全文获取类型
收费全文 | 43455篇 |
免费 | 18116篇 |
国内免费 | 59篇 |
专业分类
化学 | 55385篇 |
晶体学 | 53篇 |
力学 | 2052篇 |
数学 | 2754篇 |
物理学 | 1386篇 |
出版年
2024年 | 157篇 |
2023年 | 4079篇 |
2022年 | 1429篇 |
2021年 | 2474篇 |
2020年 | 4624篇 |
2019年 | 2317篇 |
2018年 | 2289篇 |
2017年 | 612篇 |
2016年 | 5584篇 |
2015年 | 5535篇 |
2014年 | 4961篇 |
2013年 | 5166篇 |
2012年 | 3214篇 |
2011年 | 1057篇 |
2010年 | 3430篇 |
2009年 | 3384篇 |
2008年 | 1065篇 |
2007年 | 767篇 |
2006年 | 139篇 |
2005年 | 101篇 |
1997年 | 85篇 |
1996年 | 85篇 |
1995年 | 152篇 |
1994年 | 95篇 |
1993年 | 221篇 |
1992年 | 115篇 |
1988年 | 122篇 |
1987年 | 105篇 |
1985年 | 107篇 |
1984年 | 122篇 |
1983年 | 111篇 |
1982年 | 137篇 |
1981年 | 166篇 |
1980年 | 200篇 |
1979年 | 192篇 |
1978年 | 204篇 |
1977年 | 314篇 |
1976年 | 366篇 |
1975年 | 459篇 |
1974年 | 474篇 |
1973年 | 287篇 |
1972年 | 369篇 |
1971年 | 355篇 |
1970年 | 542篇 |
1969年 | 415篇 |
1968年 | 445篇 |
1967年 | 117篇 |
1966年 | 91篇 |
1965年 | 87篇 |
1963年 | 112篇 |
排序方式: 共有10000条查询结果,搜索用时 125 毫秒
991.
Dr. Yoichi Hoshimoto Keita Ashida Yukari Sasaoka Dr. Ravindra Kumar Prof. Dr. Ken Kamikawa Prof. Dr. Xavier Verdaguer Prof. Dr. Antoni Riera Prof. Dr. Masato Ohashi Prof. Dr. Sensuke Ogoshi 《Angewandte Chemie (International ed. in English)》2017,56(28):8206-8210
The nickel(0)-catalyzed carbonylative cycloaddition of 1,5- and 1,6-ene-imines with carbon monoxide (CO) is reported. Key to this reaction is the efficient regeneration of the catalytically active nickel(0) species from nickel carbonyl complexes such as [Ni(CO)3L]. A variety of tri- and tetracyclic γ-lactams were thus prepared in excellent yields with 100 % atom efficiency. Preliminary results on asymmetric derivatives promise potential in the synthesis of enantioenriched polycyclic γ-lactams. 相似文献
992.
Yohan Gisbert Dr. Seifallah Abid Dr. Claire Kammerer Prof. Dr. Gwénaël Rapenne 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(65):16242-16249
We report the synthesis of conceptually new prototypes of molecular winches with the ultimate aim to investigate the work performed by a single ruthenium-based molecular motor anchored on a surface by probing its ability to pull a load upon electrically-driven directional rotation. According to a technomimetic design, the motor was embedded in a winch structure, with a long flexible polyethylene glycol chain terminated by an azide hook to connect a variety of molecular loads. The structure of the motor was first derivatized by means of two sequential cross-coupling reactions involving a penta(4-halogenophenyl)cyclopentadienyl hydrotris(indazolyl)borate ruthenium(II) precursor and the resulting benzylamine derivative was next exploited as key intermediate in the divergent synthesis of a family of nanowinch prototypes. A one-pot method involving sequential peptide coupling and Cu-catalyzed azide-alkyne cycloaddition was developed to yield four loaded nanowinches, with load fragments encompassing triptycene, fullerene and porphyrin moieties. 相似文献
993.
994.
Owen Zacarias Prof. Ana G. Petrovic Prof. Dr. Rinat Abzalimov Prof. Padmanava Pradhan Prof. Elise Champeil 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(57):14263-14272
Mitomycin C, (MC), an antitumor drug, is a DNA alkylating agent currently used in the clinics. Inert in its native form, MC is reduced to reactive mitosenes, which undergo nucleophilic attack by guanine or adenine bases in DNA to form monoadducts as well as interstrand crosslinks (ICLs). Although ICLs are considered the most cytotoxic lesions, the role of each individual adduct in the drug's cytotoxicity is still not fully understood. Synthetic routes have been developed to access modified oligonucleotides containing dG MC-monoadducts and dG-MC-dG ICL at a single position of their base sequences to investigate the biological effects of these adducts. However, until now, oligonucleotides containing monoadducts formed by MC at the adenine base had not been available, thus preventing the examination of the role played by these lesions in the toxicity of MC. Here, we present a route to access these substrates. Structural proof of the adducted oligonucleotides were provided by enzymatic digestion to nucleosides and high-resolution mass spectral analysis. Additionally, parent oligonucleotides containing a dG monoadduct and a dG-MC-dG ICL were also produced. The stability and physical properties of all substrates were compared via CD spectroscopy and UV melting temperature studies. Finally, virtual models were created to explore the conformational space and structural features of these MC-DNA complexes. 相似文献
995.
996.
997.
