全文获取类型
收费全文 | 647篇 |
免费 | 19篇 |
国内免费 | 7篇 |
专业分类
化学 | 496篇 |
晶体学 | 3篇 |
力学 | 24篇 |
数学 | 75篇 |
物理学 | 75篇 |
出版年
2023年 | 3篇 |
2022年 | 16篇 |
2021年 | 13篇 |
2020年 | 16篇 |
2019年 | 17篇 |
2018年 | 6篇 |
2017年 | 12篇 |
2016年 | 25篇 |
2015年 | 19篇 |
2014年 | 16篇 |
2013年 | 36篇 |
2012年 | 28篇 |
2011年 | 54篇 |
2010年 | 30篇 |
2009年 | 36篇 |
2008年 | 47篇 |
2007年 | 39篇 |
2006年 | 35篇 |
2005年 | 17篇 |
2004年 | 28篇 |
2003年 | 25篇 |
2002年 | 20篇 |
2001年 | 7篇 |
2000年 | 12篇 |
1999年 | 9篇 |
1998年 | 6篇 |
1997年 | 13篇 |
1996年 | 5篇 |
1995年 | 4篇 |
1994年 | 4篇 |
1992年 | 6篇 |
1991年 | 3篇 |
1990年 | 3篇 |
1989年 | 5篇 |
1987年 | 3篇 |
1986年 | 2篇 |
1985年 | 8篇 |
1984年 | 4篇 |
1983年 | 2篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1979年 | 6篇 |
1978年 | 3篇 |
1977年 | 2篇 |
1975年 | 4篇 |
1971年 | 2篇 |
1969年 | 2篇 |
1967年 | 3篇 |
1943年 | 2篇 |
排序方式: 共有673条查询结果,搜索用时 0 毫秒
661.
Effect of Mobile Phase on Electrospray Ionization Efficiency 总被引:1,自引:0,他引:1
Jaanus Liigand Anneli Kruve Ivo Leito Marion Girod Rodolphe Antoine 《Journal of the American Society for Mass Spectrometry》2014,25(11):1853-1861
Electrospray (ESI) ionization efficiencies (IE) of a set of 10 compounds differing by chemical nature, extent of ionization in solution (basicity), and by hydrophobicity (tetrapropylammonium and tetraethylammonium ion, triethylamine, 1-naphthylamine, N,N-dimethylaniline, diphenylphthalate, dimethylphtahalate, piperidine, pyrrolidine, pyridine) have been measured in seven mobile phases (three acetonitrile percentages 20%, 50%, and 80%, and three different pH-adjusting additives, 0.1% formic acid, 1 mM ammonia, pH 5.0 buffer combination) using the relative measurement method. MS parameters were optimized separately for each ion. The resulting relative IE data were converted into comparable logIE values by anchoring them to the logIE of tetrapropylammonium ion taking into account the differences of ionization in different solvents and thereby making the logIE values of the compounds comparable across solvents. The following conclusions were made from analysis of the data. The compounds with pK a values in the range of the solution pH values displayed higher IE at lower pH. The sensitivity of IE towards pH depends on hydrophobicity being very strong with pyridine, weaker with N,N-dimethylaniline, and weakest with 1-naphthylamine. IEs of tetraalkylammonium ions and triethylamine were expectedly insensitive towards solution pH. Surprisingly high IEs of phthalate esters were observed. The differences in solutions with different acetonitrile content and similar pH were smaller compared with the pH effects. These results highlight the importance of hydrophobicity in electrospray and demonstrate that high hydrophobicity can sometimes successfully compensate for low basicity. Graphical Abstract
? 相似文献
662.
Iron‐Catalyzed CαH Oxidation of Tertiary,Aliphatic Amines to Amides under Mild Conditions 下载免费PDF全文
Christopher J. Legacy Anqi Wang Brian J. O'Day Prof. Marion H. Emmert 《Angewandte Chemie (International ed. in English)》2015,54(49):14907-14910
De novo syntheses of amides often generate stoichiometric amounts of waste. Thus, recent progress in the field has focused on precious metal catalyzed, oxidative protocols to generate such functionalities. However, simple tertiary alkyl amines cannot be used as starting materials in these protocols. The research described herein enables the oxidative synthesis of amides from simple, noncyclic tertiary alkyl amines under synthetically useful, mild conditions through a biologically inspired approach: Fe‐catalyzed Cα? H functionalization. Mechanistic investigations provide insight into reaction intermediates and allow the development of a mild Cα? H cyanation method using the same catalyst system. The protocol was further applied to oxidize the drug Lidocaine, demonstrating the potential utility of the developed chemistry for metabolite synthesis. 相似文献
663.
