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31.
Yuanqi Gui Baian Ji Gaoyi Yi Xiuju Li Kailian Zhang Qifeng Fu 《Molecules (Basel, Switzerland)》2021,26(6)
Herein, a novel L-arginine (L-Arg)-modified polydopamine (PDA)-coated capillary (PDA/L-Arg@capillary) was firstly fabricated via the basic amino-acid-induced PDA co-deposition strategy and employed to constitute a new chiral ligand exchange capillary electrochromatography (CLE-CEC) method for the high-performance enantioseparation of D,L-amino acids (D,L-AAs) with L-Arg as the immobilized chiral ligand coordinating with the central metal ion Zn(II) as running buffer. Assisted by hydrothermal treatment, the robust immobilization of L-Arg on the capillary inner wall could be facilely achieved within 1 h, prominently improving the synthesis efficiency and simplifying the preparation procedure. The successful preparation of PDA/L-Arg coatings in the capillary was systematically characterized and confirmed using several methods. In comparison with bare and PDA-functionalized capillaries, the enantioseparation capability of the presented CLE-CEC system was significantly enhanced. Eight D,L-AAs were completely separated and three pairs were partially separated under the optimal conditions. The prepared PDA/L-Arg@capillary showed good repeatability and stability. The potential mechanism of the greatly enhanced enantioseparation performance obtained by PDA/L-Arg@capillary was also explored. Moreover, the proposed method was further utilized for studying the enzyme kinetics of L-glutamic dehydrogenase, exhibiting its promising prospects in enzyme assays and other related applications. 相似文献
32.
Marcos Juanes Rizalina T. Saragi Prof. Dr. Walther Caminati Prof. Dr. Alberto Lesarri 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(49):11402-11411
In the last decade, experiment and theory have expanded our vision of non-covalent interactions (NCIs), shifting the focus from the conventional hydrogen bond to new bridging interactions involving a variety of weak donor/acceptor partners. Whereas most experimental data originate from condensed phases, the introduction of broadband (chirped-pulse) microwave fast-passage techniques has revolutionized the field of rotational spectroscopy, offering unexplored avenues for high-resolution studies in the gas phase. We present an outlook of hot topics for rotational investigations on isolated intermolecular clusters generated in supersonic jet expansions. Rotational spectra offer very detailed structural data, easily discriminating the isomeric or isotopic composition and effectively cancelling any solvent, crystal, or matrix bias. The direct comparison with quantum mechanical predictions provides insight into the origin of the inter- and intramolecular interactions with much greater precision than any other spectroscopic technique, simultaneously serving as test-bed for fine-tuning of theoretical methods. We present recent examples of rotational investigations around three topics: oligomer formation, chiral recognition, and identification of halogen, chalcogen, pnicogen, or tetrel bonds. The selected examples illustrate the benefits of rotational spectroscopy for the structural and energetic assessment of inter-/intramolecular interactions, which may help to move from fundamental research to applications in supramolecular chemistry and crystal engineering. 相似文献
33.
Ami Saito Dr. Tomohisa Sawada Prof. Dr. Makoto Fujita 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(46):20547-20550
Porous metal complexes enable single-crystal X-ray crystallographic observation of included guests or reaction intermediates through simple soaking with the guests/substrates. Previous studies on this technique have often encountered difficulties in the observation of chiral structures because the host frameworks had no chirality. We synthesized a new metal–peptide porous complex through a folding-and-assembly strategy and utilized the chiral pore for trapping chiral guests. Chiral alcohols and ketones were successfully included within the pore. Crystallographic analyses clearly revealed not only their chemical structures but also chiral transformation events within the pore such as fixed conformations or an unstable hemiacetal formation. 相似文献
34.
