全文获取类型
收费全文 | 908篇 |
免费 | 68篇 |
国内免费 | 25篇 |
专业分类
化学 | 712篇 |
晶体学 | 12篇 |
力学 | 37篇 |
综合类 | 1篇 |
数学 | 94篇 |
物理学 | 145篇 |
出版年
2023年 | 8篇 |
2022年 | 9篇 |
2021年 | 10篇 |
2020年 | 29篇 |
2019年 | 23篇 |
2018年 | 24篇 |
2017年 | 5篇 |
2016年 | 32篇 |
2015年 | 26篇 |
2014年 | 28篇 |
2013年 | 48篇 |
2012年 | 48篇 |
2011年 | 45篇 |
2010年 | 44篇 |
2009年 | 40篇 |
2008年 | 44篇 |
2007年 | 45篇 |
2006年 | 67篇 |
2005年 | 50篇 |
2004年 | 40篇 |
2003年 | 44篇 |
2002年 | 21篇 |
2001年 | 22篇 |
2000年 | 15篇 |
1999年 | 13篇 |
1998年 | 9篇 |
1997年 | 6篇 |
1996年 | 12篇 |
1995年 | 14篇 |
1994年 | 6篇 |
1993年 | 9篇 |
1992年 | 15篇 |
1991年 | 9篇 |
1990年 | 4篇 |
1989年 | 11篇 |
1987年 | 9篇 |
1986年 | 6篇 |
1985年 | 14篇 |
1984年 | 11篇 |
1983年 | 5篇 |
1982年 | 5篇 |
1981年 | 3篇 |
1980年 | 7篇 |
1979年 | 8篇 |
1978年 | 17篇 |
1977年 | 5篇 |
1976年 | 8篇 |
1975年 | 4篇 |
1973年 | 8篇 |
1940年 | 2篇 |
排序方式: 共有1001条查询结果,搜索用时 31 毫秒
61.
Wing Ying Chow Brendan P. Norman Norman B. Roberts Lakshminarayan R. Ranganath Christian Teutloff Robert Bittl Melinda J. Duer James A. Gallagher Hartmut Oschkinat 《Angewandte Chemie (International ed. in English)》2020,59(29):11937-11942
Alkaptonuria (AKU) is a rare disease characterized by high levels of homogentisic acid (HGA); patients suffer from tissue ochronosis: dark brown pigmentation, especially of joint cartilage, leading to severe early osteoarthropathy. No molecular mechanism links elevated HGA to ochronosis; the pigment's chemical identity is still not known, nor how it induces joint cartilage degradation. Here we give key insight on HGA‐derived pigment composition and collagen disruption in AKU cartilage. Synthetic pigment and pigmented human cartilage tissue both showed hydroquinone‐resembling NMR signals. EPR spectroscopy showed that the synthetic pigment contains radicals. Moreover, we observed intrastrand disruption of collagen triple helix in pigmented AKU human cartilage, and in cartilage from patients with osteoarthritis. We propose that collagen degradation can occur via transient glycyl radicals, the formation of which is enhanced in AKU due to the redox environment generated by pigmentation. 相似文献
62.
Zhen Chen Vivian Wing‐Wah Yam 《Angewandte Chemie (International ed. in English)》2020,59(12):4840-4845
The development of size‐selective membranes with well‐defined nanopores towards the precise separation of nanometer‐sized substances is a challenging task to achieve. Here a supramolecular membrane is presented that comprises a highly oriented, honeycomb‐like, 2D supramolecular polymer on a polycarbonate filter support. It enables precise size‐selective sieving of colloidal nanoparticles (NPs). Owing to the uniform parallel‐aligned nanocavities within the 2D supramolecular polymers, the composite membrane shows a high size‐selectivity with a sub‐nanometer accuracy in the cutoff size of about 4.0 nm. In principle, the species of size‐separable particles are unlimited, as demonstrated by quantum dots, noble metal, and metal oxide NPs. This supramolecular membrane combined with filtration advances the potential of NPs in terms of their monochromatic emission and size monodispersity, and also enables rapid removal of small magnetic NP adsorbents that are otherwise difficult to capture. 相似文献
63.
