全文获取类型
收费全文 | 2844篇 |
免费 | 122篇 |
国内免费 | 8篇 |
专业分类
化学 | 2279篇 |
晶体学 | 14篇 |
力学 | 24篇 |
数学 | 257篇 |
物理学 | 400篇 |
出版年
2023年 | 23篇 |
2022年 | 46篇 |
2021年 | 149篇 |
2020年 | 91篇 |
2019年 | 100篇 |
2018年 | 94篇 |
2017年 | 86篇 |
2016年 | 115篇 |
2015年 | 94篇 |
2014年 | 98篇 |
2013年 | 172篇 |
2012年 | 194篇 |
2011年 | 237篇 |
2010年 | 113篇 |
2009年 | 94篇 |
2008年 | 148篇 |
2007年 | 195篇 |
2006年 | 164篇 |
2005年 | 142篇 |
2004年 | 108篇 |
2003年 | 90篇 |
2002年 | 89篇 |
2001年 | 36篇 |
2000年 | 26篇 |
1999年 | 18篇 |
1998年 | 19篇 |
1997年 | 24篇 |
1996年 | 20篇 |
1995年 | 9篇 |
1994年 | 11篇 |
1993年 | 11篇 |
1992年 | 7篇 |
1991年 | 8篇 |
1988年 | 5篇 |
1987年 | 6篇 |
1986年 | 5篇 |
1985年 | 14篇 |
1984年 | 4篇 |
1981年 | 10篇 |
1980年 | 11篇 |
1979年 | 7篇 |
1977年 | 4篇 |
1976年 | 4篇 |
1970年 | 5篇 |
1969年 | 8篇 |
1968年 | 3篇 |
1966年 | 4篇 |
1957年 | 4篇 |
1935年 | 4篇 |
1933年 | 4篇 |
排序方式: 共有2974条查询结果,搜索用时 234 毫秒
151.
This work is devoted to the elaboration of a practical scheme for the synthesis of dendritic derivatives of gallic acid containing a carboxylate-ω-alkylphosphonic acid group and three terminal promesogenic substituents. Two synthetic strategies toward the target compounds were examined that differ in the sequence of the introduction of the promesogenic units and ω-alkylphosphonic group. 相似文献
152.
Matthew P. Conley Murielle F. Delley Georges Siddiqi Giuseppe Lapadula Sébastien Norsic Vincent Monteil Olga V. Safonova Christophe Copéret 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(7):1903-1907
The insertion of an olefin into a preformed metal–carbon bond is a common mechanism for transition‐metal‐catalyzed olefin polymerization. However, in one important industrial catalyst, the Phillips catalyst, a metal–carbon bond is not present in the precatalyst. The Phillips catalyst, CrO3 dispersed on silica, polymerizes ethylene without an activator. Despite 60 years of intensive research, the active sites and the way the first Cr C bond is formed remain unknown. We synthesized well‐defined dinuclear CrII and CrIII sites on silica. Whereas the CrII material was a poor polymerization catalyst, the CrIII material was active. Poisoning studies showed that about 65 % of the CrIII sites were active, a far higher proportion than typically observed for the Phillips catalyst. Examination of the spent catalyst and isotope labeling experiments showed the formation of a Si–(μ‐OH)–CrIII species, consistent with an initiation mechanism involving the heterolytic activation of ethylene at CrIII O bonds. 相似文献
153.
154.
155.
Haitao Wu Vincent Coble Olga Vasalatiy Rolf E. Swenson Murali C. Krishna James B. Mitchell 《Tetrahedron letters》2014
Nitroxides can ameliorate the toxic effects of radiation during cancer therapy. Nitroxides are paramagnetic and can be used in magnetic resonance imaging (MRI) and electron paramagnetic resonance imaging (EPRI) to monitor in vivo oxidative stress status. Compound 5 (3-(N-piperidinemethyl)-2,2,5,5-tetramethyl-1-oxy-3-pyrroline) was found to be the most effective nitroxide radioprotector. An efficient synthesis for this promising radioprotector was developed. 相似文献
156.
Maria A. Simonova Elena. E. Petrova Olga A. Dmitrenko Ravilya L. Komaleva Natalia S. Shoshina Larisa V. Samokhvalova Tatiana I. Valyakina Eugene V. Grishin 《Analytical and bioanalytical chemistry》2014,406(25):6447-6452
Detection of staphylococcal toxins presents a great interest for medical diagnostics. Screening of clinical samples for the presence of several types of staphylococcal toxins using traditional methods—biological tests on animals or cell cultures as well as ELISA—is laborious. Multiplex detection methods would simplify testing. We have designed an xMAP-based assay to detect three staphylococcal toxins—enterotoxins A and B (SEA and SEB) and toxic shock syndrome toxin (TSST)—in cultural supernatants obtained from different strains of Staphylococcus aureus. The limits of detection of SEA, SEB, and TSST multiplex detection in S. aureus growth medium were 10, 1,000, and 5 pg/mL, respectively. Fifty-nine samples of S. aureus cultural supernatants were tested with the xMAP assay. The developed assay has proved highly effective detection of the natural toxins in the samples obtained due to bacterial cells cultivation. In prospect, the developed test system can be used in clinical diagnostics and in monitoring of foodstuffs and environmental objects. 相似文献
157.
