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131.
132.
Xianhai Tian Lina Song Matthias Rudolph Frank Rominger Thomas Oeser A. Stephen K. Hashmi 《Angewandte Chemie (International ed. in English)》2019,58(11):3589-3593
We herein report the unprecedented synthesis of diverse biologically important aza‐heterocycles by employing sulfilimines as nitrene transfer reagents. This class of sulfur‐based aza‐ylides had not been successfully used for gold nitrene transfer before. This work contains an efficient generation of α‐imino gold carbenes by N?S cleavage of sulfilimines. These gold carbenes undergo C?H insertion, cyclopropanation, and nucleophilic attack to form indoles (44 examples), 3‐azabicyclo[3.1.0]hexan‐2‐imines (24 examples), and imidazoles (3 examples). Our study represents a unique gold‐catalyzed reaction between alkynes and sulfur ylides, and also includes the first aza‐heterocycle synthesis that proceeds by intermolecular nitrene transfer followed by cyclopropanation of the α‐imino gold carbenes. Moreover, an unexpected synthesis of 4‐acylquinolines (3 examples) from 2‐acylphenyl sulfilimines and propargylic silyl ether derivatives by a 1,2‐hydride shift onto the α‐imino gold carbene and a subsequent Mukaiyama aldol cyclization was discovered. 相似文献
133.
The quadratic, cubic and semi-diagonal quartic force field of propene has been calculated at the MP2 level of theory employing a basis set of triple-ζ quality. A semi-experimental equilibrium structure has been derived from experimental ground state rotational constants and rovibrational interaction parameters calculated from the ab initio force field. This structure is in excellent agreement with the ab initio structure calculated at the CCSD(T) level of theory using a basis set of quintuple-ζ quality and a core correlation correction. The experimental mass-dependent rm structures are also determined and their accuracy is discussed. The use of isolated CH stretching frequencies is shown to be a good method to determine CH bond length. 相似文献
134.
M. Sc. Steffen Mader Dr. Lise Molinari Dr. Matthias Rudolph Prof. Dr. A. Stephen K. Hashmi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(10):3910-3913
Various haloalkynes are converted in the presence of a dual activation gold catalyst. Via a dual activation process a completely atom economic head‐to‐tail coupling delivers gem‐dihalogenated conjugated enynes as valuable building blocks for organic synthesis. 相似文献
135.
Lee Rudolph 《Proceedings of the American Mathematical Society》1997,125(10):3049-3050
For any knot , .
136.
D. Rudolph C. Baktash M. J. Brinkman M. Devlin H. -Q. Jin D. R. LaFosse M. Leddy I. Y. Lee A. O. Macchiavelli L. L. Riedinger D. G. Sarantites C. H. Yu 《Zeitschrift für Physik A Hadrons and Nuclei》1997,358(4):379-380
High-spin states of the isospin T z = ? 1/2 nucleus 55Ni have been identified for the first time by means of the reaction 28Si(36Ar,2αn) at 143 MeV beam energy. The Gammasphere array together with ancillary detectors was used to detect γ rays in coincidence with evaporated light particles. The level scheme of 55Ni comprising four transitions is compared to its mirror partner 55Co and shell-model calculations in the fp shell. 相似文献
137.
138.
Raman (and a few additional FT-IR) spectroscopic measurements of sodium and potassium carbonate and hydrogencarbonate in aqueous solution have been carried out over wide concentration ranges at room temperature and at elevated temperatures. The bands of the CO3(2-)(aq) and HCO3(-)(aq) species, which possess pseudo D3h and C1 symmetry respectively, have been assigned and discussed. Quantitative Raman measurements and thermodynamic calculations on KHCO3 solutions show that the salt does not dissolve congruently in aqueous solutions but forms small amounts of CO3(2-). Quantitative Raman spectroscopic measurements have also been carried out on K2CO3 solutions and the hydrolysis of the carbonate ion has been determined as a function of concentration at room temperature and as a function of temperature up to 219 degrees C. The pK2 value of carbonic acid at 23 degrees C has been established as 10.35 by Raman spectroscopy, a value that compares favourably with published thermodynamic values. 相似文献
139.
Michael Rudolph Prof. Dr. Robert Tampé Prof. Dr. Benesh Joseph 《Angewandte Chemie (International ed. in English)》2023,62(37):e202307091
ATP-binding cassette (ABC) transporters shuttle diverse substrates across biological membranes. Transport is often achieved through a transition between an inward-facing (IF) and an outward-facing (OF) conformation of the transmembrane domains (TMDs). Asymmetric nucleotide-binding sites (NBSs) are present among several ABC subfamilies and their functional role remains elusive. Here we addressed this question using concomitant NO−NO, Mn2+−NO, and Mn2+−Mn2+ pulsed electron–electron double-resonance spectroscopy of TmrAB in a time-resolved manner. This type-IV ABC transporter undergoes a reversible transition in the presence of ATP with a significantly faster forward transition. The impaired degenerate NBS stably binds Mn2+−ATP, and Mn2+ is preferentially released at the active consensus NBS. ATP hydrolysis at the consensus NBS considerably accelerates the reverse transition. Both NBSs fully open during each conformational cycle and the degenerate NBS may regulate the kinetics of this process. 相似文献
140.
A Single Methylene Group in Oligoalkylamine‐Based Cationic Polymers and Lipids Promotes Enhanced mRNA Delivery 下载免费PDF全文
Anita Jarzębińska Dr. Tamara Pasewald Jana Lambrecht Olga Mykhaylyk Linda Kümmerling Dr. Philipp Beck Dr. Günther Hasenpusch Priv.‐Doz. Dr. Carsten Rudolph Prof. Dr. Christian Plank Dr. Christian Dohmen 《Angewandte Chemie (International ed. in English)》2016,55(33):9591-9595
The development of chemically modified mRNA holds great promise as a new class of biologic therapeutics. However, the intracellular delivery and endosomal escape of mRNA encapsulated in nanoparticles has not been systematically investigated. Here, we synthesized a diverse set of cationic polymers and lipids from a series of oligoalkylamines and subsequently characterized their mRNA delivery capability. Notably, a structure with an alternating alkyl chain length between amines showed the highest transfection efficiency, which was linked to a high buffering capacity in a narrow range of pH 6.2 to 6.5. Variation in only one methylene group resulted in enhanced mRNA delivery to both the murine liver as well as porcine lungs after systemic or aerosol administration, respectively. These findings reveal a novel fundamental structure–activity relationship for the delivery of mRNA that is independent of the class of mRNA carrier and define a promising new path of exploration in the field of mRNA therapeutics. 相似文献