全文获取类型
收费全文 | 1434篇 |
免费 | 35篇 |
国内免费 | 6篇 |
专业分类
化学 | 803篇 |
晶体学 | 4篇 |
力学 | 26篇 |
数学 | 156篇 |
物理学 | 486篇 |
出版年
2021年 | 14篇 |
2020年 | 16篇 |
2019年 | 19篇 |
2018年 | 11篇 |
2017年 | 14篇 |
2016年 | 26篇 |
2015年 | 29篇 |
2014年 | 32篇 |
2013年 | 63篇 |
2012年 | 60篇 |
2011年 | 79篇 |
2010年 | 57篇 |
2009年 | 46篇 |
2008年 | 69篇 |
2007年 | 65篇 |
2006年 | 63篇 |
2005年 | 54篇 |
2004年 | 47篇 |
2003年 | 39篇 |
2002年 | 47篇 |
2001年 | 49篇 |
2000年 | 26篇 |
1999年 | 16篇 |
1998年 | 12篇 |
1997年 | 22篇 |
1996年 | 33篇 |
1995年 | 36篇 |
1994年 | 28篇 |
1993年 | 24篇 |
1992年 | 40篇 |
1991年 | 20篇 |
1990年 | 16篇 |
1989年 | 20篇 |
1988年 | 11篇 |
1987年 | 9篇 |
1986年 | 15篇 |
1985年 | 12篇 |
1984年 | 11篇 |
1983年 | 6篇 |
1981年 | 13篇 |
1980年 | 6篇 |
1979年 | 14篇 |
1978年 | 15篇 |
1977年 | 13篇 |
1976年 | 15篇 |
1975年 | 10篇 |
1974年 | 14篇 |
1973年 | 12篇 |
1972年 | 9篇 |
1969年 | 6篇 |
排序方式: 共有1475条查询结果,搜索用时 31 毫秒
1.
Gabrielle A. Leith Allison M. Rice Brandon J. Yarbrough Anna A. Berseneva Richard T. Ly Charles N. Buck III Dr. Denis Chusov Amy J. Brandt Prof. Dr. Donna A. Chen Benjamin W. Lamm Prof. Dr. Morgan Stefik Kenneth S. Stephenson Dr. Mark D. Smith Prof. Dr. Aaron K. Vannucci Dr. Perry J. Pellechia Prof. Dr. Sophya Garashchuk Prof. Dr. Natalia B. Shustova 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(15):6056-6062
The effect of donor (D)–acceptor (A) alignment on the materials electronic structure was probed for the first time using novel purely organic porous crystalline materials with covalently bound two- and three-dimensional acceptors. The first studies towards estimation of charge transfer rates as a function of acceptor stacking are in line with the experimentally observed drastic, eight-fold conductivity enhancement. The first evaluation of redox behavior of buckyball- or tetracyanoquinodimethane-integrated crystalline was conducted. In parallel with tailoring the D-A alignment responsible for “static” changes in materials properties, an external stimulus was applied for “dynamic” control of the electronic profiles. Overall, the presented D–A strategic design, with stimuli-controlled electronic behavior, redox activity, and modularity could be used as a blueprint for the development of electroactive and conductive multidimensional and multifunctional crystalline porous materials. 相似文献
2.
Corrigendum: Reactions with a Metalloid Tin Cluster {Sn10[Si(SiMe3)3]4}2−: Ligand Elimination versus Coordination Chemistry 下载免费PDF全文
3.
