全文获取类型
收费全文 | 596篇 |
免费 | 42篇 |
国内免费 | 5篇 |
专业分类
化学 | 546篇 |
力学 | 2篇 |
数学 | 74篇 |
物理学 | 21篇 |
出版年
2023年 | 7篇 |
2022年 | 6篇 |
2021年 | 9篇 |
2020年 | 21篇 |
2019年 | 17篇 |
2018年 | 8篇 |
2017年 | 8篇 |
2016年 | 24篇 |
2015年 | 27篇 |
2014年 | 36篇 |
2013年 | 36篇 |
2012年 | 61篇 |
2011年 | 70篇 |
2010年 | 46篇 |
2009年 | 25篇 |
2008年 | 37篇 |
2007年 | 30篇 |
2006年 | 20篇 |
2005年 | 17篇 |
2004年 | 11篇 |
2003年 | 9篇 |
2002年 | 11篇 |
2001年 | 6篇 |
2000年 | 8篇 |
1999年 | 6篇 |
1997年 | 5篇 |
1996年 | 2篇 |
1994年 | 2篇 |
1992年 | 2篇 |
1981年 | 4篇 |
1975年 | 2篇 |
1972年 | 4篇 |
1971年 | 2篇 |
1967年 | 2篇 |
1965年 | 3篇 |
1963年 | 5篇 |
1962年 | 2篇 |
1961年 | 3篇 |
1959年 | 5篇 |
1958年 | 6篇 |
1957年 | 4篇 |
1956年 | 3篇 |
1955年 | 2篇 |
1954年 | 5篇 |
1953年 | 1篇 |
1952年 | 3篇 |
1950年 | 1篇 |
1948年 | 4篇 |
1947年 | 2篇 |
1943年 | 2篇 |
排序方式: 共有643条查询结果,搜索用时 472 毫秒
21.
Kai Zhang Steffen Fischer Andreas Geissler Erica Brendler Kathrin Gebauer 《Cellulose (London, England)》2013,20(4):2069-2080
Synthesis of cellulose sulfates (CSs) and carboxyl cellulose sulfates (COCSs) with regioselectively or regiospecifically distributed functional groups within anhydroglucose units was reported. CS with regioselectively distributed sulfate groups at 2,3-O- or 2,6-O-position were homogeneously synthesized and cellulose trifluoroacetate (CTFA) was used as intermediates. The trifluoroacetyl groups were detected primarily at 6-O-position and their distributions could be altered by changing the amount of trifluoroacetyl anhydride (TFAA). Various sulfating agents were used for further homogeneous sulfation of CTFA. The total degree of sulfation (DSS) and the distribution of sulfate groups within the repeating units were affected by the amount of TFAA, the type and amount of sulfating agents. Subsequent homogenous 4-acetamide-TEMPO or TEMPO-mediated oxidation of CS led to COCS with carboxyl groups regiospecifically distributed at C6 position, which may be interesting structural mimics for natural occurring heparin. 相似文献
22.
Peter Fechner Oliver Bleher Melanie Ewald Kathrin Freudenberger Dominik Furin Urs Hilbig Felix Kolarov Katrin Krieg Lothar Leidner Goran Markovic Günther Proll Florian Pröll Sabrina Rau Johannes Riedt Barbara Schwarz Patricia Weber Julia Widmaier 《Analytical and bioanalytical chemistry》2014,406(17):4033-4051
This review is focused on methods for detecting small molecules and, in particular, the characterisation of their interaction with natural proteins (e.g. receptors, ion channels). Because there are intrinsic advantages to using label-free methods over labelled methods (e.g. fluorescence, radioactivity), this review only covers label-free techniques. We briefly discuss available techniques and their advantages and disadvantages, especially as related to investigating the interaction between small molecules and proteins. The reviewed techniques include well-known and widely used standard analytical methods (e.g. HPLC-MS, NMR, calorimetry, and X-ray diffraction), newer and more specialised analytical methods (e.g. biosensors), biological systems (e.g. cell lines and animal models), and in-silico approaches. 相似文献
23.
24.
25.
