全文获取类型
收费全文 | 2458篇 |
免费 | 53篇 |
国内免费 | 11篇 |
专业分类
化学 | 1836篇 |
晶体学 | 9篇 |
力学 | 61篇 |
数学 | 320篇 |
物理学 | 296篇 |
出版年
2021年 | 18篇 |
2020年 | 13篇 |
2019年 | 25篇 |
2018年 | 24篇 |
2016年 | 34篇 |
2015年 | 36篇 |
2014年 | 38篇 |
2013年 | 142篇 |
2012年 | 115篇 |
2011年 | 108篇 |
2010年 | 87篇 |
2009年 | 89篇 |
2008年 | 103篇 |
2007年 | 111篇 |
2006年 | 117篇 |
2005年 | 122篇 |
2004年 | 105篇 |
2003年 | 100篇 |
2002年 | 95篇 |
2001年 | 39篇 |
2000年 | 42篇 |
1999年 | 27篇 |
1998年 | 23篇 |
1997年 | 31篇 |
1996年 | 38篇 |
1995年 | 26篇 |
1994年 | 34篇 |
1993年 | 28篇 |
1992年 | 21篇 |
1991年 | 31篇 |
1990年 | 25篇 |
1989年 | 16篇 |
1988年 | 16篇 |
1987年 | 20篇 |
1986年 | 12篇 |
1985年 | 37篇 |
1984年 | 43篇 |
1983年 | 27篇 |
1982年 | 39篇 |
1981年 | 35篇 |
1980年 | 46篇 |
1979年 | 42篇 |
1978年 | 52篇 |
1977年 | 38篇 |
1976年 | 32篇 |
1975年 | 36篇 |
1974年 | 36篇 |
1973年 | 37篇 |
1972年 | 15篇 |
1966年 | 13篇 |
排序方式: 共有2522条查询结果,搜索用时 15 毫秒
141.
Evidence for ion–ion interactions between peptides and anions (HSO4− or ClO4−) derived from high‐acidity acids
下载免费PDF全文
![点击此处可从《Journal of mass spectrometry : JMS》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Xiaohua Liu Jean‐Claude Tabet Richard B. Cole 《Journal of mass spectrometry : JMS》2014,49(6):490-497
The existence of gas‐phase electrostatic ion–ion interactions between protonated sites on peptides ([Glu] Fibrinopeptide B, Angiotensin I and [Asn1, Val5]‐Angiotensin II) and attaching anions (ClO4? and HSO4?) derived from strong inorganic acids has been confirmed by CID MS/MS. Evidence for ion–ion interactions comes especially from the product ions formed during the first dissociation step, where, in addition to the expected loss of the anion or neutral acid, other product ions are also observed that require covalent bond cleavage (i.e. H2O loss when several carboxylate groups are present, or NH3 loss when only one carboxylate group is present). For [[Glu] Fibrinopeptide B + HSO4]?, under CID, H2O water loss was found to require less energy than H2SO4 departure. This indicates that the interaction between HSO4? and the peptide is stronger than the covalent bond holding the hydroxyl group, and must be an ion–ion interaction. The strength and stability of this type of ion‐pairing interaction are highly dependent on the accessibility of additional mobile charges to the site. Positive mobile charges such as protons from the peptide can be transferred to the attaching anion to possibly form a neutral that may depart from the complex. Alternatively, an ion–ion interaction can be disrupted by a competing proximal additional negatively charged site of the peptide that can potentially form a salt bridge with the positively charged site and thereby facilitate the attaching anion's departure. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
142.