64.
Wing Chi Yu Shi-Jian Gu Hai-Qing Lin 《The European Physical Journal B - Condensed Matter and Complex Systems》2016,89(10):212
Without any knowledge of the symmetry existing in a system, we derive the exact forms of the order parameters which show long-range correlations in the ground state of the one-dimensional (1D) extended Hubbard model using a quantum information approach. Our work demonstrates that the quantum information approach can help us to find the explicit form of the order parameter, which could not be derived systematically via traditional methods in the condensed matter theory. 相似文献
65.
Structural Manipulation of Ruthenium(II) Polypyridine Nitrone Complexes to Generate Phosphorogenic Bioorthogonal Reagents for Selective Cellular Labeling 下载免费PDF全文
Tommy Siu‐Ming Tang Dr. Hua‐Wei Liu Prof. Kenneth Kam‐Wing Lo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(28):9649-9659
We report a new class of ruthenium(II) polypyridine complexes functionalized with a nitrone group as phosphorogenic bioorthogonal probes. These complexes were very weakly emissive owing to rapid C=N isomerization of the nitrone moiety, but exhibited significant emission enhancement upon strain‐promoted alkyne–nitrone cycloaddition (SPANC) reaction with bicyclo[6.1.0]nonyne (BCN)‐modified substrates. The modification of nitrone with a dicationic ruthenium(II) polypyridine unit at the α‐C‐position and a phenyl ring at the N‐position led to remarkably accelerated reaction kinetics, which are substantially greater (up to ≈278 fold) than those of other acyclic nitrone–BCN systems. Interestingly, the complexes achieved specific cell membrane/cytosol staining upon specific labeling of an exogenous substrate, BCN‐modified decane (BCN‐C10), in live cells. Importantly, the in situ generation of the more lipophilic isoxazoline adduct in the cytoplasm resulted in increased cytotoxicity, highlighting a novel approach to apply the SPANC labeling technique in drug activation. 相似文献
66.
The structure and bonding of the chlorine atom/carbon disulfide (CS(2)/Cl) complex involved in selective photochlorination reactions with alkanes was directly probed using transient resonance Raman spectroscopy. The experimental Raman vibrational frequencies were compared to those computed from density functional theory calculations for probable structures of the CS(2)/Cl complex. Our results indicate that the S [double bond] C [double bond] S...Cl complex species is responsible for the approximately 370 nm transient absorption band observed after ultraviolet photolysis of CCl(4) in the presence of CS(2). We discuss the structure and properties of the S [double bond] C [double bond] S...Cl complex and compare them with those for the related benzene/Cl and pyridine/Cl complexes. 相似文献
67.
68.
Wing Tsang 《国际化学动力学杂志》1978,10(1):41-66
Tertiary-amyl amine has been decomposed in single-pulse shock-tube experiments. Rate expressions for several of the important primary steps are This leads to D(CH3? H) – D(NH2? H) = ?10.5 kJ and D[(CH3)3C? H] – D[(CH3)2NH2C? H] = + 6 kJ. The present and earlier comparative rate single-pulse shock-tube data when combined with high-pressure hydrazine decomposition results-(after correcting for fall off effects through RRKM calculations) gives where kr(…) is the recombination rate involving the appropriate radicals. This suggests that in this context amino radical behavior is analogous to that of alkyl radicals. If this agreement is exact, then Rate expressions for the primary step in the decomposition of a variety of primary amines have been computed. In the case of benzyl amine where data exist the agreement is satisfactory. The following differences in bond energies have been estimated: 相似文献
69.
Wing Tsang 《国际化学动力学杂志》1978,10(6):599-617
Cyclopentane has been decomposed in comparative-rate single-pulse shock-tube experiments. The pyrolytic mechanism involves isomerization to 1-pentene and also a minor pathway leading to cyclopropane and ethylene. This is followed by the decomposition of 1-pentene and cyclopropane. The rate expressions over the temperature range of 1000°–1200° K are Details of the cyclopentane decomposition processes are considered, and it appears that if the trimethylene radical is an intermediate, then ΔHf(trimethylene) ≤ 280 kJ/mol at 300°K. 相似文献
70.