全文获取类型
收费全文 | 1541篇 |
免费 | 57篇 |
国内免费 | 9篇 |
专业分类
化学 | 1032篇 |
晶体学 | 8篇 |
力学 | 35篇 |
数学 | 237篇 |
物理学 | 295篇 |
出版年
2024年 | 3篇 |
2023年 | 25篇 |
2022年 | 52篇 |
2021年 | 67篇 |
2020年 | 45篇 |
2019年 | 57篇 |
2018年 | 48篇 |
2017年 | 38篇 |
2016年 | 91篇 |
2015年 | 43篇 |
2014年 | 82篇 |
2013年 | 102篇 |
2012年 | 133篇 |
2011年 | 125篇 |
2010年 | 70篇 |
2009年 | 62篇 |
2008年 | 80篇 |
2007年 | 95篇 |
2006年 | 79篇 |
2005年 | 70篇 |
2004年 | 57篇 |
2003年 | 30篇 |
2002年 | 25篇 |
2001年 | 16篇 |
2000年 | 14篇 |
1999年 | 10篇 |
1998年 | 9篇 |
1997年 | 7篇 |
1996年 | 8篇 |
1995年 | 5篇 |
1994年 | 9篇 |
1993年 | 5篇 |
1992年 | 3篇 |
1991年 | 2篇 |
1990年 | 3篇 |
1989年 | 3篇 |
1988年 | 3篇 |
1987年 | 3篇 |
1986年 | 4篇 |
1985年 | 4篇 |
1984年 | 3篇 |
1982年 | 6篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1977年 | 4篇 |
1974年 | 1篇 |
排序方式: 共有1607条查询结果,搜索用时 15 毫秒
81.
A study of the viability of three derivatizing reagents for obtaining amino acid profiles in honey through high performance liquid chromatography (HPLC) is presented. A method using diode array detection based on a reaction with diethyl ethoxymethylene malonate (DEMM) and two other methods using fluorescence detection based on derivatization with fluorenylmethyl chloroformate (FMOC-Cl) and 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC) have been developed. The three methods yield detection limits close to the ppb level, but vary in relation to other analytical characteristics. The use of methyl chloroformate derivatives allows the profile to be obtained with the greatest sensitivity within a short time frame. On applying such methods to honey samples of diverse botanical origin, we observe that the proline values obtained are always lower than those found using the official spectrophotometric method, thereby underlining the advisability of using HPLC methods to reduce uncertainty in these results. 相似文献
82.
Diego Soto-Cabrera Inés Nogueda-Gutiérrez Mariana Torres-Olvera Anabelle Cerón-Nava Juan Rosales-Guevara 《Natural product research》2016,30(16):1885-1889
The hexanic, ethyl acetate and methanolic extracts from branches of Stenocereus stellatus were tested in both the 12-O-tetradecanoylphorbol-13-acetate (TPA) – induced ear oedema model and antimicrobial activity assay. The % of oedema inhibition, the Minimum Inhibitory Concentration (MIC), as well as the polyphenolic and flavonoid content were determined. Also, extracts were analysed by gas chromatography–mass spectrometry (GC–MS). In TPA model, the three extracts showed moderate oedema inhibition. In the antimicrobial activity assay, methanolic extract shows better MIC against all strains. The lowest MICs were for Candida albicans (31 μg/mL) and Rhizopus sp. (15 μg/mL). Also, 50.78 mg eq. of gallic acid/g extract of polyphenol and 115.12 mg eq. of catequine/g extract of flavonoids content were founded in ethyl acetate extract. In the chromatographic analysis, β-sitosterol, β-amyrine, betulin and some other molecules were identified. The results show that S. stellatus possess antimicrobial activities against some fungus species. 相似文献
83.
The electrophilic α-alkylation of ketones with alcohols was accomplished by a [Ru(DMSO)4]Cl2 catalyzed process, water being the only wasted material. The reaction can be successfully governed to produce either the expected ketones or their related alcohols only by changing the reaction conditions. When 2-aminobenzyl alcohol was used, a cyclization process took place to yield 2,3-disubstituted quinolines. 相似文献
84.
