全文获取类型
收费全文 | 578篇 |
免费 | 38篇 |
国内免费 | 9篇 |
专业分类
化学 | 452篇 |
晶体学 | 9篇 |
力学 | 10篇 |
数学 | 77篇 |
物理学 | 77篇 |
出版年
2023年 | 7篇 |
2022年 | 12篇 |
2021年 | 14篇 |
2020年 | 25篇 |
2019年 | 20篇 |
2018年 | 20篇 |
2017年 | 16篇 |
2016年 | 24篇 |
2015年 | 28篇 |
2014年 | 26篇 |
2013年 | 33篇 |
2012年 | 50篇 |
2011年 | 45篇 |
2010年 | 18篇 |
2009年 | 17篇 |
2008年 | 23篇 |
2007年 | 28篇 |
2006年 | 28篇 |
2005年 | 24篇 |
2004年 | 22篇 |
2003年 | 14篇 |
2002年 | 21篇 |
2001年 | 9篇 |
2000年 | 9篇 |
1999年 | 5篇 |
1998年 | 4篇 |
1997年 | 3篇 |
1996年 | 6篇 |
1995年 | 2篇 |
1994年 | 4篇 |
1993年 | 3篇 |
1992年 | 7篇 |
1991年 | 3篇 |
1989年 | 3篇 |
1987年 | 4篇 |
1986年 | 2篇 |
1985年 | 4篇 |
1984年 | 5篇 |
1983年 | 4篇 |
1982年 | 6篇 |
1981年 | 3篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1976年 | 3篇 |
1975年 | 2篇 |
1973年 | 2篇 |
1972年 | 2篇 |
1970年 | 1篇 |
1948年 | 3篇 |
1929年 | 2篇 |
排序方式: 共有625条查询结果,搜索用时 0 毫秒
21.
This article is a highlight of the study by Maclean et al. in this issue of Photochemistry and Photobiology describing the sporicidal effects 405 nm visible light alone on endospores of the Clostridium and Bacillus genera. 1.73 kJ cm?2 was capable of reducing endospore colony‐forming units by up to 4‐log10. These findings have never been previously demonstrated and may be incorporated into decontamination methods that span medical, military and food preparatory applications. 相似文献
22.
23.
Tyler T. Clikeman Dr. Igor V. Kuvychko Dr. Natalia B. Shustova Dr. Yu‐Sheng Chen Dr. Alexey A. Popov Dr. Olga V. Boltalina Prof. Steven H. Strauss 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(16):5070-5080
The sequential addition of CN? or CH3? and electrophiles to three perfluoroalkylfullerenes (PFAFs), Cs‐C70(CF3)8, C1‐C70(CF3)10, and Cs‐p‐C60(CF3)2, was carried out to determine the most reactive individual fullerene C atoms (as opposed to the most reactive C?C bonds, which has previously been studied). Each PFAF reacted with CH3? or CN? to generate metastable PFAF(CN)? or PFAF(CH3)22? species with high regioselectivity (i.e., one or two predominant isomers). They were treated with electrophiles E+ to generate PFAF(CN)(E) or PFAF(CH3)2(E)2 derivatives, also with high regioselectivity (E+=CN+, CH3+, or H+). All of the predominant products, characterized by mass spectrometry and 19F NMR spectroscopy, are new compounds. Some could be purified by HPLC to give single isomers. Two of them, C70(CF3)8(CN)2 and C70(CF3)10(CH3)2(CN)2, were characterized by single‐crystal X‐ray diffraction. DFT calculations were used to propose whether a particular reaction is under kinetic or thermodynamic control. 相似文献
24.
Erica D. Couch Dr. Tyler J. Auvil Prof. Anita E. Mattson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(27):8283-8287
The enhanced catalytic activity of difluoroboronate ureas proved to be essential as an acidity amplifier to promote metal‐free O?H and S?H insertion reactions of α‐aryldiazoacetates in high yield. This methodology was found to be generally applicable to a broad substrate scope and presents a conceptually new approach for organocatalytic diazo insertion reactions. Mechanistic investigations suggest that the reaction pathway involves a urea‐induced protonation of the α‐aryldiazoester. 相似文献
25.