Joanna Augustynowicz Olga G. Długosz-Grochowska Anna M. Kostecka-Gugała Maria Leja Michał K. Kruczek Adam Świderski 《Central European Journal of Chemistry》2014,12(4):519-527
This study was focused on the analysis of the contents (by HPLC-DAD) and antioxidant activity of phenolic compounds of aquatic higher plant Callitriche cophocarpa. The novelty of the work was: 1) the study of the species which is almost unknown in the context of investigations of bio-active compounds and, 2) the application of a unique L-band electron resonance spectroscopy (L-band EPR) to measure antioxidant activity of samples. The results were compared with those obtained for microalgae Chlorella and Spirulina which are widely distributed as the diet supplements. The obtained results are very promising with respect to the freeze-dried material of Callitriche, which revealed both high level of phenolic compounds (33 mg g?1 dry weight) and antioxidant activity (0.14 g of reduced DPPH· g?1 dry weight). An isoform of sinapic acid appeared to be the main fraction in this sample. The average content of the total phenolic compounds in Callitriche freeze-dried samples was ca. 43 or 25 times higher than in the case of the Chlorella or Spirulina samples, respectively. These samples showed also 16 times lower scavenging activity in relation to freeze-dried Callitriche material. 相似文献
158.
Olga Yuryevna Ridzel Henryk Kalbe Vytautas Astašauskas Pavel Kuksa Alessandra Bellissimo Wolfgang S. M. Werner 《Surface and interface analysis : SIA》2022,54(5):487-500
Reflection electron energy loss spectroscopy (REELS) spectra were measured for seven insulating organic compounds (DNA, Irganox 1010, Kapton, polyethylene [PE], poly(methyl methacrylate) [PMMA], polystyrene [PS] and polytetrafluoroethylene [PTFE]). Optical constants and energy band gaps were extracted from the measured REELS spectra after elimination of multiple electron scattering via a deconvolution and fitting the normalised single scattering energy loss spectra to Drude and Drude–Lindhard model dielectric functions, constrained by the Kramers–Kronig sum and f-sum rules. Satisfactory agreement is found for those optical constants for which literature data exists. For PTFE, the observed features in the optical data correspond to its electronic structure. 相似文献
159.
Alisa D. Kharlamova Anton S. Abel Alexei D. Averin Olga A. Maloshitskaya Vitaly A. Roznyatovskiy Evgenii N. Savelyev Boris S. Orlinson Ivan A. Novakov Irina P. Beletskaya 《Molecules (Basel, Switzerland)》2021,26(7)
N-heteroaryl substituted adamantane-containing amines are of substantial interest for their perspective antiviral and psychotherapeutic activities. Chlorine atom at alpha-position of N-heterocycles has been substituted by the amino group using convenient nucleophilic substitution reactions with a series of adamantylalkylamines. The prototropic equilibrium in these compounds was studied using NMR spectroscopy. The introduction of the second amino substituent in 4-amino-6-chloropyrimidine, 2-amino-chloropyrazine, and 1-amino-3-chloroisoquinoline was achieved using Pd(0) catalysis. 相似文献
160.
Elizaveta D. Gladkova Arina A. Chepanova Ekaterina S. Ilina Alexandra L. Zakharenko Jhannes Reynisson Olga A. Luzina Konstantin P. Volcho Olga I. Lavrik Nariman F. Salakhutdinov 《Molecules (Basel, Switzerland)》2021,26(7)
A new type of berberine derivatives was obtained by the reaction of berberrubine with aliphatic sulfonyl chlorides. The new polycyclic compounds have a sultone ring condensed to C and D rings of a protoberberine core. The reaction conditions were developed to facilitate the formation of sultones with high yields without by-product formation. Thus, it was shown that the order of addition of reagents affects the composition of the reaction products: when sulfochlorides are added to berberrubine, their corresponding 9-O-sulfonates are predominantly formed; when berberrubine is added to pre-generated sulfenes, sultones are the only products. The reaction was shown to proceed stereo-selectively and the cycle configuration was confirmed by 2D NMR spectroscopy. The inhibitory activity of the synthesized sultones and their 12-brominated analogs against the DNA-repair enzyme tyrosyl-DNA phosphodiesterase 1 (Tdp1), an important target for a potential antitumor therapy, was studied. All derivatives were active in the micromolar and submicromolar range, in contrast to the acyclic analogs and 9-O-sulfonates, which were inactive. The significance of the sultone cycle and bromine substituent in binding with the enzyme was confirmed using molecular modeling. The active inhibitors are mostly non-toxic to the HeLa cancer cell line, and several ligands show synergy with topotecan, a topoisomerase 1 poison in clinical use. Thus, novel berberine derivatives can be considered as candidates for adjuvant therapy against cancer. 相似文献