Viktoria Weber Marion Ettenauer Ingrid Linsberger Fritz Loth Katrin Thümmler Andreas Feldner Steffen Fischer Dieter Falkenhagen 《Macromolecular Symposia》2010,294(2):90-95
Therapeutic apheresis is established as supportive therapy for various diseases, such as hypercholesterolemia, autoimmune diseases, liver failure, and sepsis. In combined membrane-adsorption systems, the patient's plasma is continuously separated from whole blood by means of a hollow fiber filter, and pathogenic factors are removed from the plasma by selective or specific adsorbents. While adsorbent particles with a size range of 300–800 µm are used in conventional systems, we are currently developing a system based on adsorbent microparticles (1–5 µm), the Microspheres-Based Detoxification System (MDS). The characteristics of the matrix used for immobilization of specific ligands influence the performance of the resulting adsorbents. Desirable matrix characteristics are an open porous structure with an inner surface accessible for target molecules, mechanical stability, narrow particle size distribution, and ease of derivatization. In addition, biocompatibility is a critical issue, since the particles are in direct contact with the patient's plasma. Cellulose represents an ideal support matrix, as it combines all the above-mentioned features, and cellulosic polymers are widely applied in medicine and generally regarded as biocompatible. Cellulose microparticles can be activated using e.g. sodium periodate and functionalized with Polymyxin B or anti-tumor necrosis factor (TNF) antibodies to generate specific adsorbents for endotoxins or TNF. In summary, cellulose microparticles represent an excellent matrix as basis for adsorbent development in blood purification. 相似文献
664.
665.
Sacha J. Pidot Marion Herisse Liam Sharkey Liselle Atkin Jessica L. Porter Torsten Seemann Benjamin P. Howden Mark A. Rizzacasa Timothy P. Stinear 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(12):4036-4041
The nargenicin family of antibiotics are macrolides containing a rare ether‐bridged cis‐decalin motif. Several of these compounds are highly active against multi‐drug resistant organisms. Despite the identification of the first members of this family almost 40 years ago, the genetic basis for the production of these molecules and the enzyme responsible for formation of the oxa bridge, remain unknown. Here, the 85 kb nargenicin biosynthetic gene cluster was identified from a human pathogenic Nocardia arthritidis isolate and this locus is solely responsible for nargenicin production. Further investigation of this locus revealed a putative iron‐α‐ketoglutarate‐dependent dioxygenase, which was found to be responsible for the formation of the ether bridge from the newly identified deoxygenated precursor, 8,13‐deoxynargenicin. Uncovering the nargenicin biosynthetic locus provides a molecular basis for the rational bioengineering of these interesting antibiotic macrolides. 相似文献
666.
Mahé L Dutriez T Courtiade M Thiébaut D Dulot H Bertoncini F 《Journal of chromatography. A》2011,1218(3):534-544
Extending the knowledge on sulfur-containing compounds is crucial for the petroleum industry because they contribute to atmospheric pollution by combustion. Most of them are concentrated in heavy petroleum cuts, such as vacuum gas oils (VGOs). However, the resolution of the existing analytical methods does not allow a quantitative speciation of S-compounds contained in VGOs. Therefore, a high temperature GC×GC chromatograph hyphenated to a SCD was implemented in this study to obtain a quantitative S-compounds speciation. Firstly, various thermally stable stationary phases, in particular the new ionic liquid IL59 and Mega Wax-HT, were investigated in 1D-GC as a way to reduce the number of columns sets to be used in GC×GC. Consequently, several normal and reversed configurations of these columns were selected and tested in GC×GC. Then, a decision method was applied to facilitate the choice of the best combination of columns. Finally, the most adapted methods led to an innovative group type quantification and to a quantitative distribution of heavy sulfur species contained in a VGO sample. These results represent a major step towards the study of S-compounds in heavy petroleum cuts. 相似文献
667.
668.
Dr. Lenka Pallova Dr. Laura Abella Marion Jean Dr. Nicolas Vanthuyne Cécile Barthes Dr. Laure Vendier Prof. Jochen Autschbach Dr. Jeanne Crassous Dr. Stéphanie Bastin Dr. Vincent César 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(17):e202200166
The first chiral helicene-NHC gold(I) complexes efficient in enantioselective catalysis were prepared. The L-shaped chiral ligand is composed of an imidazo[1,5-a]pyridin-3-ylidene (IPy) scaffold laterally substituted by a configurationally stable [5]-helicenoid unit. The chiral information was introduced in a key post-functionalization step of a NHC-gold(I) complex bearing a symmetrical anionic fluoreno[5]helicene substituent, leading to a racemic mixture of complexes featuring three correlated elements of chirality, namely central, axial and helical chirality. After HPLC enantiomeric resolution, X-ray crystallography and theoretical calculations enabled structural and stereochemical characterization of these configurationally stable NHC-gold(I) complexes. The high potential in asymmetric catalysis is demonstrated in the benchmark cycloisomerization of N-tethered 1,6-enynes with up to 95 : 5 er. 相似文献
669.
670.
Marion Pommet Andréas Redl Marie-Hélène Morel Sandra Domenek Stéphane Guilbert 《Macromolecular Symposia》2003,197(1):207-218
Proteins, as heteropolymers, offer a large range of possible interactions and chemical reactions. The thermoplastic behavior of proteins has been studied in order to produce bioplastics by thermal or thermomechanical processes such as mixing, extrusion or hot molding. The extrusion trials were performed by using a co-rotating twin-screw extruder, recording torque, temperature and die pressure. Batch mixing was done in a two blade counter-rotating mixer, with continuous recording of torque and product temperature. Proteins were alternatively extruded, mixed or hot molded under a large range of processing conditions. Protein aggregation during each process was estimated from the accumulation of SDS-insoluble protein fraction. Protein aggregation evidences a cross-linking reaction the activation energy of which was dependent on the thermoplastic process used. The increase in network density appears to be induced by the severity of the treatment: temperature and shear strongly affect the structural characteristics of the protein-based bioplastics. 相似文献