全文获取类型
收费全文 | 911篇 |
免费 | 28篇 |
国内免费 | 4篇 |
专业分类
化学 | 651篇 |
晶体学 | 4篇 |
力学 | 18篇 |
数学 | 140篇 |
物理学 | 130篇 |
出版年
2023年 | 8篇 |
2022年 | 27篇 |
2021年 | 47篇 |
2020年 | 41篇 |
2019年 | 26篇 |
2018年 | 23篇 |
2017年 | 17篇 |
2016年 | 41篇 |
2015年 | 35篇 |
2014年 | 46篇 |
2013年 | 55篇 |
2012年 | 54篇 |
2011年 | 64篇 |
2010年 | 41篇 |
2009年 | 45篇 |
2008年 | 75篇 |
2007年 | 48篇 |
2006年 | 44篇 |
2005年 | 33篇 |
2004年 | 28篇 |
2003年 | 24篇 |
2002年 | 24篇 |
2001年 | 8篇 |
2000年 | 11篇 |
1999年 | 8篇 |
1998年 | 5篇 |
1997年 | 7篇 |
1996年 | 6篇 |
1995年 | 6篇 |
1994年 | 4篇 |
1993年 | 3篇 |
1992年 | 5篇 |
1991年 | 2篇 |
1990年 | 2篇 |
1989年 | 2篇 |
1988年 | 3篇 |
1987年 | 3篇 |
1986年 | 4篇 |
1985年 | 3篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1978年 | 2篇 |
1977年 | 1篇 |
1970年 | 1篇 |
1937年 | 1篇 |
1936年 | 1篇 |
排序方式: 共有943条查询结果,搜索用时 234 毫秒
131.
James Mitchell Naveena Yanamala Yi Lei Tan Eric E. Gardner Kalyan C. Tirupula Fernanda Balem Mordechai Sheves Daniel Nietlispach Judith Klein‐Seetharaman 《Photochemistry and photobiology》2019,95(3):787-802
The chlorophyll‐derivative chlorin e6 (Ce6) identified in the retinas of deep‐sea ocean fish is proposed to play a functional role in red bioluminescence detection. Fluorescence and 1H NMR spectroscopy studies with the bovine dim‐light photoreceptor, rhodopsin, indicate that Ce6 weakly binds to it with μm affinity. Absorbance spectra prove that red light sensitivity enhancement is not brought about by a shift in the absorbance maximum of rhodopsin. 19F NMR experiments with samples where 19F labels are either placed at the cytoplasmic binding site or incorporated as fluorinated retinal indicate that the cytoplasmic domain is highly perturbed by binding, while little to no changes are detected near the retinal. Binding of Ce6 also inhibits G‐protein activation. Chemical shift changes in 1H‐15N NMR spectroscopy of 15N‐Trp labeled bovine rhodopsin reveal that Ce6 binding perturbs the entire structure. These results provide experimental evidence that Ce6 is an allosteric modulator of rhodopsin. 相似文献
132.
Roly J. Armstrong Wasim M. Akhtar Tom A. Young Fernanda Duarte Timothy J. Donohoe 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(36):12688-12692
Hydrogen borrowing catalysis serves as a powerful alternative to enolate alkylation, enabling the direct coupling of ketones with unactivated alcohols. However, to date, methods that enable control over the absolute stereochemical outcome of such a process have remained elusive. Here we report a catalytic asymmetric method for the synthesis of enantioenriched cyclohexanes from 1,5‐diols via hydrogen borrowing catalysis. This reaction is mediated by the addition of a chiral iridium(I) complex, which is able to impart high levels of enantioselectivity upon the process. A series of enantioenriched cyclohexanes have been prepared and the mode of enantioinduction has been probed by a combination of experimental and DFT studies. 相似文献
133.
dos Reis Lima Fernanda Maria Silva Saimon Moraes da Silva Freires André Goulart Marília Oliveira Fonseca Damos Flavio Santos de Cassia Silva Luz Rita 《Journal of Solid State Electrochemistry》2019,23(3):725-734
Journal of Solid State Electrochemistry - This paper reports the development of a photoelectrochemical platform based on indium tin oxide (ITO) electrode modified with carboxyl-functionalized... 相似文献
134.
