全文获取类型
收费全文 | 460篇 |
免费 | 13篇 |
国内免费 | 3篇 |
专业分类
化学 | 237篇 |
力学 | 13篇 |
数学 | 103篇 |
物理学 | 123篇 |
出版年
2023年 | 4篇 |
2022年 | 8篇 |
2021年 | 22篇 |
2020年 | 7篇 |
2019年 | 12篇 |
2018年 | 25篇 |
2017年 | 8篇 |
2016年 | 26篇 |
2015年 | 18篇 |
2014年 | 18篇 |
2013年 | 36篇 |
2012年 | 34篇 |
2011年 | 32篇 |
2010年 | 24篇 |
2009年 | 18篇 |
2008年 | 25篇 |
2007年 | 25篇 |
2006年 | 15篇 |
2005年 | 13篇 |
2004年 | 9篇 |
2003年 | 17篇 |
2002年 | 11篇 |
2001年 | 4篇 |
2000年 | 6篇 |
1999年 | 3篇 |
1998年 | 4篇 |
1997年 | 5篇 |
1996年 | 4篇 |
1994年 | 3篇 |
1993年 | 2篇 |
1992年 | 3篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1986年 | 4篇 |
1985年 | 1篇 |
1984年 | 5篇 |
1983年 | 2篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1975年 | 2篇 |
1973年 | 2篇 |
1972年 | 1篇 |
1971年 | 1篇 |
1968年 | 1篇 |
1960年 | 1篇 |
1948年 | 1篇 |
1943年 | 2篇 |
1935年 | 1篇 |
1873年 | 1篇 |
排序方式: 共有476条查询结果,搜索用时 15 毫秒
81.
82.
Armaforte E Mancebo-Campos V Bendini A Desamparados Salvador M Fregapane G Cerretani L 《Journal of separation science》2007,30(15):2401-2406
The hydrophilic extract of virgin olive oil contains several phenolic compounds such as simple phenols, lignans, and secoiridoids that have been widely studied in recent years. Interest in the hydrophilic extract has also been extended to the fraction of oxidized phenols that form during storage as a consequence of oxidative stress. The present investigation compares the two most commonly used extraction methods, namely liquid-liquid extraction and SPE, on fresh virgin olive oil and that kept at different temperatures in the presence of oxygen to promote the formation of oxidative products. The selective retention of these natural and oxidized phenolic compounds in relation to the extraction method was assessed. Quantification of eight identified phenolic molecules and 11 unknown peaks was performed by HPLC-DAD/MSD. 相似文献
83.
Seraglia R Molin L Tonidandel L Pucciarelli S Agostini M Urso ED Bedin C Quaia M Nitti D Traldi P 《Journal of mass spectrometry : JMS》2007,42(12):1606-1612
In an investigation devoted to the search for plasma markers for colorectal cancer (CRC), carried out by matrix-assisted laser desorption/ionization (MALDI) mass spectrometry, a series of overexpressed peptides were identified in the plasma of patients. Among them the peptide with molecular weight 903 Da was the most abundant one, with a mean +/- (SD) relative abundance of 37 +/- 17% and a frequency over 60%. Interestingly, also in plasma samples of ten subjects affected by familial adenomatous polyposis (FAP), the peptide with molecular weight 903 was overexpressed. In this investigation, MALDI/MS/MS experiments were carried out on the ion at m/z 904 detected in the MALDI mass spectra of CRC and FAP patients. The data analysis by SwissProt.2007.01.09 indicates that this peptide is due to the sequence RPPGFSPF, found in the kininogen-1 precursor, which is an alpha-2-thiol proteinase inhibitor. In the case of subjects affected by a particular FAP syndrome, the MALDI/MS/MS spectra were quite different from those obtained from CRC and FAP patients. In fact, two sequences have been evidenced: RPPGFSPF belonging to kininogen-1 precursor, and PRKSSSSR belonging to Forkhead box protein 01A. 相似文献
84.
Favaro G di Nunzio MR Gentili PL Romani A Becker RS 《The journal of physical chemistry. A》2007,111(27):5948-5953
The widely investigated photobehaviors of 9-bromo and 9,10-di-bromoanthracenes have been revisited here to clarify the competition among different relaxation paths of their lowest two electronic excited states. The results obtained show that these two molecules exhibit a parallel photobehavior, which depends on the excited electronic and vibronic transition, the medium viscosity, and the temperature. The first electronic state of either of these does not exhibit photochemistry in fluid solution or rigid matrices (80 K). The fluorescence emission occurs with a very low quantum yield (approximately 10(-2)) at room temperature but with a very high quantum yield (0.9 to approximately 1) at 80 K. When exciting in the second electronic transition, the fluorescence intensity is lower than when exciting in S1 at both room temperature and low temperature due to competition with the observed photocleavage of the C-Br bond. The reaction yield decreases as the temperature decreases and depends on the viscosity of the solvent; the higher the viscosity, the lower the observed yield of photochemistry. Temperature and viscosity effects are a consequence of the fact that the radicals produced by C-Br bond breakage cannot escape from the solvent cage and, moreover, quickly recombine within the cage giving the appearance that no photochemistry occurred. The presence of photochemistry in S(2) and its absence in S(1) is principally due to the fact that S(2) has a pi,sigma* character in the C-Br bond, whereas the S(1) state has its origin from a pi,pi* delocalized configuration. 相似文献
85.
