全文获取类型
收费全文 | 3668篇 |
免费 | 210篇 |
国内免费 | 392篇 |
专业分类
化学 | 3431篇 |
晶体学 | 4篇 |
力学 | 65篇 |
综合类 | 91篇 |
数学 | 119篇 |
物理学 | 560篇 |
出版年
2024年 | 6篇 |
2023年 | 50篇 |
2022年 | 204篇 |
2021年 | 154篇 |
2020年 | 108篇 |
2019年 | 101篇 |
2018年 | 97篇 |
2017年 | 147篇 |
2016年 | 135篇 |
2015年 | 126篇 |
2014年 | 132篇 |
2013年 | 207篇 |
2012年 | 309篇 |
2011年 | 249篇 |
2010年 | 204篇 |
2009年 | 247篇 |
2008年 | 248篇 |
2007年 | 264篇 |
2006年 | 193篇 |
2005年 | 165篇 |
2004年 | 143篇 |
2003年 | 95篇 |
2002年 | 108篇 |
2001年 | 64篇 |
2000年 | 78篇 |
1999年 | 70篇 |
1998年 | 51篇 |
1997年 | 47篇 |
1996年 | 44篇 |
1995年 | 33篇 |
1994年 | 32篇 |
1993年 | 23篇 |
1992年 | 23篇 |
1991年 | 21篇 |
1990年 | 14篇 |
1989年 | 11篇 |
1988年 | 14篇 |
1987年 | 8篇 |
1986年 | 15篇 |
1985年 | 4篇 |
1984年 | 10篇 |
1982年 | 8篇 |
1981年 | 2篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1976年 | 1篇 |
排序方式: 共有4270条查询结果,搜索用时 15 毫秒
81.
Colorimetric and Spectrofluorimetric Methods for the Determination of Melatonin in Tablets and Serum
Abstract Two sensitive and accurate colorimetric and spectrofluonmetric methods, are presented for the determination of melatonin in tablets and serum. The first method utilizes the reactions of p-dimethylaminobenzaldehyde in hydrochloric acid (van Urk reagent)-ferric chloride in sulphuric acid (Salkowski reagent) mixture. The blue color of the resulting reaction product is measured at 630 nm. The second method is based on the reaction of melatonin with o-phthalaldehyde in acid medium which yields highly fluorescent condensation product that is measured at 465 nm as emission wavelength, using excitation wavelength at 355 nm. No interference was observed from tableting additives, and the applicability of the methods was examined by analysing tablets containing melatonin (single and combined with pyridoxine). Mean percentage recoveries from tablets were found to be 99.9+0.31 for single and 100.5+0.15 for combined tablets using colorimetric method, while by applying spectrofluorimetric method the recoveries were found to be 100.610.41 for single and 100.2+0.39 for combined tablets. Furthermore, the proposed methods were extended to the in-vitro determination of melatonin in serum. The detection limits are 0.27 ug ml?1 for colorimetric method and 0.00035 ug ml?1 for spectrofluorimetric method. 相似文献
82.
83.
Jiangman Liu 《Analytical letters》2013,46(11):1804-1815
A sensitive method for the determination of total chromium in real samples by flow injection–chemiluminescence (FI–CL) analysis was proposed. It was found that the CL intensity from luminol–lysozyme reaction could be markedly quenched, and the decrease of CL intensity was linear with the logarithm of Cr(III) concentrations over the range of 5.0 to 4000 pg mL?1 with a detection limit of 2.0 pg mL?1 (3σ) and relative standard deviations (RSDs) of 3.0, 2.6, and 2.0% for 10, 100, and 1000 pg mL?1 Cr(III) (n = 7), respectively. At a flow rate of 2.0 mL min?1, the whole process including sampling and washing could be accomplished within 36 s. The proposed CL method was successfully applied to the determination of total chromium in pharmaceutical capsules, a dietary supplement, and spiked human serum samples, with recoveries from 92.2 to 108.4% and RSDs of less than 4.0%. Using the homemade FI–CL model, the binding constant (K = 4.38 × 106 L mol?1) and the binding sites (n ≈ 1) of Cr(III) to lysozyme were given. 相似文献
84.