Asymmetric multicomponent reactions involve the preparation of chiral compounds by the reaction of three or more reagents added simultaneously. This kind of addition and reaction has some advantages over classic divergent reaction strategies, such as lower costs, time, and energy, as well as environmentally friendlier aspects. All these advantages, together with the high level of stereoselectivity attained in some of these reactions, will force chemists in industry as in academia to adopt this new strategy of synthesis, or at least to consider it as a viable option. The positive aspects as well as the drawbacks of this strategy are discussed in this Review. 相似文献
85.
86.
Diego Gamallo-Lorenzo 《Analytica chimica acta》2005,542(2):287-295
Microwave energy has been novelty applied to speed up a tetramethylammonium hydroxide (TMAH) alkaline digestion of seaweed samples and to assist distillation of iodine from seaweed alkaline digests. Iodide in the alkaline digests from seaweed and distilled iodine, reduced back to iodine in a hydroxylamine hydrochloride solution, was determined by a catalytic spectrophotometric method based on the catalytic effect of iodide on the oxidation of As(III) by Ce(IV) in H2SO4/HCl medium (Sandell-Kolthoff reaction). The determination of iodide was directly performed in the alkaline digests, while total iodine was assessed by analyzing the hydroxylamine hydrochloride solution after the distillation process. Microwave-assisted alkaline digestion was performed using 7.5 mL of TMAH and irradiating samples at 670 W for two 5.5 min steps. Microwave-assisted distillation was carried out using 4.0 mL of the alkaline digest and 3 mL of a 2.2 M hydrochloric acid and 0.05% (m/v) sodium nitrite solution, with a microwave power at 670 W for two 90 s steps. The distillate (iodine vapor) was bubbled in 10 mL of a 500 μg mL−1 hydroxylamine hydrochloride solution (accepting solution). The linear calibration ranges were 0.30-20.0 and 0.40-20.0 μg L−1 for iodide determination and total iodine determination, respectively. The limit of detection was 9.2 μg g−1 for iodide and 28.5 μg g−1 for total iodine. Repeatability of the overall procedures, expressed as R.S.D. for 11 determinations, was 2.6% for 196.3 μg g−1 of iodide measured after microwave-assisted alkaline digestion, and 5.8% for 954.3 μg g−1 of total iodine by microwave-assisted alkaline digestion followed by microwave-assisted distillation. Finally, accuracy of the methods was assessed by analyzing the NIST-09 (Sargasso) certified reference material and the methods were applied to the determination of iodide and total iodine in different Atlantic edible seaweed samples with satisfactory results. 相似文献
87.
Dr. Jorge Pascual Dr. Diego Di Girolamo Marion A. Flatken Mahmoud H. Aldamasy Guixiang Li Dr. Meng Li Prof. Antonio Abate 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(12):e202103919
In 2020 dimethyl sulfoxide (DMSO), the ever-present solvent for tin halide perovskites, was identified as an oxidant for SnII. Nonetheless, alternatives are lacking and few efforts have been devoted to replacing it. To understand this trend it is indispensable to learn the importance of DMSO on the development of tin halide perovskites. Its unique properties have allowed processing compact thin-films to be integrated into tin perovskite solar cells. Creative approaches for controlling the perovskite crystallization or increasing its stability to oxidation have been developed relying on DMSO-based inks. However, increasingly sophisticated strategies appear to lead the field to a plateau of power conversion efficiency in the range of 10–15 %. And, while DMSO-based formulations have performed in encouraging means so far, we should also start considering their potential limitations. In this concept article, we discuss the benefits and limitations of DMSO-based tin perovskite processing. 相似文献
88.
