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71.
Based on the fact that anthracene (Anth) possesses much higher similarity in electron-releasing ability to porphyrin nucleus than the other polyacenes, the dimeric octaethylporphyrin (OEP) derivatives 4 and 5 (OEP–Anth–OEP) were synthesized and their structure–property relationships were examined, as compared with related OEP dimers 1–3. Among them, the derivative 4 showed enormously high electronic communication between two terminal OEP rings, potentially providing a suitable unit of the electronic structure for molecular design of the OEP devices operating with less energy and with higher sensitivity to outside stimuli. 相似文献
72.
73.
Yutaka Aoyagi Kei Ozawa Tatsuya Kobayashi Tomoyo Hasuda Ming-Yu Gui Yong-Ri Jin Xu-Wen Li Haruhiko Fukaya Reiko Yano Yukio Hitotsuyanagi Koichi Takeya 《Tetrahedron》2014
Transformation of plant-origin 7,14-dihydroxy-ent-kaurenes to ent-abietanes having a cis-fused α-methylene γ-lactones was accomplished efficiently under the Mitsunobu reaction conditions. The yields of the desired products were apparently influenced by the steric hindrance at C-1. The cytotoxic activity on P388 murine leukemia cells of the ent-abietanes having cis-fused α-methylene γ-lactones produced were assayed. 相似文献
74.
N. Kuroda S. Ulmer D. J. Murtagh S. Van Gorp Y. Nagata M. Diermaier S. Federmann M. Leali C. Malbrunot V. Mascagna O. Massiczek K. Michishio T. Mizutani A. Mohri H. Nagahama M. Ohtsuka B. Radics S. Sakurai C. Sauerzopf K. Suzuki M. Tajima H. A. Torii L. Venturelli B. Wünschek J. Zmeskal N. Zurlo H. Higaki Y. Kanai E. Lodi Rizzini Y. Nagashima Y. Matsuda E. Widmann Y. Yamazaki 《Hyperfine Interactions》2015,235(1-3):13-20
In order to test CPT symmetry between antihydrogen and its counterpart hydrogen, the ASACUSA collaboration plans to perform high precision microwave spectroscopy of ground-state hyperfine splitting of antihydrogen atom in-flight. We have developed an apparatus (“cusp trap”) which consists of a superconducting anti-Helmholtz coil and multiple ring electrodes. For the preparation of slow antiprotons and positrons, Penning-Malmberg type traps were utilized. The spectrometer line was positioned downstream of the cusp trap. At the end of the beamline, an antihydrogen beam detector was located, which comprises an inorganic Bismuth Germanium Oxide (BGO) single-crystal scintillator housed in a vacuum duct and surrounding plastic scintillators. A significant fraction of antihydrogen atoms flowing out the cusp trap were detected. 相似文献
75.
Molecularly Designed Nanoparticles by Dispersion of Self‐Assembled Organosiloxane‐Based Mesophases 下载免费PDF全文
Shigeru Sakamoto Yasuhiro Tamura Dr. Hideo Hata Dr. Yasuhiro Sakamoto Prof. Atsushi Shimojima Prof. Kazuyuki Kuroda 《Angewandte Chemie (International ed. in English)》2014,53(35):9173-9177
The design of siloxane‐based nanoparticles is important for many applications. Here we show a novel approach to form core–shell silica nanoparticles of a few nanometers in size through the principle of “dispersion of ordered mesostructures into single nanocomponents”. Self‐assembled siloxane–organic hybrids derived from amphiphilic alkyl‐oligosiloxanes were postsynthetically dispersed in organic solvent to yield uniform nanoparticles consisting of dense lipophilic shells and hydrophilic siloxane cores. In situ encapsulation of fluorescent dyes into the nanoparticles demonstrated their ability to function as nanocarriers. 相似文献
76.