Dr. Anna‐Barbara Gerber Prof. Christian J. Leumann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(22):6990-7006
We present the synthesis of the isobicyclo‐DNA building blocks with the nucleobases A, C, G and T, as well as biophysical and biological properties of oligonucleotides derived thereof. The synthesis of the sugar part was achieved in 5 steps starting from a known intermediate of the tricyclo‐DNA synthesis. Dodecamers containing single isobicyclo‐thymidine incorporations, fully modified A‐ and T‐containing sequences, and fully modified oligonucleotides containing all four bases were synthesized and characterized. Isobicyclo‐DNA forms stable duplexes with natural nucleic acids with a pronounced preference for DNA over RNA as complements. The most stable duplexes, however, arise by self‐pairing. Isobicyclo‐DNA forms preferentially B‐DNA‐like duplexes with DNA and A‐like duplexes with complementary RNA as determined by circular dichroism (CD) spectroscopy. Self‐paired duplexes show a yet unknown structure, as judged from CD spectroscopy. Biochemical tests revealed that isobicyclo‐DNA is stable in fetal bovine serum and does not elicit RNaseH activity. 相似文献
85.
《Tetrahedron letters》2014,55(50):6919-6921
We succeeded in the asymmetric nitroaldol (Henry) reaction of aromatic aldehydes with nitromethane using human serum albumin (HSA) in water at neutral pH. The reaction of 4-nitrobenzaldehyde smoothly proceeded for 24 h at 30 °C to afford the corresponding (R)-2-nitro-1-(4-nitrophenyl)ethanol (27% ee). Lowering the reaction temperature to 0 °C improved the enantioselectivity (53% ee). Although the denatured HSA also catalyzed the coupling reaction, no enantioselectivity was observed. The reaction was also applicable to other substrates bearing various substitutions on the benzene ring, and the ee of (R)-1-(biphenyl-4-yl)-2-nitroethanol was up to 79% ee. 相似文献
86.
Joanna Klebeko Paula Ossowicz-Rupniewska Ewelina
witek Joanna Szachnowska Ewa Janus Stefka G. Taneva Elena Krachmarova Maya Guncheva 《Molecules (Basel, Switzerland)》2022,27(1)
In recent years, numerous studies have shown that conversion of conventional drugs in ionic liquid (IL) formulation could be a successful strategy to improve their physicochemical properties or suggest a new route of administration. We report the synthesis and detailed characterization of eight salicylic acid-based ILs (SA-ILs) containing cation non-polar or aromatic amino acid esters. Using in vitro assays, we preliminary evaluated the therapeutic potency of the novel SA-ILs. We observed that conversion of the SA into ionic liquids led to a decrease in its cytotoxicity toward NIH/3T3 murine embryo fibroblasts and human HaCaT keratinocytes. It should be mentioned is that all amino acid alkyl ester salicylates [AAOR][SA] inhibit the production of the proinflammatory cytokine IL-6 in LPS-stimulated keratinocytes. Moreover, keratinocytes, pretreated with [PheOMe][SA] and [PheOPr][SA] seem to be protected from LPS-induced inflammation. Finally, the novel compounds exhibit a similar binding affinity to bovine serum albumin (BSA) as the parent SA, suggesting a similar pharmacokinetic profile. These preliminary results indicate that SA-ILs, especially those with [PheOMe], [PheOPr], and [ValOiPr] cation, have the potential to be further investigated as novel topical agents for chronic skin diseases such as psoriasis and acne vulgaris. 相似文献
87.
In previous research, we showed that ‘texts that tell a story’ exhibit a statistical structure that is not Maxwell–Boltzmann but Bose–Einstein. Our explanation is that this is due to the presence of ‘indistinguishability’ in human language as a result of the same words in different parts of the story being indistinguishable from one another, in much the same way that ’indistinguishability’ occurs in quantum mechanics, also there leading to the presence of Bose–Einstein rather than Maxwell–Boltzmann as a statistical structure. In the current article, we set out to provide an explanation for this Bose–Einstein statistics in human language. We show that it is the presence of ‘meaning’ in ‘texts that tell a story’ that gives rise to the lack of independence characteristic of Bose–Einstein, and provides conclusive evidence that ‘words can be considered the quanta of human language’, structurally similar to how ‘photons are the quanta of electromagnetic radiation’. Using several studies on entanglement from our Brussels research group, we also show, by introducing the von Neumann entropy for human language, that it is also the presence of ‘meaning’ in texts that makes the entropy of a total text smaller relative to the entropy of the words composing it. We explain how the new insights in this article fit in with the research domain called ‘quantum cognition’, where quantum probability models and quantum vector spaces are used in human cognition, and are also relevant to the use of quantum structures in information retrieval and natural language processing, and how they introduce ‘quantization’ and ‘Bose–Einstein statistics’ as relevant quantum effects there. Inspired by the conceptuality interpretation of quantum mechanics, and relying on the new insights, we put forward hypotheses about the nature of physical reality. In doing so, we note how this new type of decrease in entropy, and its explanation, may be important for the development of quantum thermodynamics. We likewise note how it can also give rise to an original explanatory picture of the nature of physical reality on the surface of planet Earth, in which human culture emerges as a reinforcing continuation of life. 相似文献
88.