Reactions with a Metalloid Tin Cluster {Sn10[Si(SiMe3)3]4}2−: Ligand Elimination versus Coordination Chemistry 下载免费PDF全文
Dr. Claudio Schrenk Birgit Gerke Prof. Dr. Rainer Pöttgen Dr. Andre Clayborne Prof. Dr. Andreas Schnepf 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(22):8222-8228
Chemistry that uses metalloid tin clusters as a starting material is of fundamental interest towards understanding the reactivity of such compounds. Since we identified {Sn10[Si(SiMe3)3]4}2? 7 as an ideal candidate for such reactions, we present a further step in the understanding of metalloid tin cluster chemistry. In contrast to germanium chemistry, ligand elimination seems to be a major reaction channel, which leads to the more open metalloid cluster {Sn10[Si(SiMe3)3]3}? 9 , in which the Sn core is only shielded by three Si(SiMe3)3 ligands. Compound 9 is obtained through different routes and is crystallised together with two different countercations. Besides the structural characterisation of this novel metalloid tin cluster, the electronic structure is analysed by 119Sn Mössbauer spectroscopy. Additionally, possible reaction pathways are discussed. The presented first step into the chemistry of metalloid tin clusters thus indicates that, with respect to metalloid germanium clusters, more reaction channels are accessible, thereby leading to a more complex reaction system. 相似文献
4.
Birgit U. Jaki Anton Bzhelyansky Guido F. Pauli 《Magnetic resonance in chemistry : MRC》2021,59(1):7-15
In the last two decades, quantitative NMR (qNMR) has become increasingly important for the analysis of pharmaceuticals, chemicals, and natural products including dietary supplements. For the purpose of quality control and chemical standardization of a large variety of pharmaceutical, chemical, and medicinal products, qNMR has proven to be a valuable orthogonal quantification method and a compelling alternative to chromatographic techniques. This work reviews a fundamental component of the early development of qNMR, reflected in the pioneering work of the late George M. Hanna during the years between 1984 and 2006 at the US Food and Drug Administration (FDA). Because Hanna performed the majority of his groundbreaking work on a 90‐MHz instrument, his legacy output connects with recent progress in low‐field benchtop NMR instrumentation. Hanna gradually established the utility of qNMR for the routine quality control analyses practiced in pharmaceutical and related operations well ahead of his peers. His work has the potential to inspire new developments in qNMR applied to small molecules of biomedical importance. 相似文献
5.
Dynamics of Fluorescent Dyes Attached to G‐Quadruplex DNA and their Effect on FRET Experiments 下载免费PDF全文
Siri Søndergaard Dr. Mikayel Aznauryan Emil K. Haustrup Prof. Birgit Schiøtt Prof. Victoria Birkedal Prof. Ben Corry 《Chemphyschem》2015,16(12):2562-2570
FRET spectroscopy is a promising approach for investigating the dynamics of G‐quadruplex DNA folds and improving the targeting of G‐quadruplexes by potential anticancer compounds. To better interpret such experiments, classical and replica‐exchange molecular dynamics simulations and fluorescence‐lifetime measurements are used to understand the behavior of a range of Cy3‐based dyes attached to the 3′ end of G‐quadruplex DNA. The simulations revealed that the dyes interact extensively with the G‐quadruplex. Identification of preferred dye positions relative to the G‐quadruplex in the simulations allows the impact of dye–DNA interactions on FRET results to be determined. All the dyes show significant deviations from the common approximation of being freely rotating and not interacting with the host, but one of the Cy3 dye analogues is slightly closer to this case. 相似文献
6.
7.
Philipp Seitz Dr. Manik Bhosale Luisa Rzesny Anselm Uhlmann Dr. Jan S. Wössner Robin Wessling Prof. Dr. Birgit Esser 《Angewandte Chemie (International ed. in English)》2023,62(43):e202306184
With their bent π-systems, cyclic conjugation and inherent cavities, conjugated nanohoops are attractive for organic electronics applications. For ease of processing and morphological stability, an incorporation into polymers is desirable, but to date was hampered with few exceptions by synthetic difficulties. We herein present a unique strategy for the synthesis of conjugated nanohoop polymers using a dibenzo[a,e]pentalene (DBP) as central connector. We demonstrate this versatility by synthesizing three electronically diverse copolymers with dithienyldiketo(pyrrolopyrrol), fluorene and carbazole comonomers, and report the first donor-acceptor nanohoop polymer. Optoelectronic investigations reveal the prevalence of cyclic or linear conjugation, depending on the comonomer unit, and ambipolar electrochemical properties through the antiaromatic character of the DBP units. As the first report on using conjugated nanohoops for charge storage as positive electrode materials, we show a significant improvement in battery performance in a nanohoop-containing polymer compared to an equivalent nanohoop-free reference polymer. We believe this study will pave the way for the synthesis of a diverse range of nanohoop polymers and further stimulate their exploration for charge storage in batteries. 相似文献
8.