Susith R. Galle Kankanamge Jianbo Ma Dr. Robert T. Mackin Dr. Fedra M. Leonik Prof. Carol M. Taylor Prof. Igor V. Rubtsov Prof. Daniel G. Kuroda 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(39):17160-17165
Hydrogen bonds (H bonds) play a major role in defining the structure and properties of many substances, as well as phenomena and processes. Traditional H bonds are ubiquitous in nature, yet the demonstration of weak H bonds that occur between a highly polarized C−H group and an electron-rich oxygen atom, has proven elusive. Detailed here are linear and nonlinear IR spectroscopy experiments that reveal the presence of H bonds between the chloroform C−H group and an amide carbonyl oxygen atom in solution at room temperature. Evidence is provided for an amide solvation shell featuring two clearly distinguishable chloroform arrangements that undergo chemical exchange with a time scale of about 2 ps. Furthermore, the enthalpy of breaking the hydrogen bond is found to be 6–20 kJ mol−1. Ab-initio computations support the findings of two distinct solvation shells formed by three chloroform molecules, where one thermally undergoes hydrogen-bond making and breaking. 相似文献
77.
Dr. Reiko Ueoka Dr. Roy A. Meoded Alejandro Gran-Scheuch Dr. Agneya Bhushan Prof. Dr. Marco W. Fraaije Prof. Dr. Jörn Piel 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(20):7835-7839
Bacterial trans-acyltransferase polyketide synthases (trans-AT PKSs) are multimodular megaenzymes that biosynthesize many bioactive natural products. They contain a remarkable range of domains and module types that introduce different substituents into growing polyketide chains. As one such modification, we recently reported Baeyer–Villiger-type oxygen insertion into nascent polyketide backbones, thereby generating malonyl thioester intermediates. In this work, genome mining focusing on architecturally diverse oxidation modules in trans-AT PKSs led us to the culturable plant symbiont Gynuella sunshinyii, which harbors two distinct modules in one orphan PKS. The PKS product was revealed to be lobatamide A, a potent cytotoxin previously only known from a marine tunicate. Biochemical studies show that one module generates glycolyl thioester intermediates, while the other is proposed to be involved in oxime formation. The data suggest varied roles of oxygenation modules in the biosynthesis of polyketide scaffolds and support the importance of trans-AT PKSs in the specialized metabolism of symbiotic bacteria. 相似文献
78.
Dr. Reiko Ueoka Dr. Roy A. Meoded Alejandro Gran‐Scheuch Dr. Agneya Bhushan Prof. Dr. Marco W. Fraaije Prof. Dr. Jörn Piel 《Angewandte Chemie (International ed. in English)》2020,59(20):7761-7765
Bacterial trans‐acyltransferase polyketide synthases (trans‐AT PKSs) are multimodular megaenzymes that biosynthesize many bioactive natural products. They contain a remarkable range of domains and module types that introduce different substituents into growing polyketide chains. As one such modification, we recently reported Baeyer–Villiger‐type oxygen insertion into nascent polyketide backbones, thereby generating malonyl thioester intermediates. In this work, genome mining focusing on architecturally diverse oxidation modules in trans‐AT PKSs led us to the culturable plant symbiont Gynuella sunshinyii, which harbors two distinct modules in one orphan PKS. The PKS product was revealed to be lobatamide A, a potent cytotoxin previously only known from a marine tunicate. Biochemical studies show that one module generates glycolyl thioester intermediates, while the other is proposed to be involved in oxime formation. The data suggest varied roles of oxygenation modules in the biosynthesis of polyketide scaffolds and support the importance of trans‐AT PKSs in the specialized metabolism of symbiotic bacteria. 相似文献
79.
Hirofumi Kuroda Ikuyoshi Tomita Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》1996,34(8):1597-1604
Tri-n-butylphosphine-catalyzed polyadditions of activated internal diynes (bifunctional β-substituted propiolate, 1B and 1C ) with diols are described. Although a terminal bispropiolate ( 1A ) could not produce soluble polymers, with secondary diols, the polyaddition of 1B or 1C with primary as well as secondary diols gave corresponding polymers ( 3 , only composed of E isomeric units) in high yield. The rate of the present polyaddition was estimated by a model reaction of benzyl alcohol with methyl 2-heptynoate ( 4 ), from which the introduction of alkyl groups at the β-position of propiolate moieties was found to decrease the rate of the reaction by 80 times. Furthermore, the rate-determining step on this polymerization system was speculated to be a protonation step of zwitterionic intermediates with protons from diols. © 1996 John Wiley & Sons, Inc. 相似文献
80.