Comparison of the activation time effects and the internal energy distributions for the CID,PQD and HCD excitation modes
下载免费PDF全文
![点击此处可从《Journal of mass spectrometry : JMS》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Farid Ichou Adrian Schwarzenberg Denis Lesage Sandra Alves Christophe Junot Xavier Machuron‐Mandard Jean‐Claude Tabet 《Journal of mass spectrometry : JMS》2014,49(6):498-508
Reproducibility among different types of excitation modes is a major bottleneck in the field of tandem mass spectrometry library development in metabolomics. In this study, we specifically evaluated the influence of collision voltage and activation time parameters on tandem mass spectrometry spectra for various excitation modes [collision‐induced dissociation (CID), pulsed Q dissociation (PQD) and higher‐energy collision dissociation (HCD)] of Orbitrap‐based instruments. For this purpose, internal energy deposition was probed using an approach based on Rice–Rampserger–Kassel–Marcus modeling with three thermometer compounds of different degree of freedom (69, 228 and 420) and a thermal model. This model treats consecutively the activation and decomposition steps, and the survival precursor ion populations are characterized by truncated Maxwell–Boltzmann internal energy distributions. This study demonstrates that the activation time has a significant impact on MS/MS spectra using the CID and PQD modes. The proposed model seems suitable to describe the multiple collision regime in the PQD and HCD modes. Linear relationships between mean internal energy and collision voltage are shown for the latter modes and the three thermometer molecules. These results suggest that a calibration based on the collision voltage should provide reproducible for PQD, HCD to be compared with CID in tandem in space instruments. However, an important signal loss is observed in PQD excitation mode whatever the mass of the studied compounds, which may affect not only parent ions but also fragment ions depending on the fragmentation parameters. A calibration approach for the CID mode based on the variation of activation time parameter is more appropriate than one based on collision voltage. In fact, the activation time parameter in CID induces a modification of the collisional regime and thus helps control the orientation of the fragmentation pathways (competitive or consecutive dissociations). Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
143.
High‐Yield Formation of Substituted Tetracyanobutadienes from Reaction of Ynamides with Tetracyanoethylene
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Marie Betou Nicolas Kerisit Esme Meledje Dr. Yann R. Leroux Dr. Claudine Katan Dr. Jean‐François Halet Dr. Jean‐Claude Guillemin Dr. Yann Trolez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(31):9553-9557
A high‐yielding sequence of [2+2] cycloaddition–retroelectrocyclization of ynamides with tetracyanoethylene (TCNE) is described. The reaction provided tetracyanobutadiene (TCBD) species, which were characterized by various techniques. DFT and TD‐DFT calculations were also performed to complement experimental findings. 相似文献
144.
Nathalie Azaroual Jamal El Bakali Delphine Le Broc Carole Deghaye Amaury Farce Philippe Chavatte Régis Millet Claude Vaccher Emmanuelle Lipka-Belloli 《Journal of inclusion phenomena and macrocyclic chemistry》2014,78(1-4):265-274
Three selective CB2 cannabinoid receptor ligands have recently been discovered to be promising anti-inflammatory agents but their low water solubility hinder their per os administration. The popularity of the cyclodextrins, from a pharmaceutical standpoint lies on their ability to interact with poorly water-soluble drugs and improve their solubility. Herein, three experimental approaches for calculating the stability constant of complexes between the selective CB2 ligands and either the β-CD or the HP-β-CD, were tested: nuclear magnetic resonance, micellar electrokinetic chromatography and high performance liquid chromatography in reversed phase. In NMR studies the calculated K values were relatively high and were between 1486 and 3571 M?1 with β-CD. With HP-β-CD they were between 1203 and 2650 M?1. Concerning the two others techniques the K values were found lower. In MECK studies with β-CD they were between 308 and 792 M?1 and with HP-β-CD between 124 and 764 M?1. Finally in RP-HPLC studies with β-CD, they were between 539 and 1144 M?1 and with HP-β-CD between 196 and 396 M?1. These calculated constants suggest that a complexation phenomenon occurs. A model for inclusion of one of the CB2 ligands in the β-CD was then proposed from molecular modeling studies. 相似文献
145.
In this work, the influence of metallic dopant addition in 10 wt % Ni/γ-Al2O3 catalyst on the material physico-chemical properties and catalytic activity for the toluene steam reforming was studied. Seventeen doped Ni/γ-Al2O3 catalysts were synthesized by the sol–gel process. The aim of this study was to determine which elements were the most suitable for the doping of 10 wt % Ni/γ-Al2O3 catalysts. The influence of the dopants was studied through different physico-chemical techniques. It appeared that some dopants showed lower catalytic performances due to high carbon deactivation. On the contrary, some dopants increased the resistance to coking while also improving the catalytic activity. Different mechanisms were proposed to explain these modifications of catalytic behavior. Among all doped Ni/γ-Al2O3 catalysts, the samples that combined Mn + Mo or Co + Mo dopants showed the best catalytic performances at 650 °C. Both samples showed high toluene reforming activity and low amounts of carbon deposit. 相似文献
146.
