全文获取类型
收费全文 | 709篇 |
免费 | 53篇 |
国内免费 | 1篇 |
专业分类
化学 | 638篇 |
晶体学 | 3篇 |
力学 | 4篇 |
数学 | 50篇 |
物理学 | 68篇 |
出版年
2023年 | 12篇 |
2022年 | 12篇 |
2021年 | 14篇 |
2020年 | 24篇 |
2019年 | 22篇 |
2018年 | 8篇 |
2017年 | 12篇 |
2016年 | 26篇 |
2015年 | 34篇 |
2014年 | 36篇 |
2013年 | 38篇 |
2012年 | 51篇 |
2011年 | 72篇 |
2010年 | 47篇 |
2009年 | 34篇 |
2008年 | 62篇 |
2007年 | 57篇 |
2006年 | 36篇 |
2005年 | 23篇 |
2004年 | 34篇 |
2003年 | 22篇 |
2002年 | 31篇 |
2001年 | 8篇 |
2000年 | 11篇 |
1999年 | 4篇 |
1998年 | 7篇 |
1997年 | 1篇 |
1996年 | 2篇 |
1995年 | 3篇 |
1993年 | 2篇 |
1988年 | 1篇 |
1985年 | 2篇 |
1982年 | 2篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 3篇 |
1973年 | 1篇 |
1972年 | 2篇 |
1925年 | 1篇 |
排序方式: 共有763条查询结果,搜索用时 15 毫秒
41.
Zagdoun A Casano G Ouari O Lapadula G Rossini AJ Lelli M Baffert M Gajan D Veyre L Maas WE Rosay M Weber RT Thieuleux C Coperet C Lesage A Tordo P Emsley L 《Journal of the American Chemical Society》2012,134(4):2284-2291
A new nitroxide-based biradical having a long electron spin-lattice relaxation time (T(1e)) has been developed as an exogenous polarization source for DNP solid-state NMR experiments. The performance of this new biradical is demonstrated on hybrid silica-based mesostructured materials impregnated with 1,1,2,2-tetrachloroethane radical containing solutions, as well as in frozen bulk solutions, yielding DNP enhancement factors (ε) of over 100 at a magnetic field of 9.4 T and sample temperatures of ~100 K. The effects of radical concentration on the DNP enhancement factors and on the overall sensitivity enhancements (Σ(?)) are reported. The relatively high DNP efficiency of the biradical is attributed to an increased T(1e), which enables more effective saturation of the electron resonance. This new biradical is shown to outperform the polarizing agents used so far in DNP surface-enhanced NMR spectroscopy of materials, yielding a 113-fold increase in overall sensitivity for silicon-29 CPMAS spectra as compared to conventional NMR experiments at room temperature. This results in a reduction in experimental times by a factor >12,700, making the acquisition of (13)C and (15)N one- and two-dimensional NMR spectra at natural isotopic abundance rapid (hours). It has been used here to monitor a series of chemical reactions carried out on the surface functionalities of a hybrid organic-silica material. 相似文献
42.
Appel EA Lee VY Nguyen TT McNeil M Nederberg F Hedrick JL Swope WC Rice JE Miller RD Sly J 《Chemical communications (Cambridge, England)》2012,48(49):6163-6165
Organocatalytic ring opening polymerization (OROP) is used to effect the rapid, scalable, room temperature formation of size-controlled, highly uniform, polyvalent, nanogel star polymer nanoparticles of biodegradable composition. 相似文献
43.