Direct X‐ray Observation of Trapped CO2 in a Predesigned Porphyrinic Metal–Organic Framework 下载免费PDF全文
Jacob A. Johnson Dr. Shuang Chen Tyler C. Reeson Dr. Yu‐Sheng Chen Prof. Xiao Cheng Zeng Prof. Jian Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(25):7632-7637
Metal–organic frameworks (MOFs) are emerging microporous materials that are promising for capture and sequestration of CO2 due to their tailorable binding properties. However, it remains a grand challenge to pre‐design a MOF with a precise, multivalent binding environment at the molecular level to enhance CO2 capture. Here, we report the design, synthesis, and direct X‐ray crystallographic observation of a porphyrinic MOF, UNLPF‐2, that contains CO2‐specific single molecular traps. Assembled from an octatopic porphyrin ligand with [Co2(COO)4] paddlewheel clusters, UNLPF‐2 provides an appropriate distance between the coordinatively unsaturated metal centers, which serve as the ideal binding sites for in situ generated CO2. The coordination of CoII in the porphyrin macrocycle is crucial and responsible for the formation of the required topology to trap CO2. By repeatedly releasing and recapturing CO2, UNLPL‐2 also exhibits recyclability. 相似文献
26.
D. Thao Nguyen Matthias Freitag Christian Gutheil Dr. Kai Sotthewes Dr. Bonnie J. Tyler Dr. Marcus Böckmann Mowpriya Das Friederike Schlüter Prof. Dr. Nikos L. Doltsinis Prof. Dr. Heinrich F. Arlinghaus Prof. Dr. Bart Jan Ravoo Prof. Dr. Frank Glorius 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(32):13754-13759
27.
Adedamola S. Arojojoye R. Tyler Mertens Samuel Ofori Sean R. Parkin Samuel G. Awuah 《Molecules (Basel, Switzerland)》2020,25(23)
Herein is reported the synthesis of two Au(III) complexes bearing the (R,R)-(–)-2,3-Bis(tert-butylmethylphosphino)quinoxaline (R,R-QuinoxP*) or (S,S)-(+)-2,3-Bis(tert-butylmethylphosphino)quinoxaline (S,S-QuinoxP*) ligands. By reacting two stoichiometric equivalents of HAuCl4.3H2O to one equivalent of the corresponding QuinoxP* ligand, (R,R)-(–)-2,3-Bis(tert-butylmethylphosphino)quinoxalinedichlorogold(III) tetrachloroaurates(III) (1) and (S,S)-(+)-2,3-Bis(tert-butylmethylphosphino)quinoxalinedichlorogold(III) tetrachloroaurates(III) (2) were formed, respectively, in moderate yields. The structure of (S,S)-(+)-2,3-Bis(tert-butylmethylphosphino)quinoxalinedichlorogold(III) tetrachloroaurates(III) (2) was further confirmed by X-ray crystallography. The antiproliferative activities of the two compounds were evaluated in a panel of cell lines and exhibited promising results comparable to auranofin and cisplatin with IC50 values between 1.08 and 4.83 µM. It is noteworthy that in comparison to other platinum and ruthenium enantiomeric complexes, the two enantiomers (1 and 2) do not exhibit different cytotoxic effects. The compounds exhibited stability in biologically relevant media over 48 h as well as inert reactivity to excess glutathione at 37 °C. These results demonstrate that the Au(III) atom, stabilized by the QuinoxP* ligand, can provide exciting compounds for novel anticancer drugs. These complexes provide a new scaffold to further develop a robust and diverse library of chiral phosphorus Au(III) complexes. 相似文献
28.
