全文获取类型
收费全文 | 644篇 |
免费 | 23篇 |
国内免费 | 2篇 |
专业分类
化学 | 565篇 |
晶体学 | 3篇 |
力学 | 6篇 |
数学 | 43篇 |
物理学 | 52篇 |
出版年
2023年 | 9篇 |
2022年 | 24篇 |
2021年 | 18篇 |
2020年 | 15篇 |
2019年 | 16篇 |
2018年 | 13篇 |
2017年 | 14篇 |
2016年 | 21篇 |
2015年 | 17篇 |
2014年 | 18篇 |
2013年 | 36篇 |
2012年 | 41篇 |
2011年 | 65篇 |
2010年 | 22篇 |
2009年 | 32篇 |
2008年 | 55篇 |
2007年 | 52篇 |
2006年 | 28篇 |
2005年 | 32篇 |
2004年 | 17篇 |
2003年 | 15篇 |
2002年 | 13篇 |
2001年 | 5篇 |
2000年 | 3篇 |
1999年 | 2篇 |
1997年 | 2篇 |
1993年 | 6篇 |
1991年 | 4篇 |
1990年 | 2篇 |
1989年 | 4篇 |
1987年 | 2篇 |
1984年 | 4篇 |
1981年 | 3篇 |
1978年 | 6篇 |
1977年 | 3篇 |
1976年 | 5篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1973年 | 4篇 |
1968年 | 2篇 |
1954年 | 2篇 |
1937年 | 2篇 |
1936年 | 2篇 |
1934年 | 2篇 |
1932年 | 3篇 |
1928年 | 1篇 |
1922年 | 1篇 |
1919年 | 3篇 |
1898年 | 1篇 |
1879年 | 1篇 |
排序方式: 共有669条查询结果,搜索用时 0 毫秒
121.
A series of stilbazolium dimers were synthesized and investigated as sterically demanding ligands targeting the norepinephrine transporter (NET). The environmentally sensitive fluorescence of the dyes enables their use as self-reporting ligands; binding to and displacement from NET can be monitored by fluorescence microscopy. 相似文献
122.
Michael addition reaction of α-branched aldehydes to β-nitroacrylates was successfully carried out by using a mixed catalyst consisting of a primary amino acid, L-phenylalanine, and its lithium salt to give β-formyl-β'-nitroesters having a quaternary carbon centre in good yields (up to 85%) with high enantioselectivity (up to 98% ee). By using benzyl β-nitroacrylates as Michael acceptors, the obtained β-formyl-β'-nitroesters were converted into various 4,4-disubstituted pyrrolidine-3-carboxylic acids including analogues of gabapentin (Neurotin(?)) in one step from the Michael adducts in high yields. 相似文献
123.
Phenyl cations are smoothly generated by the photoheterolytic cleavage of an Ar-LG bond (LG = leaving group). With the aim of evaluating the scope of the method, a series of 4-methoxy-2-(trimethylsilyl)phenyl derivatives (sulfonic, LG = MeSO(3) and CF(3)SO(3), phosphate, LG = (EtO)(2)(O)PO esters and the corresponding chloride) have been compared as probes for evaluating the leaving group ability. The photocleavage was a general reaction, with the somewhat surprising order (EtO)(2)(O)PO ~ Cl > CF(3)SO(3) > MeSO(3) (Φ = 0.50 to 0.16 in CF(3)CH(2)OH and lower values in MeCN-H(2)O). The ensuing reactions did not depend on the LGs but only on the structure of the phenyl cation (the silyl group tuned the triplet to singlet intersystem crossing and the electrophilicity) and on the medium (formation of a complex with water slowed the electrophilic reactions). 相似文献
124.
High-Quality Protein Crystal Growth of Mouse Lipocalin-Type Prostaglandin D Synthase in Microgravity
Inaka K Takahashi S Aritake K Tsurumura T Furubayashi N Yan B Hirota E Sano S Sato M Kobayashi T Yoshimura Y Tanaka H Urade Y 《Crystal growth & design》2011,11(6):2107-2111
Lipocalin-type prostaglandin (PG) D synthase (L-PGDS) catalyzes the isomerization of PGH(2) to PGD(2) and is involved in the regulation of pain and of nonrapid eye movement sleep and the differentiation of male genital organs and adipocytes, etc. L-PGDS is secreted into various body fluids and binds various lipophilic compounds with high affinities, acting also as an extracellular transporter. Mouse L-PGDS with a C65A mutation was previously crystallized with citrate or malonate as a precipitant, and the X-ray crystallographic structure was determined at 2.0 ? resolution. To obtain high-quality crystals, we tried, unsuccessfully, to crystallize the C65A mutant in microgravity under the same conditions used in the previous study. After further purifying the protein and changing the precipitant to polyethylene glycol (PEG) 8000, high-quality crystals were grown in microgravity. The precipitant solution was 40% (w/v) PEG 8000, 100 mM sodium chloride, and 100 mM HEPES-NaOH (pH 7.0). Crystals grew on board the International Space Station for 11 weeks in 2007, yielding single crystals of the wild-type L-PGDS and the C65A mutant, both of which diffracted at around 1.0 ? resolution. The crystal quality was markedly improved through the use of a high-viscosity precipitant solution in microgravity, in combination with the use of a highly purified protein. 相似文献
125.