Dissolved organic matter is an important component of the global carbon cycle that allows the distribution of carbon and nutrients. Therefore, analysis of soil dissolved organic matter helps us to better understand climate change impacts as it is the most dynamic and reactive fraction in terrestrial ecosystems. Its characterization at the molecular level is still challenging due to complex mixtures of hundreds of compounds at low concentration levels in percolating water. This work presents simple methods, such as thermochemolysis– or derivatization–gas chromatography, as an alternative for the analysis of fatty acids in dissolved organic matter without any purification step. The variables of the protocols were examined to optimize the processing conditions for the C9–C18 range. As a proof of concept, fatty acid distributions of soil percolating water samples from a long-term field experiment were successfully assessed. The variability of dissolved organic acid distributions was pronounced through depth profile and soil treatment but no major change in composition was observed. However, although the optimization was done from C9 to C18, detection within the C6-C32 fatty acids range was performed for all samples. 相似文献
147.
148.
Claude Tournut 《Macromolecular Symposia》1994,82(1):99-109
After a brief presentation of the standard non-functionalized copolymers of vinylidene fluoride, the preparation of new functionalized copolymers is described, by copolymerization of vinylidene fluoride, with other fluoromonomers and non-fluorinated monomers including at least one hydroxy or other functional group. The copolymers are analysed by the conventional methods. Examples of formulation show that these new copolymers are able to give coatings applicable outdoors and offering the same excellent durability as PVDF. 相似文献
149.
Giménez-Romero D Agrisuelas J García-Jareño JJ Gregori J Gabrielli C Perrot H Vicente F 《Journal of the American Chemical Society》2007,129(22):7121-7126
This paper demonstrates the importance of the structural changeover in controlling the physical-chemical properties of hexacyanometalate-like materials (Prussian Blue). A meticulous in situ study of compositional variations using electroacoustic impedance techniques associated to electrogravimetric techniques in hexacyanoferrates containing K+ alkali metals reveals the existence of a nanostructural changeover coupled to a change of the magnetic properties of these electromagnetic materials. In the same way, the electroacoustic impedance techniques can be useful both in the understanding and in the in situ monitoring of the structural changeovers and the magnetic behavior of all kinds of materials. 相似文献
150.
Adrián Schwarzenberg Farid Ichou Richard B. Cole Xavier Machuron‐Mandard Christophe Junot Denis Lesage Jean‐Claude Tabet 《Journal of mass spectrometry : JMS》2013,48(5):576-586
Organophosphorus compounds have played important roles as pesticides, chemical warfare agents and extractors of radioactive material. Structural elucidation of phosphonates poses a particular challenge because their initial forms can be hydrolyzed, thus, degradation products may predominate in samples acquired in the field. The analysis of non‐volatile organophosphorus compounds and their degradation products is possible using electrospray tandem mass spectrometry ESI‐MS/MS. Here, we present a generic strategy that allows the unambiguous identification of substituents for two families of organophosphorus compounds: the phosphonates and phosphates. General fragmentation rules were deduced based on the study of decomposition pathways of 55 organophosphorus esters, including examples found in the literature. Multistage MS (MSn) experiments at high resolution in a hybrid mass spectrometer provide accurate mass measurements, whereas collision‐induced dissociation experiments in a triple quadrupole give access to small fragment ions. The creation of a specific nomenclature for each possible structure of organophosphorus compound, depending on the alkyl side chain linked to the oxygen, was achieved by applying these fragmentation rules. This led to the creation of an ‘identification tree’ based upon the unique consecutive decomposition pathways uncovered for each individual compound. Hence, seven structural motifs were created that orient an unequivocal identification using the ‘identification tree’. Despite the similar structures of the ensemble of phosphate and phosphonate esters, distinct identifications based upon characteristic neutral losses and diagnostic fragment ions were possible in all cases. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献