全文获取类型
收费全文 | 1049篇 |
免费 | 41篇 |
国内免费 | 9篇 |
专业分类
化学 | 849篇 |
晶体学 | 2篇 |
力学 | 4篇 |
数学 | 120篇 |
物理学 | 124篇 |
出版年
2023年 | 8篇 |
2022年 | 11篇 |
2021年 | 19篇 |
2020年 | 16篇 |
2019年 | 24篇 |
2018年 | 11篇 |
2017年 | 8篇 |
2016年 | 31篇 |
2015年 | 30篇 |
2014年 | 31篇 |
2013年 | 50篇 |
2012年 | 71篇 |
2011年 | 85篇 |
2010年 | 65篇 |
2009年 | 52篇 |
2008年 | 69篇 |
2007年 | 57篇 |
2006年 | 44篇 |
2005年 | 52篇 |
2004年 | 55篇 |
2003年 | 29篇 |
2002年 | 43篇 |
2001年 | 20篇 |
2000年 | 17篇 |
1999年 | 17篇 |
1998年 | 14篇 |
1997年 | 21篇 |
1996年 | 14篇 |
1995年 | 9篇 |
1994年 | 5篇 |
1993年 | 11篇 |
1992年 | 8篇 |
1991年 | 6篇 |
1990年 | 7篇 |
1988年 | 4篇 |
1987年 | 8篇 |
1986年 | 5篇 |
1985年 | 4篇 |
1984年 | 3篇 |
1982年 | 5篇 |
1981年 | 5篇 |
1980年 | 8篇 |
1979年 | 8篇 |
1978年 | 4篇 |
1975年 | 3篇 |
1973年 | 4篇 |
1972年 | 3篇 |
1969年 | 7篇 |
1939年 | 2篇 |
1924年 | 2篇 |
排序方式: 共有1099条查询结果,搜索用时 15 毫秒
61.
Susanne Bhr Sabine Brinkmann‐Chen Marc Garcia‐Borrs John M. Roberts Dimitris E. Katsoulis K. N. Houk Frances H. Arnold 《Angewandte Chemie (International ed. in English)》2020,59(36):15507-15511
Compared to the biological world's rich chemistry for functionalizing carbon, enzymatic transformations of the heavier homologue silicon are rare. We report that a wild‐type cytochrome P450 monooxygenase (P450BM3 from Bacillus megaterium, CYP102A1) has promiscuous activity for oxidation of hydrosilanes to give silanols. Directed evolution was applied to enhance this non‐native activity and create a highly efficient catalyst for selective silane oxidation under mild conditions with oxygen as the terminal oxidant. The evolved enzyme leaves C?H bonds present in the silane substrates untouched, and this biotransformation does not lead to disiloxane formation, a common problem in silanol syntheses. Computational studies reveal that catalysis proceeds through hydrogen atom abstraction followed by radical rebound, as observed in the native C?H hydroxylation mechanism of the P450 enzyme. This enzymatic silane oxidation extends nature's impressive catalytic repertoire. 相似文献
62.
Joanna Witos Erno Karjalainen Heikki Tenhu Susanne K. Wiedmer 《Journal of separation science》2020,43(12):2495-2505
Amphiphilic diblock copolymers consisting of a hydrophobic core containing a polymerized ionic liquid and an outer shell composed of poly(N‐isoprolylacrylamide) were investigated by capillary electrophoresis and asymmetrical flow‐field flow fractionation. The polymerized ionic liquid comprised poly(2‐(1‐butylimidazolium‐3‐yl)ethyl methacrylate tetrafluoroborate) with a constant block length (n = 24), while the length of the poly(N‐isoprolylacrylamide) block varied (n = 14; 26; 59; 88). Possible adsorption of the block copolymer on the fused silica capillary, due to alterations in the polymeric conformation upon a change in the temperature (25 and 45 °C), was initially studied. For comparison, the effect of temperature on the copolymer conformation/hydrodynamic size was determined with the aid of asymmetrical flow‐field flow fractionation and light scattering. To get more information about the hydrophilic/hydrophobic properties of the synthesized block copolymers, they were used as a pseudostationary phase in electrokinetic chromatography for the separation of some model compounds, that is, benzoates and steroids. Of particular interest was to find out whether a change in the length or concentration of the poly(N‐isoprolylacrylamide) block would affect the separation of the model compounds. Overall, our results show that capillary electrophoresis and asymmetrical flow‐field flow fractionation are suitable methods for characterizing conformational changes of such diblock copolymers. 相似文献
63.