Dr. Gang Liao Dr. Tao Zhang Zhi-Keng Lin Prof. Dr. Bing-Feng Shi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(45):19941-19954
Transition metal-catalyzed enantioselective functionalization of C−H bond, the most abundant functionality in organic molecules, has emerged as an expedient synthetic approach to streamline the synthesis of complex chiral molecules. Despite significant progress, traditional directing group-enabled strategies require additional steps for the installation and removal of directing groups from the target molecule. The recently developed asymmetric C−H functionalization using chiral transient directing groups (cTDGs) offers a promising alternative that can circumvent this obstacle and therefore simplify the process. In this Minireview, we briefly discuss the advent and recent advances of this emerging concept, with an emphasis on discussing the creation of various stereogenic centers and the developments of cTDGs. Applications in natural product synthesis and ligand derivatizations are also discussed. We hope this Minireview will highlight the great potential of this strategy and help to inspire further endeavors. 相似文献
35.
Yukimasa Aida Juntaro Nogami Dr. Haruki Sugiyama Prof. Dr. Hidehiro Uekusa Prof. Dr. Ken Tanaka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(55):12579-12588
The enantioselective synthesis of polycyclic aromatic hydrocarbon (PAH)-based planar chiral cyclophanes was achieved for the first time by the rhodium-catalyzed intramolecular regio- and enantioselective [2+2+2] cycloaddition of tethered diyne-benzofulvenes followed by stepwise oxidative transformations. The thus synthesized planar chiral bent cyclophanes, that possess bent p-terphenyl- and 9-fluorenone-cores, were converted to 9-fluorenol-based ones with excellent ee values of >99 % by diastereoselective 1,2-reduction. These 9-fluorenol-based cyclophanes exhibited high fluorescence quantum yields, which were significantly higher than that of an acyclic reference molecule (78–82 % vs. 48 %). The bending effect on the chiroptical property was also examined, which revealed that the anisotropy factors (gabs values) for electronic circular dichroism (ECD) of these 9-fluorenol-based planar chiral bent cyclophanes increase as the tether length becomes shorter. 相似文献
36.
The effective action of chiral QCD2 was studied in
two-dimensional non-commutative space-time by using path integral
approach. It is shown that vector boson has a mass generation and
the effective Lagrangian contains a term corresponding to a
Wess-Zumino-Witten-like term. 相似文献
37.
Changji Liu Yuanyuan Huang Fangrong Hu Yiwen E Xiaoxiang Dong Yong Yang Yanping Jin Xinlong Xu 《Annalen der Physik》2020,532(3):1900398
Inspired by the chiral structure from mode interaction, a chiral terahertz metamaterial and its complementary structure with the coexistence of asymmetric transmission and circular dichroism response are designed. The asymmetric transmission happens in the presence of electric and magnetic modes perpendicular to each other, resulting from intrinsic chirality under normal incidence. Circular dichroism exists in the presence of electric and magnetic modes parallel to each other under oblique incidence because of extrinsic chirality. Both asymmetric transmission and circular dichroism are enhanced by complementary structures, benefitting from the coupling between adjacent units. The maximum of chiral parameter κ can achieve 450, which is one hundred times higher than previously reported. The chiral response can be tuned by the incident angle and is sensitive to the environmental refractive index. The results highlight the potential applications of these metamaterials in chiral sensing and polarization transformation devices. 相似文献
38.
毛细管电泳法分离联萘酚对映体 总被引:4,自引:1,他引:4
利用新的手性选择剂苄基氯化辛可宁,在非水相中成功地分离了联萘酚的对映体,并对分离的机理作了初步地探讨。 相似文献
39.
40.
M. G. Vinogradov L. S. Gorshkova V. A. Pavlov O. V. Mikhalev G. V. Chel'tsova I. V. Razmanov V. A. Ferapontov O. R. Malyshev G. L. Heise 《Russian Chemical Bulletin》2000,49(3):460-465
New stereoselective reducing reagents were preparedin situ by modification of NaAlH4 with various chiral diols. The efficiency of 1,4- and 1,3-diols as chiral auxiliaries in the reactions of alkyl aryl ketones
with modified NaAlH4 was considerably higher than that of 1,2-diols. The effect of the nature of the achiral ligand additionally introduced into
the chiral hydride reagent on the enantioselectivity of ketone reduction was studied. It was proposed that the sodium cation
does not necessarily participate at the stage governing the reaction stereochemistry.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp 459–464, March, 2000. 相似文献