Fernanda das Neves Costa Ricardo Moreira Borges Gilda Guimares Leito Gerold Jerz 《Journal of separation science》2019,42(8):1528-1541
Salicornia species have just been introduced to the European market as a vegetable named ‘samphire’, ‘green asparagus’, or ‘sea asparagus’. Due to its increasing attention, and associated value, minor compounds of Salicornia gaudichaudiana Moq were investigated. The use of countercurrent chromatography and mass spectrometry enabled the search for known, as well as potentially novel natural products. Their identification was achieved based on molecular weights and mass‐spectrometric fragmentation data. Low detection limits enabled the visualization of all compounds with their identification in almost real time close to the preparative countercurrent chromatography experiment. A list of known natural products from Salicornia genus guided the identification process of compounds occurring in Salicornia gaudichaudiana Moq by tandem mass spectrometry fragment comparison. The natural product classes were divided into four groups: chlorogenic acid derivatives; flavonoid derivatives; pentacyclic triterpenoid saponins; and other compounds. 相似文献
135.
136.
Silicon is an important element for plants at their structure and physiology and plays an important role in bone mineralization and soft tissue development in human beings. Furthermore, its determination is being requested more frequently due to nutritional requirements. However, the methods found in the literature to determine silicon in this type of samples require a sample preparation step, which makes them time-consuming and provides high uncertainties. In this paper, a method for the determination of silicon in plants by wavelength dispersive X-ray fluorescence (WD-XRF) spectrometry has been developed. Horsetail (Equisetum arvense L.) and nettle leaf (Urtica dioica) have been used as a source of silicon due to its medical use. Sample preparation involved calcining the sample at 700°C and preparing fused beads from the calcined sample. Calibration standards for WD-XRF measurement were prepared by mixing certified reference materials and chemical products to reproduce the samples matrix. The linear range for silicon concentration ranges from 6 to 55 wt% SiO2. The validation of the method was performed measuring a reference material (NCS DC73349 Bush branches and leaves) and comparing the results obtained by WD-XRF with those obtained by an independent method by atomic absorption spectrometry. The developed methodology is rapid and accurate, provides low uncertainties, and is environmentally friendly, as it does require the use of less hazardous reagents. 相似文献
137.
Danilo Antonio Giarola Paulo Rogério Catarini da Silva Alexandre Urbano Fernanda Midori de Oliveira César Ricardo Texeira Tarley Luiz Henrique Dall’Antonia 《Journal of Solid State Electrochemistry》2014,18(2):497-504
Nickel hydroxide films were electrosynthesized in the presence of different diluted surfactant solutions by galvanostatic electroprecipitation. Lamellar α-Ni(OH)2 films are obtained using cationic surfactant cetyltrimethylammonium bromide (CTAB), anionic surfactant sodium dodecyl sulfate (SDS), and also neutral surfactant Tween® 80. The films were structurally and morphologically characterized by X-ray diffraction, thermal gravimetric analysis, Fourier transform infrared spectroscopy, and scanning electron microscopy, and electrochemically by cyclic voltammetry and electrochemical quartz crystal microbalance (EQCM). The results evidenced that SDS remains intercalated between the lamellae of α-Ni(OH)2. Albeit the presence of CTAB and Tween® 80, it was noticed in FTIR spectra that the surfactants did not intercalate. The morphology was affected by the presence of different surfactants. All studied surfactants displaced the oxidation potential (E O) of Ni2+/Ni3+ process to less positive values. Also, the presence of surfactants improved the electrode charge efficiency and the charge response for the same number of moles of nickel ions deposited. The ratio of the charge and frequency change is 4.4 times bigger for films deposited with SDS when compared with pure α-Ni(OH)2 films. 相似文献
138.