Bernardo Duarte Renato Mamede Irina A. Duarte Isabel Caador Susanne E. Tanner Marisa Silva David Jacinto Teresa Cruz Vanessa F. Fonseca 《Molecules (Basel, Switzerland)》2022,27(4)
The stalked barnacle Pollicipes pollicipes is an abundant species on the very exposed rocky shore habitats of the Spanish and Portuguese coasts, constituting also an important economical resource, as a seafood item with high commercial value. Twenty-four elements were measured by untargeted total reflection X-ray fluorescence spectroscopy (TXRF) in the edible peduncle of stalked barnacles sampled in six sites along the Portuguese western coast, comprising a total of 90 individuals. The elemental profile of 90 individuals originated from several geographical sites (N = 15 per site), were analysed using several chemometric multivariate approaches (variable in importance partial least square discriminant analysis (VIP-PLS-DA), stepwise linear discriminant analysis (S-LDA), linear discriminant analysis (LDA), random forests (RF) and canonical analysis of principal components (CAP)), to evaluate the ability of each approach to trace the geographical origin of the animals collected. As a suspension feeder, this species introduces a high degree of background noise, leading to a comparatively lower classification of the chemometric approaches based on the complete elemental profile of the peduncle (canonical analysis of principal components and linear discriminant analysis). The application of variable selection approaches such as the VIP-PLS-DA and S-LDA significantly increased the classification accuracy (77.8% and 84.4%, respectively) of the samples according to their harvesting area, while reducing the number of elements needed for this classification, and thus the background noise. Moreover, the selected elements are similar to those selected by other random and non-random approaches, reinforcing the reliability of this selection. This untargeted analytical procedure also allowed to depict the degree of risk, in terms of human consumption of these animals, highlighting the geographical areas where these delicacies presented lower values for critical elements compared to the standard thresholds for human consumption. 相似文献
64.
65.
Christian Balischewski Dr. Biswajit Bhattacharyya Dr. Eric Sperlich Dr. Christina Günter Alkit Beqiraj Prof. Dr. Tillmann Klamroth Dr. Karsten Behrens Stefan Mies Alexandra Kelling Susanne Lubahn Lea Holtzheimer Anne Nitschke Prof. Dr. Andreas Taubert 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(64):e202201068
Fifteen N-butylpyridinium salts – five monometallic [C4Py]2[MBr4] and ten bimetallic [C4Py]2[M0.5aM0.5bBr4] (M=Co, Cu, Mn, Ni, Zn) – were synthesized, and their structures and thermal and electrochemical properties were studied. All the compounds are ionic liquids (ILs) with melting points between 64 and 101 °C. Powder and single-crystal X-ray diffraction show that all ILs are isostructural. The electrochemical stability windows of the ILs are between 2 and 3 V. The conductivities at room temperature are between 10−5 and 10−6 S cm−1. At elevated temperatures, the conductivities reach up to 10−4 S cm−1 at 70 °C. The structures and properties of the current bromide-based ILs were also compared with those of previous examples using chloride ligands, which illustrated differences and similarities between the two groups of ILs. 相似文献
66.
Inis Jenemann Susanne Kiefer E. Robens 《Journal of Thermal Analysis and Calorimetry》2008,94(3):607-612
The short survey covers the development of the balance since its invention in the Neolithic era. Scales have been used most
probably first as tools in trading, but already in Old Egyptian papyrus its use in techniques is documented. Its theory was
cleared by Aristotle and Archimedes and at least at that time it was used as a scientific instrument. Today the balance is
still the most widely used instrument in science and there are still improvements. 相似文献
67.
68.
MaxwellD. Cummings Jimmy Lindberg Tse‐I Lin Herman deKock Oliver Lenz Elisabet Lilja Sara Fellnder Vera Baraznenok Susanne Nystrm Magnus Nilsson Lotta Vrang Michael Edlund sa Rosenquist Bertil Samuelsson Pierre Raboisson Kenneth Simmen 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2010,122(9):1552-1552
69.
Shyjumon Ibrahimkutty Daniel Issenmann Stefan Schleef Anke‐Susanne Müller Yves‐Laurent Mathis Biliana Gasharova Erhart Huttel Ralph Steininger Jörg Göttlicher Tilo Baumbach Albrecht Bartels Christof Janke Anton Plech 《Journal of synchrotron radiation》2011,18(4):539-545
A high‐repetition‐rate pump–probe experiment is presented, based on the asynchronous sampling approach. The low‐α mode at the synchrotron ANKA can be used for a time resolution down to the picosecond limit for the time‐domain sampling of the coherent THz emission as well as for hard X‐ray pump–probe experiments, which probe structural dynamics in the condensed phase. It is shown that a synchronization of better than 1 ps is achieved, and examples of phonon dynamics of semiconductors are presented. 相似文献
70.