Tyler B. J. Pinter Karl J. Koebke Vincent L. Pecoraro 《Angewandte Chemie (International ed. in English)》2020,59(20):7678-7699
The relationship between protein structure and function is one of the greatest puzzles within biochemistry. De novo metalloprotein design is a way to wipe the board clean and determine what is required to build in function from the ground up in an unrelated structure. This Review focuses on protein design efforts to create de novo metalloproteins within alpha‐helical scaffolds. Examples of successful designs include those with carbonic anhydrase or nitrite reductase activity by incorporating a ZnHis3 or CuHis3 site, or that recapitulate the spectroscopic properties of unique electron‐transfer sites in cupredoxins (CuHis2Cys) or rubredoxins (FeCys4). This work showcases the versatility of alpha helices as scaffolds for metalloprotein design and the progress that is possible through careful rational design. Our studies cover the invariance of carbonic anhydrase activity with different site positions and scaffolds, refinement of our cupredoxin models, and enhancement of nitrite reductase activity up to 1000‐fold. 相似文献
29.
D. Thao Nguyen Matthias Freitag Christian Gutheil Kai Sotthewes Bonnie J. Tyler Marcus Bckmann Mowpriya Das Friederike Schlüter Nikos L. Doltsinis Heinrich F. Arlinghaus Bart Jan Ravoo Frank Glorius 《Angewandte Chemie (International ed. in English)》2020,59(32):13651-13656
A novel photoresponsive and fully conjugated N‐heterocyclic carbene (NHC) has been synthesized that combines the excellent photophysical properties of arylazopyrazoles (AAPs) with an NHC that acts as a robust surface anchor (AAP‐BIMe). The formation of self‐assembled monolayers (SAMs) on gold was proven by ToF‐SIMS and XPS, and the organic film displayed a very high stability at elevated temperatures. This stability was also reflected in a high desorption energy, which was determined by temperature‐programmed SIMS measurements. E‐/Z‐AAP‐BIMe@Au photoisomerization resulted in reversible alterations of the surface energy (i.e. wettability), the surface potential (i.e. work function), and the conductance (i.e. resistance). The effects could be explained by the difference in the dipole moment of the isomers. Furthermore, sequential application of a dummy ligand by microcontact printing and subsequent backfilling with AAP‐BIMe allowed its patterning on gold. To the best of our knowledge, this is the first example of a photoswitchable NHC on a gold surface. These properties of AAP‐BIMe@Au illustrate its suitability as a molecular switch for electronic devices. 相似文献
30.
Alexander M. Powell J. Tyler Whitehouse 《Foundations of Computational Mathematics》2016,16(2):395-423
Consistent reconstruction is a method for producing an estimate \(\widetilde{x} \in {\mathbb {R}}^d\) of a signal \(x\in {\mathbb {R}}^d\) if one is given a collection of \(N\) noisy linear measurements \(q_n = \langle x, \varphi _n \rangle + \epsilon _n\), \(1 \le n \le N\), that have been corrupted by i.i.d. uniform noise \(\{\epsilon _n\}_{n=1}^N\). We prove mean-squared error bounds for consistent reconstruction when the measurement vectors \(\{\varphi _n\}_{n=1}^N\subset {\mathbb {R}}^d\) are drawn independently at random from a suitable distribution on the unit-sphere \({\mathbb {S}}^{d-1}\). Our main results prove that the mean-squared error (MSE) for consistent reconstruction is of the optimal order \({\mathbb {E}}\Vert x - \widetilde{x}\Vert ^2 \le K\delta ^2/N^2\) under general conditions on the measurement vectors. We also prove refined MSE bounds when the measurement vectors are i.i.d. uniformly distributed on the unit-sphere \({\mathbb {S}}^{d-1}\) and, in particular, show that in this case, the constant \(K\) is dominated by \(d^3\), the cube of the ambient dimension. The proofs involve an analysis of random polytopes using coverage processes on the sphere. 相似文献