Justyna Stefanowicz-Hajduk Anna Hering Magdalena Gucwa Katarzyna Sztormowska-Achranowicz Mariusz Kowalczyk Agata Soluch J. Renata Ochocka 《Molecules (Basel, Switzerland)》2022,27(7)
Kalanchoe species are succulents with anti-inflammatory, antioxidant, and analgesic properties, as well as cytotoxic activity. One of the most popular species cultivated in Europe is Kalanchoe daigremontiana Raym.-Hamet and H. Perrier. In our study, we analyzed the phytochemical composition of K. daigremontiana water extract using UHPLC-QTOF-MS and estimated the cytotoxic activity of the extract on human ovarian cancer SKOV-3 cells by MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assay, flow cytometry, luminometric, and fluorescent microscopy techniques. The expression levels of 92 genes associated with cell death were estimated via real-time PCR. The antioxidant activity was assessed via flow cytometry on human keratinocyte HaCaT cell line. The DPPH (2,2-diphenyl-1-picrylhydrazyl) radical and FRAP (ferric-reducing antioxidant power) assays were also applied. We identified twenty bufadienolide compounds in the water extract and quantified eleven. Bersaldegenin-1,3,5-orthoacetate and bryophyllin A were present in the highest amounts (757.4 ± 18.7 and 573.5 ± 27.2 ng/mg dry weight, respectively). The extract showed significant antiproliferative and cytotoxic activity, induced depolarization of the mitochondrial membrane, and significantly arrested cell cycle in the S and G2/M phases of SKOV-3 cells. Caspases-3, 7, 8, and 9 were not activated during the treatment, which indicated non-apoptotic cell death triggered by the extract. Additionally, the extract increased the level of oxidative stress in the cancer cell line. In keratinocytes treated with menadione, the extract moderately reduced the level of oxidative stress. This antioxidant activity was confirmed by the DPPH and FRAP assays, where the obtained IC50 values were 1750 ± 140 and 1271.82 ± 53.25 μg/mL, respectively. The real-time PCR analysis revealed that the extract may induce cell death via TNF receptor (tumor necrosis factor receptor) superfamily members 6 and 10. 相似文献
89.
Francesca Felice Maria Michela Cesare Luca Fredianelli Marinella De Leo Veronica Conti Alessandra Braca Rossella Di Stefano 《Molecules (Basel, Switzerland)》2022,27(8)
Tomatoes and their derivates represent an important source of natural biologically active components. The present study aims to investigate the protective effect of tomato peel extracts, grown in normal (RED-Ctr) or in drought stress (RED-Ds) conditions, on an experimental model of sarcopenia. The phenolic profile and total polyphenols content (TPC) of RED-Ctr and RED-Ds were determined by Ultra High-Performance Liquid Chromatography (UHPLC) analyses coupled to electrospray ionization high-resolution mass spectrometry (ESI-HR-MS). Human skeletal muscle myoblasts (HSMM) were differentiated in myotubes, and sarcopenia was induced by dexamethasone (DEXA) treatment. Differentiation and sarcopenia were evaluated by both real-time PCR and immunofluorescent techniques. Data show that myosin heavy chain 2 (MYH2), troponin T (TNNT1), and miogenin (MYOG) were expressed in differentiated myotubes. 5 μg Gallic Acid Equivalent (GAE/mL) of TPC from RED-Ds extract significantly reduced muscle atrophy induced by DEXA. Moreover, Forkhead BoxO1 (FOXO1) expression, involved in cell atrophy, was significantly decreased by RED-Ds extract. The protective effect of tomato peel extracts depended on their qualitative polyphenolic composition, resulting effectively in the in vitro model of sarcopenia. 相似文献
90.
邻菲咯啉合铜配合物与牛血清白蛋白的相互作用 总被引:1,自引:0,他引:1
利用荧光光谱法研究了两种配合物,[Cu(phen)(L-Phe)(H2O)]ClO4(1)(L-Phe为L-苯丙氨酸根)和[Cu(phen)(Gly)(H2O)]ClO4·2.5H2O(2)(Cly为甘氨酸根),与牛血清白蛋白(BSA)的相互作用。结果表明,牛血清白蛋白的荧光强度随着配合物浓度的增大而逐渐降低,配合物(2)与BSA的结合常数大于配合物(1)与BSA的结合常数,牛血清白蛋白对配合物的结合位点数为1,荧光猝灭作用机理为静态猝灭. 相似文献