Sabrina Elkhanoufi Rachele Stefania Diego Alberti Simona Baroni Silvio Aime Prof. Simonetta Geninatti Crich 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(17):e202104563
The assessment of unregulated level of enzyme activity is a crucial parameter for early diagnoses in a wide range of pathologies. In this study, we propose the use of electron paramagnetic resonance (EPR) as an easy method to probe carboxylesterase (CE) enzymatic activity in vitro. For this application, were synthesized two amphiphilic, nitroxide containing esters, namely Tempo-C12 (T-C12) and Tempo-2-C12 (T-2-C12). They exhibit low solubility in water and form stable micelles in which the radicals are EPR almost silent, but the hydrolysis of the ester bond yields narrows and intense EPR signals. The intensity of the EPR signals is proportional to the enzymatic activity. CEs1, CEs2 and esterase from porcine liver (PLE) were investigated. The obtained results show that T-C12 and T-2-C12-containing systems display a much higher selectivity toward the CEs2, with a Limit of Detection of the same order of those ones obtained with optical methods. 相似文献
89.
Dr. Joaquim Torra Dr. Felipe Viela Dr. Diego Megías Dr. Begoña Sot Prof. Cristina Flors 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(19):e202200026
CRANAD-2 is a fluorogenic curcumin derivative used for near-infrared detection and imaging in vivo of amyloid aggregates, which are involved in neurodegenerative diseases. We explore the performance of CRANAD-2 in two super-resolution imaging techniques, namely stimulated emission depletion (STED) and single-molecule localization microscopy (SMLM), with markedly different fluorophore requirements. By conveniently adapting the concentration of CRANAD-2, which transiently binds to amyloid fibrils, we show that it performs well in both techniques, achieving a resolution in the range of 45–55 nm. Correlation of SMLM with atomic force microscopy (AFM) validates the resolution of fine features in the reconstructed super-resolved image. The good performance and versatility of CRANAD-2 provides a powerful tool for near-infrared nanoscopic imaging of amyloids in vitro and in vivo. 相似文献
90.
Diego Alberto Lomelí-Rosales Adalberto Zamudio-Ojeda Oscar Kevin Reyes-Maldonado Morelia Eunice Lpez-Reyes Georgina Cristina Basulto-Padilla Edgar Jos Lopez-Naranjo Víctor Manuel Zuiga-Mayo Gilberto Velzquez-Jurez 《Molecules (Basel, Switzerland)》2022,27(5)
So far, several studies have focused on the synthesis of metallic nanoparticles making use of extracts from the fruit of the plants from the genus Capsicum. However, as the fruit is the edible, and highly commercial, part of the plant, in this work we focused on the leaves, a part of the plant that is considered agro-industrial waste. The biological synthesis of gold (AuNPs) and silver (AgNPs) nanoparticles using aqueous extracts of root, stem and leaf of Capsicum chinense was evaluated, obtaining the best results with the leaf extract. Gold and silver nanoparticles synthesized using leaf extract (AuNPs-leaf and AgNPs-leaf, respectively) were characterized by UV-visible spectrophotometry (UV-Vis), Fourier Transform Infrared Spectroscopy with Attenuated Total Reflection (FTIR-ATR), X-ray Photoelectron Spectroscopy (XPS), Ultra Hight Resolution Scanning Electron Microscopy coupled to Energy-Dispersive X-ray spectroscopy (UHR-SEM-EDX) and Transmission Electron Microscopy (TEM), and tested for their antioxidant and antimicrobial activities. In addition, different metabolites involved in the synthesis of nanoparticles were analyzed. We found that by the use of extracts derived from the leaf, we could generate stable and easy to synthesize AuNPs and AgNPs. The AuNPs-leaf were synthesized using microwave radiation, while the AgNPs-leaf were synthesized using UV light radiation. The antioxidant activity of the extract, determined by ABTS, showed a decrease of 44.7% and 60.7% after the synthesis of the AuNPs-leaf and AgNPs-leaf, respectively. After the AgNPs-leaf synthesis, the concentration of polyphenols, reducing sugars and amino acids decreased by 15.4%, 38.7% and 46.8% in the leaf extract, respectively, while after the AuNPs-leaf synthesis only reducing sugars decreased by 67.7%. These results suggest that these groups of molecules are implicated in the reduction/stabilization of the nanoparticles. Although the contribution of these compounds in the synthesis of the AuNPs-leaf and the AgNPs-leaf was different. Finally, the AgNPs-leaf inhibited the growth of S. aureus, E. coli, S. marcescens and E. faecalis. All of them are bacterial strains of clinical importance due to their fast antibiotic resistance development. 相似文献