Melanie Egli Alicia Hartmann Helena Rapp Wright Keng Tiong Ng Frdric B. Piel Leon P. Barron 《Molecules (Basel, Switzerland)》2021,26(18)
The rapid source identification and environmental risk assessment (ERA) of hundreds of chemicals of emerging concern (CECs) in river water represent a significant analytical challenge. Herein, a potential solution involving a rapid direct-injection liquid chromatography–tandem mass spectrometry method for the quantitative determination of 102 CECs (151 qualitatively) in river water is presented and applied across six rivers in Germany and Switzerland at high spatial resolution. The method required an injection volume of only 10 µL of filtered sample, with a runtime of 5.5 min including re-equilibration with >10 datapoints per peak per transition (mostly 2 per compound), and 36 stable isotope-labelled standards. Performance was excellent from the low ng/L to µg/L concentration level, with 260 injections possible in any 24 h period. The method was applied in three separate campaigns focusing on the ERA of rivers impacted by wastewater effluent discharges (1 urban area in the Basel city region with 4 rivers, as well as 1 semi-rural and 1 rural area, each focusing on 1 river). Between 25 and 40 compounds were quantified directly in each campaign, and in all cases small tributary rivers showed higher CEC concentrations (e.g., up to ~4000 ng/L in total in the R. Schwarzach, Bavaria, Germany). The source of selected CECs could also be identified and differentiated from other sources at pre- and post- wastewater treatment plant effluent discharge points, as well as the effect of dilution downstream, which occurred over very short distances in all cases. Lastly, ERA for 41 CECs was performed at specific impacted sites, with risk quotients (RQs) at 1 or more sites estimated as high risk (RQ > 10) for 1 pharmaceutical (diclofenac), medium risk (RQ of 1–10) for 3 CECs (carbamazepine, venlafaxine, and sulfamethoxazole), and low risk (RQ = 0.1–1.0) for 7 CECs (i.e., RQ > 0.1 for 11 CECs in total). The application of high-throughput methods like this could enable a better understanding of the risks of CECs, especially in low flow/volume tributary rivers at scale and with high resolution. 相似文献
44.
45.
Melanie Schmidlehner Felix Faschinger Lorenz Michael Reith Martin Ertl Wolfgang Schoefberger 《应用有机金属化学》2013,27(7):395-405
In this study, novel water‐soluble corrole amino acid conjugates were synthesized and characterized. The coupling reaction of A2B‐ and A3‐corroles with glycine ethyl ester and taurine under strong basic conditions proved to be successful and yielded di‐ and trifunctionalized corrole amino acid conjugates in good yields. The subsequent metalation of the corrole/amino acid conjugates broadens the scope for applications considerably. As examples, we herein show the catalytic activity of the Mn(III) A3‐corrole towards O2 evolution. First we employed tert‐butyl hydroperoxide (t‐BuOOH) as oxidant to obtain the Mn(V)oxo species and tetrabutyl ammonium hydroxide (TBAH) as hydroxide donor agent. Furthermore, the binding properties of the non‐metalated and the Mn(III) A3‐corrole/amino sulfonic acid conjugates and transport of proteins were investigated and the conjugates exhibited binding to human serum albumin (HSA). Finally, a novel Ga(III) A3‐corrole/amino sulfonic acid derivative was synthesized and we briefly describe the photophysical properties of this compound. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
46.
47.
48.
Burford N Eelman MD Mahony DE Morash M 《Chemical communications (Cambridge, England)》2003,(1):146-147
Solutions containing BiCl3, bismuth subsalicylate or Bi(NO3)3 with L-cysteine, DL-homocysteine, D-methionine or glutathione have been examined by electrospray mass spectrometry. Prominent peaks are assigned to bismuth complexes of these biomolecules and provide insight towards understanding the bioactivity of bismuth compounds. 相似文献
49.
Dr. Pablo Pinacho Dr. Donatella Loru Dr. Tatjana Šumanovac Dr. Marina Šekutor Prof. Dr. Melanie Schnell 《Chemphyschem》2023,24(23):e202300561
We report on the synthesis and characterization using high-resolution rotational spectroscopy of three bulky thioethers that feature an adamantyl group connected to a sulfur atom. Detailed experimental and theoretical structures are provided and compared with the 1,1′-diadamantyl ether. In addition, we expand on previous findings concerning microsolvation of adamantyl derivatives by investigating the cluster formation between these thioethers and a water molecule. The investigation of such clusters provides valuable insights into the sulfur-centered hydrogen bonding in thioethers with increasing size and steric repulsion. 相似文献