron‐transfer as a key step in this reaction. This novel and facile reaction is also observed in small cys‐containing peptides indicating a possible role for this chemistry in protein ozonolysis. 相似文献
186.
Dr. Sabine Lennarz MSc Therese Christine Alich Dr. Tony Kelly Dr. Michael Blind Prof. Dr. Heinz Beck Prof. Dr. Günter Mayer 《Angewandte Chemie (International ed. in English)》2015,54(18):5369-5373
Cellular behavior is orchestrated by the complex interactions of a myriad of intracellular signal transduction pathways. To understand and investigate the role of individual components in such signaling networks, the availability of specific inhibitors is of paramount importance. We report the generation and validation of a novel variant of an RNA aptamer that selectively inhibits the mitogen‐activated kinase pathway in neurons. We demonstrate that the aptamer retains function under intracellular conditions and that application of the aptamer through the patch‐clamp pipette efficiently inhibits mitogen‐activated kinase‐dependent synaptic plasticity. This approach introduces synthetic aptamers as generic tools, readily applicable to inhibit different components of intraneuronal signaling networks with utmost specificity. 相似文献
187.
The covalent boron–diol interaction enables elaborate design of boronic acid‐based saccharide sensors. Over the last decade, this research topic has been well developed thanks to the integration of boronic acid chemistry with a range of techniques, including supramolecular chemistry, materials chemistry, surface modification, and nanotechnology. New sensing strategies and platforms have been introduced and remarkable progress has been achieved to fully utilize the unique property of boron–diol interaction and to improve the binding affinity towards different targets, especially under physiological conditions. In this review, the latest progress over the past 30 months (from late 2012 to early 2015) is highlighted and discussed to shed light on this versatile and promising platform for saccharide sensing. 相似文献
188.
189.
We consider random subgraphs of a fixed graph with large minimum degree. We fix a positive integer k and let Gk be the random subgraph where each independently chooses k random neighbors, making kn edges in all. When the minimum degree then Gk is k‐connected w.h.p. for ; Hamiltonian for k sufficiently large. When , then Gk has a cycle of length for . By w.h.p. we mean that the probability of non‐occurrence can be bounded by a function (or ) where . © 2016 Wiley Periodicals, Inc. Random Struct. Alg., 50, 143–157, 2017 相似文献
190.
John R. Britnell Neil Saunders Tony Skyner 《Journal of Pure and Applied Algebra》2017,221(11):2647-2665
A finite group G is exceptional if it has a quotient Q whose minimal faithful permutation degree is greater than that of G. We say that Q is a distinguished quotient.The smallest examples of exceptional p-groups have order . For an odd prime p, we classify all pairs where G has order and Q is a distinguished quotient. (The case has already been treated by Easdown and Praeger.) We establish the striking asymptotic result that as p increases, the proportion of groups of order with at least one exceptional quotient tends to 1/2. 相似文献