Lellouche JP Senthil G Joseph A Buzhansky L Bruce I Bauminger ER Schlesinger J 《Journal of the American Chemical Society》2005,127(34):11998-12006
Novel bis-heterocyclic mono- and dicarboxylated dipyrrole and dicarbazole monomers have been synthesized in a modular manner. Their oxidative polymerization around magnetite nanosized particles has been investigated and optimized toward new magnetic magnetite-polydipyrrole/polydicarbazole nanocomposites (NCs) of a core-shell morphology. These NCs were thoroughly characterized by FT-IR, TGA (Thermal Gravimetric Analysis), low- and high-resolution TEM/HR-TEM microscopies, and M?ssbauer spectroscopy along with magnetization studies. Exploiting the versatile COOH chemistry (activation by water-soluble diimides) introduced by the polymeric shell, DNA hybridization experiments have been conducted onto NC surfaces using an efficient blue-colored HRP-based enzymatic screening biological system. Highly parallel NC-supported DNA hybridization experimentations revealed that these NCs presented an interesting potential for DNA-based diagnostic applications. 相似文献
126.
We consider the problem of discriminating between states of a specified set with maximum confidence. For a set of linearly independent states unambiguous discrimination is possible if we allow for the possibility of an inconclusive result. For linearly dependent sets an analogous measurement is one which allows us to be as confident as possible that when a given state is identified on the basis of the measurement result, it is indeed the correct state. 相似文献
127.
Vladimír Mastihuba Pavel Čepec Silvia Vlčková Erika Farkašová Mária Mastihubová Pavel Bobal 《Chemical Papers》2014,68(6):745-750
Two lipases, Novozyme 435 (lipase B from Candida Antarctica) and Lipozyme TL IM (Thermomyces lanuginosus) were used successfully for the kinetic resolution of racemic 1-(2-furyl)-3-pentanol, the key intermediate in synthesis of the bark beetle pheromone, chalcogran. The desired S-(+)-enantiomer was prepared in enantiomeric excesses higher than 98 % and with yields of 26.3 % and 32.5 %, respectively. Methyl tert-butyl ether and vinyl acetate were found to be the best reaction media and the acetyl donor to achieve fast and effective resolution. 相似文献
128.
Rodolfo Nino‐Fong Laurie A. McDuffee Blanca P. Esparza Gonzalez M. Ramesh Kumar Erika F. Merschrod S. Kristin M. Poduska 《Macromolecular bioscience》2013,13(3):348-355
The in vitro viability, osteogenic differentiation, and mineralization of four different equine mesenchymal stem cells (MSCs) from bone marrow, periosteum, muscle, and adipose tissue are compared, when they are cultured with different collagen‐based scaffolds or with fibrin glue. The results indicate that bone marrow cells are the best source of MSCs for osteogenic differentiation, and that an electrochemically aggregated collagen gives the highest cell viability and best osteogenic differentiation among the four kinds of scaffolds studied.
129.
Cartigny B Azaroual N Imbenotte M Mathieu D Parmentier E Vermeersch G Lhermitte M 《Talanta》2008,74(4):1075-1078
The determination and quantification of glyphosate in serum using (1)H NMR spectroscopy is reported. This method permitted serum samples to be analysed without derivatization or any other sample pre-treatment, using 3-trimethylsilyl 2,2',3,3'-tetradeuteropropionic acid (TSP-d(4)) as a qualitative and quantitative standard. Characterization of the herbicide N-(phosphonomethyl)glycine was performed by analysing chemical shifts and coupling constant patterns. Quantification was performed by relative integration of CH(2)-P protons to the TSP-d(4) resonance peak. The method was tested for repeatability (n=5) and yielded coefficients of variation of 1% and 3%, respectively: detection and quantification limits were also determined and were 0.03 and 0.1mmol/L, respectively. The method was applied to the quantification of glyphosate in a case of acute poisoning. 相似文献
130.
A Hot‐Segment‐Based Approach for the Design of Cross‐Amyloid Interaction Surface Mimics as Inhibitors of Amyloid Self‐Assembly 下载免费PDF全文
Dr. Erika Andreetto Dipl.‐Chem. Eleni Malideli Dr. Li‐Mei Yan Dipl.‐Ing. Michael Kracklauer MSc. Karine Farbiarz Dipl.‐Chem. Marianna Tatarek‐Nossol Prof. Dr. Gerhard Rammes M. Sc. Elke Prade Tatjana Neumüller Dr. Andrea Caporale M. Sc. Anna Spanopoulou B. Sc. Maria Bakou Prof. Dr. Bernd Reif Prof. Dr. Aphrodite Kapurniotu 《Angewandte Chemie (International ed. in English)》2015,54(44):13095-13100
The design of inhibitors of protein–protein interactions mediating amyloid self‐assembly is a major challenge mainly due to the dynamic nature of the involved structures and interfaces. Interactions of amyloidogenic polypeptides with other proteins are important modulators of self‐assembly. Here we present a hot‐segment‐linking approach to design a series of mimics of the IAPP cross‐amyloid interaction surface with Aβ (ISMs) as nanomolar inhibitors of amyloidogenesis and cytotoxicity of Aβ, IAPP, or both polypeptides. The nature of the linker determines ISM structure and inhibitory function including both potency and target selectivity. Importantly, ISMs effectively suppress both self‐ and cross‐seeded IAPP self‐assembly. Our results provide a novel class of highly potent peptide leads for targeting protein aggregation in Alzheimer’s disease, type 2 diabetes, or both diseases and a chemical approach to inhibit amyloid self‐assembly and pathogenic interactions of other proteins as well. 相似文献