F.O. Schumann I.S. Brandt Z. Wei J. Kirschner F. Giebels H. Gollisch R. Feder 《Progress in Surface Science》2021,96(2):100629
The emission of electron pairs from surfaces has the power to reveal details about the electron–electron interaction in condensed matter. This process, stimulated by a primary electron or photon beam, has been studied both in experiment and theory over the last two decades. An additional pathway, namely positron–electron pair emission, holds the promise to provide additional information. It is based on the notion that the Pauli exclusion principle does not need to be considered for this process.We have commissioned a laboratory based positron source and performed a systematic study on a variety of solid surfaces. In a symmetric emission geometry we can explore the fact that positron and electron are distinguishable particles. Following fundamental symmetry arguments we have to expect that the available energy is shared unequally among positron and electron. Experimentally we observe such a behavior for all materials studied. We find an universal feature for all materials in the sense that on average the positron carries a larger fraction of the available energy. This is qualitatively accounted for by a simplified scattering model. Numerical results, which we obtained by a microscopic theory of positron–electron emission from surfaces, reveal however that there are also cases in which the electron carries more energy. Whether the positron or the electron is more energetic depends on details of the bound electron state and of the emission geometry. The coincidence intensity is strongly material dependent and there exists an almost monotonic relation between the singles and coincidence intensity. These results resemble the findings obtained in electron and photon stimulated electron pair emission. An additional reaction channel is the emission of an electron pair upon positron impact. We will discuss the energy distributions and the material dependence of the coincidence signal which shows similar features as those for positron–electron pairs. 相似文献
9.
Dr. Anna Pakhomova Birgit Fuchs Prof. Dr. Leonid S. Dubrovinsky Prof. Dr. Natalia Dubrovinskaia Prof. Dr. Hubert Huppertz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(19):6007-6014
Based on the results from previous high-pressure experiments on the gadolinite-type mineral datolite, CaBSiO4(OH), the behavior of the isostructural borates β-HfB2O5 and β-ZrB2O5 have been studied by synchrotron-based in situ high-pressure single-crystal X-ray diffraction experiments. On compression to 120 GPa, both borate layer-structures are preserved. Additionally, at ≈114 GPa, the formation of a second phase can be observed in both compounds. The new high-pressure modification γ-ZrB2O5 features a rearrangement of the corner-sharing BO4 tetrahedra, while still maintaining the four- and eight-membered rings. The new phase γ-HfB2O5 contains ten-membered rings including the rare structural motif of edge-sharing BO4 tetrahedra with exceptionally short B−O and B⋅⋅⋅B distances. For both structures, unusually high coordination numbers are found for the transition metal cations, with ninefold coordinated Hf4+, and tenfold coordinated Zr4+, respectively. These findings remarkably show the potential of cold compression as a low-energy pathway to discover metastable structures that exhibit new coordinations and structural motifs. 相似文献
10.
David Adner Marcus Korb Charles Lochenie Birgit Weber Heinrich Lang 《无机化学与普通化学杂志》2015,641(7):1243-1246
The synthesis and characterisation of the hexanuclear copper(II) carboxylate complex [Cu(O2CCHPhOC2H4OC2H4OCH3)2]6 ( 1 ) is described. Single‐crystal X‐ray structure analysis reveals that the copper(II) ions are arranged in a six‐membered ring which adopts a chair‐like conformation. The copper(II) ions are bridged by μ2‐ and μ3‐coordinating carboxylates. The magnetic behavior of 1 was measured between 2 and 300 K, revealing at low temperature a weak antiferromagnetic interaction. The χM(T) dependency was fitted mathematically with one coupling constant J1 and a paramagnetic impurity α. 相似文献