Luca Sancineto Carmine Ostacolo David Ortega-Alarcon Ana Jimenez-Alesanco Laura Ceballos-Laita Sonia Vega Olga Abian Adrian Velazquez-Campoy Silvia Moretti Agnieszka Dabrowska Pawel Botwina Aleksandra Synowiec Anna Kula-Pacurar Krzysztof Pyrc Nunzio Iraci Claudio Santi 《Molecules (Basel, Switzerland)》2021,26(19)
The COVID-19 pandemic outbreak prompts an urgent need for efficient therapeutics, and repurposing of known drugs has been extensively used in an attempt to get to anti-SARS-CoV-2 agents in the shortest possible time. The glycoside rutin shows manifold pharmacological activities and, despite its use being limited by its poor solubility in water, it is the active principle of many pharmaceutical preparations. We herein report our in silico and experimental investigations of rutin as a SARS-CoV-2 Mpro inhibitor and of its water solubility improvement obtained by mixing it with l-arginine. Tests of the rutin/l-arginine mixture in a cellular model of SARS-CoV-2 infection highlighted that the mixture still suffers from unfavorable pharmacokinetic properties, but nonetheless, the results of this study suggest that rutin might be a good starting point for hit optimization. 相似文献
86.
Riccardo Destro Emanuele Ortoleva Giorgio Modena Lucia Pasquato Vittorio Lucchini 《Helvetica chimica acta》2001,84(4):860-866
Four‐membered ring thiosulfonium ions may be obtained quantitatively and under mild conditions by anionotropic rearrangement of C‐(tert‐butyl)‐substituted thiiranium ion precursors. Thus, t‐4‐(tert‐butyl)‐r‐1,2,2,c‐3‐tetramethylthietanium tetrafluoroborate or hexachloroantimonate ( 2a or 2b , resp.) were formed from thiiranium ion 1 . The thietanium salts 2a and 2b were characterized by X‐ray crystal‐structure analysis. Their cation geometry was also optimized by ab initio calculations at the RHF/6‐31G*//RHF/6‐31G* level, as were those of its stereoisomer 3 and of the unsubstituted S‐methylthietanium ion 5 . Comparison of 2 , 3 , and 5 with 4 – the only other thietanium ion studied by XRD, where the C‐atoms of the thioniacyclobutane ring are part of a trinorbornane skeleton – indicates that, in these systems, relief from substituent overcrowding is easily achieved by a folding of the four‐membered ring along the line connecting the two opposite C‐atoms. The corresponding ring‐deformation normal mode has a calculated frequency as low as 109 cm−1 in ion 5 , to be compared with a frequency of 138 cm−1 in methylcyclobutane. For thietanium ion 2 , the frequencies of the two normal modes involving such ring deformation have calculated values of 61 and 85 cm−1. 相似文献
87.
Beat Grolimund Emanuele Boselli Konrad Grob Renato Amad Giovanni Lercker 《Journal of separation science》1998,21(7):378-382
Solvent trapping reconcentrates volatile components after injection or on-line transfer of large volumes. When an early vapor exit is used, typically after a 5–10 m × 0.53 mm i.d. uncoated precolumn, the solvent trapping process differs from that described previously. The visual experiments and the conclusions drawn therefrom, as described in a previous paper, are supplemented with chromatographic results. They show that even hexane can be quantitatively analyzed in 250 μl of a pentane solution. Injection of a volume of 250 μl by vaporizer/precolumn solvent splitting was used in the analysis of gasoline in drinking water. Conditions for the transfer of a 1000 μl volume can easily be adjusted through detection of the front end of the flooded zone by a thermocouple mounted on the outer wall of the precolumn. 相似文献
88.
89.
Bin Yang Marina Lledos Riaz Akhtar Giuseppe Ciccone Long Jiang Emanuele Russo Sunil Rajput Chunyu Jin Maria Galini Faidra Angelereou Thomas Arnold Jonathan Rawle Massimo Vassalli Maria Marlow Dave J. Adams Mischa Zelzer 《Chemical science》2021,12(42):14260
Controlling supramolecular self-assembly across multiple length scales to prepare gels with localised properties is challenging. Most strategies concentrate on fabricating gels with heterogeneous components, where localised properties are generated by the stimuli-responsive component. Here, as an alternative approach, we use a spiropyran-modified surface that can be patterned with light. We show that light-induced differences in surface chemistry can direct the bulk assembly of a low molecular weight gelator, 2-NapAV, meaning that mechanical gel properties can be controlled by the surface on which the gel is grown. Using grazing incidence X-ray diffraction and grazing incidence small angle X-ray scattering, we demonstrate that the origin of the different gel properties relates to differences in the architectures of the gels. This provides a new method to prepare a single domain (i.e., chemically homogeneous) hydrogel with locally controlled (i.e., mechanically heterogeneous) properties.A mechanical pattern is created in a hydrogel film by pre-patterning the underlying surface chemistry. This allows spatial variation of the viscous component of the gel, controlling dissipative forces in the gel film without altering gel chemistry. 相似文献
90.
Emanuele Pugliese Claudio Castellano Matteo Marsili Luciano Pietronero 《The European Physical Journal B - Condensed Matter and Complex Systems》2009,67(3):319-327
We introduce and study a model of an interacting population of agents who collaborate in groups which compete for limited
resources. Groups are formed by random matching agents and their worth is determined by the sum of the efforts deployed by
agents in group formation. Agents, on their side, have to share their effort between contributing to their group’s chances
to outcompete other groups and resource sharing among partners, when the group is successful. A simple implementation of this
strategic interaction gives rise to static and evolutionary properties with a very rich phenomenology. A robust emerging feature
is the separation of the population between agents who invest mainly in the success of their group and agents who concentrate
in getting the largest share of their group’s profits. 相似文献