Olga Begou Kathrin Weber Bibiana Beckmann Dimitrios Tsikas 《Molecules (Basel, Switzerland)》2021,26(11)
In consideration of its relatively constant urinary excretion rate, creatinine (2-amino-1-methyl-5H-imidazol-4-one, MW 113.1) in urine is a useful endogenous biochemical parameter to correct the urinary excretion rate of numerous endogenous and exogenous substances. Reliable measurement of creatinine by gas chromatography (GC)-based methods requires derivatization of its amine and keto groups. Creatinine exists in equilibrium with its open form creatine (methylguanidoacetic acid, MW 131.1), which has a guanidine and a carboxylic group. Trimethylsilylation and trifluoroacetylation of creatinine and creatine are the oldest reported derivatization methods for their GC-mass spectrometry (MS) analysis in human serum using flame- or electron-ionization. We performed GC-MS studies on the derivatization of creatinine (d0-creatinine), [methylo-2H3]creatinine (d3-creatinine, internal standard) and creatine (d0-creatine) with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) using standard derivatization conditions (60 min, 60 °C), yet in the absence of any base. Reaction products were characterized both in the negative-ion chemical ionization (NICI) and in the positive-ion chemical ionization (PICI) mode. Creatinine and creatine reacted with BSTFA to form several derivatives. Their early eluting N,N,O-tris(trimethylsilyl) derivatives (8.9 min) were found to be useful for the precise and accurate measurement of the sum of creatinine and creatine in human urine (10 µL, up to 20 mM) by selected-ion monitoring (SIM) of m/z 271 (d0-creatinine/d0-creatine) and m/z 274 (d3-creatinine) in the NICI mode. In the PICI mode, SIM of m/z 256, m/z 259, m/z 272 and m/z 275 was performed. BSTFA derivatization of d0-creatine from a freshly prepared solution in distilled water resulted in formation of two lMate-eluting derivatives (14.08 min, 14.72 min), presumably creatinyl-creatinine, with the creatininyl residue existing in its enol form (14.08 min) and keto form (14.72 min). Our results suggest that BSTFA derivatization does not allow specific analysis of creatine and creatinine by GC-MS. Preliminary analyses suggest that pentafluoropropionic anhydride (PFPA) is also not useful for the measurement of creatinine in the presence of creatine. Both BSTFA and PFPA facilitate the conversion of creatine to creatinine. Specific measurement of creatinine in urine is possible by using pentafluorobenzyl bromide in aqueous acetone. 相似文献
26.
27.
Kathrin Brmmel Sarah Maskri Ivan Maisuls Christian Paul Konken Marius Rieke Zoltan Peth Cristian A. Strassert Oliver Koch Albrecht Schwab Bernhard Wünsch 《Angewandte Chemie (International ed. in English)》2020,59(21):8277-8284
Small‐molecule probes for the in vitro imaging of KCa3.1 channel‐expressing cells were developed. Senicapoc, showing high affinity and selectivity for the KCa3.1 channels, was chosen as the targeting component. BODIPY dyes 15 – 20 were synthesized and connected by a CuI‐catalyzed azide–alkyne [3+2]cycloaddition with propargyl ether senicapoc derivative 8 , yielding fluorescently labeled ligands 21 – 26 . The dimethylpyrrole‐based imaging probes 25 and 26 allow staining of KCa3.1 channels in NSCLC cells. The specificity was shown by removing the punctate staining pattern by pre‐incubation with senicapoc. The density of KCa3.1 channels detected with 25 and by immunostaining was identical. The punctate structure of the labeled channels could also be observed in living cells. Molecular modeling showed binding of the senicapoc‐targeting component towards the binding site within the ion channel and orientation of the linker with the dye along the inner surface of the ion channel. 相似文献
28.
29.
Xinjiang Cui Wu Li Kathrin Junge Zhaofu Fei Matthias Beller Paul J. Dyson 《Angewandte Chemie (International ed. in English)》2020,59(19):7501-7507
Core–shell nanocatalysts are attractive due to their versatility and stability. Here, we describe cobalt nanoparticles encapsulated within graphitic shells prepared via the pyrolysis of a cationic poly‐ionic liquid (PIL) with a cobalt(II) chloride anion. The resulting material has a core–shell structure that displays excellent activity and selectivity in the self‐dehydrogenation and hetero‐dehydrogenation of primary amines to their corresponding imines. Furthermore, the catalyst exhibits excellent activity in the synthesis of secondary imines from substrates with various reducible functional groups (C=C, C≡C and C≡N) and amino acid derivatives. 相似文献
30.
Jrg Schappel Kathrin Schmidt Elisabeth Klemm 《Journal of polymer science. Part A, Polymer chemistry》2005,43(16):3574-3587
A Sonogashira polycondensation reaction has been used to synthesize copolymers consisting of alternating oligo(p‐phenyleneethynylene) with a precise block length as an electron‐rich component and 1,4‐bis(2‐phenylene‐2‐cyanovinylene)benzene or 2,6‐bis(2‐pyridinylene‐ethynylene)pyridine as an electron‐poor component. The copolymers differ in the length of the phenyleneethynylene block (trimer or pentamer) and the content of the electron‐poor component. The length of the phenyleneethynylene block has no influence on the maximum wavelength. The electron‐poor cyano‐block component lowers the optical band‐gap energy of the copolymers. The value is equivalent to that of poly(cyano‐phenylenevinylene) (CN‐PPV) (2.3–2.4 eV). © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3574–3587, 2005 相似文献