Wan-Yue Diao Dan Xie Yan-Fei Li Ru Jiang Fang-Yu Tao Prof. Hai-Zhu Sun Prof. Xing-Long Wu Dr. Xiao-Ying Zhang Prof. Jing-Ping Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(31):8168-8177
Lithium metal anodes (LMAs) with high energy density have recently captured increasing attention for development of next-generation batteries. However, practical viability of LMAs is hindered by the uncontrolled Li dendrite growth and infinite dimension change. Even though constructing 3D conductive skeleton has been regarded as a reliable strategy to prepare stable and low volume stress LMAs, engineering the renewable and lithiophilic conductive scaffold is still a challenge. Herein, a robust conductive scaffold derived from renewable cellulose paper, which is coated with reduced graphene oxide and decorated with lithiophilic Au nanoparticles, is engineered for LMAs. The graphene cellulose fibres with high surface area can reduce the local current density, while the well-dispersed Au nanoparticles can serve as lithiophilic nanoseeds to lower the nucleation overpotential of Li plating. The coupled relationship can guarantee uniform Li nucleation and unique spherical Li growth into 3D carbon matrix. Moreover, the natural cellulose paper possesses outstanding mechanical strength to tolerate the volume stress. In virtue of the modulated deposition behaviour and near-zero volume change, the hybrid LMAs can achieve reversible Li plating/stripping even at an ultrahigh current density of 10 mA cm−2 as evidenced by high Coulombic efficiency (97.2 % after 60 cycles) and ultralong lifespan (1000 cycles) together with ultralow overpotential (25 mV). Therefore, this strategy sheds light on a scalable approach to multiscale design versatile Li host, promising highly stable Li metal batteries to be feasible and practical. 相似文献
998.
Die Chen Dr. Shu Yang Huayi Han Lingbo Song Dr. Dan Huang Xiao Lin Dr. Xiaoping Xu Dr. Qianfan Yang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(45):11627-11632
DNA computation is considered a fascinating alternative to silicon-based computers; it has evoked substantial attention and made rapid advances. Besides realizing versatile functions, implementing spatiotemporal control of logic operations, especially at the cellular level, is also of great significance to the development of DNA computation. However, developing simple and efficient methods to restrict DNA logic gates performing in live cells is still a challenge. In this work, a series of DNA logic gates was designed by taking full advantage of the diversity and programmability of the G-quadruplex (G4) structure. More importantly, by further using the high affinity and specific endocytosis of cells to aptamer G4, an INHIBIT logic gate has been realized whose operational site is precisely restricted to specific live cells. The design strategy might have great potential in the field of molecular computation and smart bio-applications. 相似文献
999.
Jessica E. Waters Georg Berger Dr. Andrew J. Peel Dr. Raúl García-Rodríguez Dr. Andrew D. Bond Prof. Dominic S. Wright 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(47):12036-12040
Supramolecular main group chemistry is a developing field which parallels the conventional domain of metallo-organic chemistry. Little explored building blocks in this area are main group metal-based ligands which have the appropriate donor symmetry to build desired molecular or extended arrangements. Tris(pyridyl) main group ligands (E(py)3, E=main group metal) are potentially highly versatile building blocks since shifting the N-donor arms from the 2- to the 3-positions and 4-positions provides a very simple way of changing the ligand character from mononuclear/chelating to multidentate/metal-bridging. Here, the coordination behaviour of the first main group metal tris(4-pyridyl) ligands, E(4-py)3 (E=Sb, Bi, Ph−Sn) is explored, as well as their ability to build metal-organic frameworks (MOFs). The complicated topology of these MOFs shows a marked influence on the counter anion and on the ability of the E(4-py)3 ligands to switch coordination mode, depending on the steric and donor character of the bridgehead. This structure-directing influence of the bridgehead provides a potential building strategy for future molecular and MOF design in this area. 相似文献
1000.
Dr. Eduard Baal Marius Klein Dr. Klaus Harms Prof. Dr. Jörg Sundermeyer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(49):12610-12618
The synthesis of 2,9-diaza-1,3,8,10-tetratriflato-dibenzoperylene (DDP 3 a ) and corresponding 2,9-dimethyl-1,3,8,10-tetratriflato-dibenzoperylene (DBP 3 b ) has been developed at multigram scale via reduction of one of the industrially most important high-performance dyes, perylene-3,4,9,10-tetracarboxylic diimide (PTCDI), and of the corresponding dihydroxy peropyrenequinone precursor. The focus of this paper is on the reactivity pattern of 3 a as key intermediate towards highly functionalized 2,9-diazadibenzopyrelenes (DDPs) obtained via catalytic substitution of four triflate by aryl, heteroaryl, alkynyl, aminyl, and O-phosphanyl substituents. The influence of electron-donating substituents (OSiMe3, OPt-Bu2, N-piperidinyl), electron-withdrawing (OTf, 3,5-bis-trifluoromethyl-phenyl), and of electron-rich π-conjugated (2-thienyl, 4-tert-butylphenyl, trimethylsilyl-ethynyl) substituents on optoelectronic and structural properties of these functionalized DDPs has been investigated via XRD analyses, UV/Vis, PL spectroscopy, and by electroanalytical CV. These results were correlated to results of DFT and TD-DFT calculations. Thus, functionalized DPPs with easily tunable HOMO and LUMO energies and gap became available via a new and reliable synthetic strategy starting from readily available PTCDI. 相似文献