全文获取类型
收费全文 | 7047篇 |
免费 | 357篇 |
国内免费 | 72篇 |
专业分类
化学 | 5144篇 |
晶体学 | 61篇 |
力学 | 144篇 |
综合类 | 1篇 |
数学 | 626篇 |
物理学 | 1500篇 |
出版年
2023年 | 36篇 |
2022年 | 59篇 |
2021年 | 120篇 |
2020年 | 116篇 |
2019年 | 153篇 |
2018年 | 119篇 |
2017年 | 94篇 |
2016年 | 243篇 |
2015年 | 201篇 |
2014年 | 273篇 |
2013年 | 427篇 |
2012年 | 502篇 |
2011年 | 542篇 |
2010年 | 358篇 |
2009年 | 327篇 |
2008年 | 440篇 |
2007年 | 408篇 |
2006年 | 402篇 |
2005年 | 370篇 |
2004年 | 307篇 |
2003年 | 268篇 |
2002年 | 240篇 |
2001年 | 143篇 |
2000年 | 134篇 |
1999年 | 74篇 |
1998年 | 62篇 |
1997年 | 71篇 |
1996年 | 79篇 |
1995年 | 63篇 |
1994年 | 50篇 |
1993年 | 69篇 |
1992年 | 61篇 |
1991年 | 54篇 |
1990年 | 49篇 |
1989年 | 55篇 |
1988年 | 36篇 |
1987年 | 36篇 |
1986年 | 35篇 |
1985年 | 37篇 |
1984年 | 26篇 |
1983年 | 24篇 |
1982年 | 23篇 |
1981年 | 33篇 |
1980年 | 23篇 |
1979年 | 27篇 |
1978年 | 17篇 |
1977年 | 27篇 |
1976年 | 22篇 |
1975年 | 18篇 |
1974年 | 23篇 |
排序方式: 共有7476条查询结果,搜索用时 15 毫秒
91.
Supercritical fluid extraction (SFE) of the fluoroquinolones norfloxacin and ofloxacin from chicken breast muscles was examined. A liquid chromatography with fluorescence detection was used for the determination of the fluoroquinolones. Extraction conditions of the SFE were optimized by determining the extraction parameters to achieve a sufficiently high recovery of each fluoroquinolone in fortified-muscle samples. Recovery values for the extraction of the fluoroquinolones using the SFE ranged from 70 to 87%. Chickens were treated orally with each fluoroquinolone and their muscles were extracted at set time intervals for time-course determination of the fluoroquinolones in chickens. The SFE combined with liquid chromatographic analysis showed that the concentrations of the fluoroquinolones decreased gradually with time in the chicken muscles after oral treatment, giving a concentration less than 5 ng/ml in 120 h. No further sample cleanup procedures were required after the SFE. These results suggest that SFE method is an extraction method for the determination of norfloxacin and ofloxacin in chicken muscle. 相似文献
92.
CHIP-mediated hyperubiquitylation of tau promotes its self-assembly into the insoluble tau filaments
Ji Hyeon Kim Jeeyoung Lee Won Hoon Choi Seoyoung Park Seo Hyeong Park Jung Hoon Lee Sang Min Lim Ji Young Mun Hyun-Soo Cho Dohyun Han Young Ho Suh Min Jae Lee 《Chemical science》2021,12(15):5599
The tau protein is a highly soluble and natively unfolded protein. Under pathological conditions, tau undergoes multiple post-translational modifications (PTMs) and conformational changes to form insoluble filaments, which are the proteinaceous signatures of tauopathies. To dissect the crosstalk among tau PTMs during the aggregation process, we phosphorylated and ubiquitylated recombinant tau in vitro using GSK3β and CHIP, respectively. The resulting phospho–ub-tau contained conventional polyubiquitin chains with lysine 48 linkages, sufficient for proteasomal degradation, whereas unphosphorylated ub-tau species retained only one–three ubiquitin moieties. Mass-spectrometric analysis of in vitro reconstituted phospho–ub-tau revealed seven additional ubiquitylation sites, some of which are known to stabilize tau protofilament stacking in the human brain with tauopathy. When the ubiquitylation reaction was prolonged, phospho–ub-tau transformed into insoluble hyperubiquitylated tau species featuring fibrillar morphology and in vitro seeding activity. We developed a small-molecule inhibitor of CHIP through biophysical screening; this effectively suppressed tau ubiquitylation in vitro and delayed its aggregation in cultured cells including primary cultured neurons. Our biochemical findings point to a “multiple-hit model,” where sequential events of tau phosphorylation and hyperubiquitylation function as a key driver of the fibrillization process, thus indicating that targeting tau ubiquitylation may be an effective strategy to alleviate the course of tauopathies.Multiple-hit model for tau aggregation, where sequential events of tau phosphorylation and hyperubiquitylation function as a key driver of the fibrillization process. 相似文献
93.
Easily accessible N-acyl-2-triphenylphosphonioglycinate tetrafluoroborates react smoothly with trimethylphosphite in the presence of methyltriphenylphosphonium iodide to give N-acyl-2-(dimethoxyphosphoryl)glycinates in good or very good yields. The dimethoxyphosphorylglycinates may be isolated by column chromatography, or used directly for the Wadsworth-Emmons synthesis of α,β-dehydro-α-amino acids in a one-pot procedure without purification. 相似文献
94.
A general strategy is proposed to assign aliphatic side-chain resonances of large 13C,15N-labeled proteins without deuteration, using 4D 13C,15N-edited NOESY and MQ-(H)CCH-TOCSY experiments on the basis of prior assignments of backbone and 13Cbeta resonances. The strategy has been tested on a 214 residue protein (DdCAD-1) and applied to a chain-selectively 13C,15N-labeled hemoglobin (65 kDa). About 96 and 80% aliphatic side-chain spins in DdCAD-1 and hemoglobin have been assigned, respectively. The strategy proposed here will be very useful for the structure determination and dynamics characterization of large proteins by NMR. 相似文献
95.