Érica Aparecida de Oliveira Bluma Linkowski Faintuch Daniele Seo Angélica Bueno Barbezan Ana Funari Roselaine Campos Targino Ana Maria Moro 《Applied biochemistry and biotechnology》2018,185(4):863-874
Early and accurate detection of primary or metastatic tumors is of great value in staging, treatment management, and prognosis. Tumor angiogenesis plays an essential role in the growth, invasion, and metastatic spread of solid cancers, and so, is a promising approach for tumor imaging. The GX1 (CGNSNPKSC) peptide was identified by phage display library and has been investigated as a marker for human cancers. This study aims to evaluate the 99mTc-HYNIC-PEG4-c (GX1) as a biomarker for tumor imaging. Our results showed that GX1 specifically binds to tumor cells in vitro. SKMEL28 and MDA-MB231 cells achieved total binding peak at 60 min of incubation. For B16F10 and MKN45 cells, the total and specific binding were similar during all time points, while A549 cell line showed rapid cellular total uptake of the tracer at 30 min of incubation. Biodistribution showed low non-specific uptakes and rapid renal excretion. Melanoma tumors showed enhanced GX1 uptake in animal model at 60 min, and it was significantly blocked by cold peptide. The radiotracer showed tumor specificity, especially in melanomas that are highly vascularized tumors. In this sense, it should be considered in future studies, aiming to evaluate degree of angiogenesis, progression, and invasion of tumors. 相似文献
139.
Karina Basso Santiago Gilce Maria Piana Bruno José Conti Eliza de Oliveira Cardoso Bruna Fernanda Murbach Teles Andrade Mirella Rossitto Zanutto 《Natural product research》2018,32(12):1441-1445
Propolis is a bee product with several biological properties. This study aimed at investigating a propolis-containing mouthwash, its organoleptic properties, microbial contamination and its antibacterial action in vitro. This mouthwash was assessed in vivo to control dental plaque in humans. The presence of microorganisms was analyzed and the minimum inhibitory concentration against Streptococcus mutans was determined. A comparative study was done in vivo using propolis, chlorhexidine, and propolis plus chlorhexidine in lower concentrations for 14 days. Dental plaque was analyzed by the Patient Hygiene Performance (PHP) index. The odontological product was yellow, cloudy, free of microbial contamination, and exerted an inhibitory action in vitro. Individuals who used a propolis-containing mouthwash for 14 consecutive days in combination or not to chlorhexidine showed a similar PHP index to chlorhexidine alone. The product exerted an antibacterial action in vitro and in vivo, exhibiting a positive action in the control of dental plaque. 相似文献
140.
Fernanda Moreira Tatiane de Andrade Maranhão Almir Spinelli 《Journal of Solid State Electrochemistry》2018,22(5):1303-1313
A carbon paste electrode (CPE) modified with Fe3O4 nanoparticles (Fe3O4 NP) and the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (IL BMI.PF6) was employed for the electroanalytical determination of estrone (E1) by square-wave voltammetry (SWV). At the modified electrode, cyclic voltammograms of E1 in B–R buffer (pH 12.0) showed an adsorption-controlled irreversible oxidation peak at around +0.365 V. The anodic current increased by a factor of five times and the peak potential shifted 65 mV to less positive values compared with the unmodified CPE. Under optimized conditions, the calibration curve obtained showed two linear ranges: from 4.0 to 9.0 μmol L?1 and from 9.0 to 100.0 μmol L?1. The limits of detection (LOD) and quantification (LOQ) attained were 0.47 and 4.0 μmol L?1, respectively. The proposed modified electrode was applied to the determination of E1 in pork meat samples. Data provided by the proposed modified electrode were compared with data obtained by UV–vis spectroscopy. The outstanding performance of the electrochemical device indicates that Fe3O4 NP and the IL BMI.PF6 are promising materials for the preparation of chemically modified electrodes for the determination of E1. 相似文献