Hohyun Kim Hyeongjin Roh Seung-Bock Yeom Hee Joo Lee Sang Beom Han 《Chromatographia》2003,58(3-4):235-240
Summary A sensitive and selective liquid chromatographic method coupled with electrospray ionization tandem mass spectrometry (LC–ESI–MS–MS) has been developed for quantification of felodipine in human and dog plasma. Compounds were separated on a 2.0 mm × 150 mm, 5.0 m particle, C8 column with 1 m m ammonium acetate–acetonitrile, 20:80, pH 6.0, as mobile phase at a flow rate of 200 L min–1. Nifedipine was used as internal standard. Plasma samples were extracted with diethyl ether, the centrifuged upper layer was evaporated, the residue was reconstituted with mobile phase, and the reconstituted samples were injected. The analytical column lasted for at least 1000 injections. By use of multiple reaction monitoring (MRM) mode in MS–MS felodipine and nifedipine were detected without severe interference from the human or dog plasma matrix. Felodipine produced a protonated precursor ion ([M + H]+) at m/z 384 and a corresponding product ion at m/z 338. And internal standard (nifedipine) produced a protonated precursor ion ([M + H]+) at m/z 347 and a corresponding product ion at m/z 315. Detection of felodipine in human and dog plasma was accurate and precise, with a limit of quantification of 0.05 ng mL–1. The method has been successfully applied to preliminary pharmacokinetic study of felodipine in human and dog plasma. 相似文献
96.
Microwave synthesis,characterization and catalytic properties of titanium-incorporated ZSM-5 zeolite
Taihuan Jin Young Kyu Hwang Do-Young Hong Sung Hwa Jhung Jin-Soo Hwang San-Eon Park Young Ho Kim Jong-San Chang 《Research on Chemical Intermediates》2007,33(6):501-512
Titanium-incorporated ZSM-5 zeolites (Si/Al = 50–200 and Si/Ti = 70) were successfully synthesized in a one-step sol-gel process
under microwave irradiation. The characteristics of Ti-ZSM-5 zeolites were investigated using X-ray power diffraction, UV/Vis-DRS,
FT-IR spectroscopy and solid-state 27Al-NMR to monitor the physico-chemical properties. Simultaneously, the acidic properties were characterized by the NH3-TPD profile. The characterization results revealed that the Ti4+ and Al3+ ions were well incorporated into the framework of Ti-ZSM-5 zeolite. The prepared zeolite was moderately active but selective
in the dehydration of methanol to dimethyl ether. 相似文献
97.
Native non‐covalently bonded protein‐protein and protein‐substrate complexes are of great interest and have been extensively studied by electrospray ionization mass spectrometry (ESI‐MS). Multiply charged protein homomultimeric complexes are shown to form by ESI‐MS. This study addresses factors that can artificially induce the formation of multiply charged protein homomultimeric complexes. Cytochrome c (Cyt c) and ubiquitin, which are monomers in solution, were found to generate (Cyt c)mn+ by electrospray ionization (ESI). The homomultimeric complexes were not limited to dimeric complexes but include also multiply charged trimers, tetramers, and pentamers. The observation of these homomultimeric complexes has never been revealed from a Cyt c solution at the concentration as low as 10 μM. Increasing the concentration of Cyt c enhanced the formation of (Cyt c)mn+ as expected; however, the protein concentration does not affect the relative intensities of monomeric and dimeric complexes. Additionally the enrichment of NH4OH also promotes the formation of (Cyt c)mn+. Notably, source collision‐induced dissociations (source‐CID) of (Cyt c)mn+ alter the charge state distribution (CSD) and may lead to an incorrect interpretation of Cyt c conformations. Hence, extra care should be taken when using CSD to interpret the conformation of a protein derived from ESI‐MS. 相似文献
98.
[reaction: see text]Reaction of indole amides 5 with tributylstannane gave spiroindolenines 9 which are readily converted into spiropyrrolidinyloxindoles. This tricyclic system is found in a number of interesting natural products. 相似文献
99.
Optical sensors based on hybrid DNA/conjugated polymer complexes 总被引:2,自引:0,他引:2
Ho HA Béra-Abérem M Leclerc M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(6):1718-1724
Single-stranded DNA (ss-DNA) can specifically bind to various targets, including a complementary ss-DNA, ions, proteins, drugs, and so forth. When binding takes place, the oligonucleotide probe often undergoes a conformational transition. This conformational change of the negatively charged ss-DNA can be detected by using a water-soluble, cationic polythiophene derivative, which transduces the complex formation into an optical (colorimetric or fluorometric) signal without any labeling of the probe or the target. This simple and rapid methodology has enabled the specific and sensitive detection of nucleic acids and human thrombin. This new biophotonic tool can easily be applied to the detection of various other biomolecules and is also useful in the high-throughput screening of new drugs. 相似文献
100.
Eun-Ku Lee Kwang-Deog Jung Oh-Shim Joo Yong-Gun Shul 《Reaction Kinetics and Catalysis Letters》2004,83(1):25-30
The room temperature wet catalytic oxidation was conducted in a batch reactor with V/MgO catalyst. The XRD study of the catalyst
used indicated that V/MgO could not only oxidize H2S to sulfur selectively, but also prevent the sulfidation of metal oxide
effectively at the room temperature. The XPS study indicated that the H2S oxidation with V/MgO could proceed by a redox mechanism
(V5+↔ V4+) and that V3+ formation (V4+→ V3+), was responsible for the deactivation of V/MgO.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献