全文获取类型
收费全文 | 1626篇 |
免费 | 51篇 |
国内免费 | 2篇 |
专业分类
化学 | 1078篇 |
晶体学 | 6篇 |
力学 | 19篇 |
数学 | 215篇 |
物理学 | 361篇 |
出版年
2024年 | 3篇 |
2023年 | 13篇 |
2022年 | 55篇 |
2021年 | 49篇 |
2020年 | 41篇 |
2019年 | 43篇 |
2018年 | 29篇 |
2017年 | 28篇 |
2016年 | 78篇 |
2015年 | 51篇 |
2014年 | 63篇 |
2013年 | 66篇 |
2012年 | 126篇 |
2011年 | 147篇 |
2010年 | 111篇 |
2009年 | 68篇 |
2008年 | 101篇 |
2007年 | 137篇 |
2006年 | 81篇 |
2005年 | 66篇 |
2004年 | 53篇 |
2003年 | 38篇 |
2002年 | 29篇 |
2001年 | 14篇 |
2000年 | 16篇 |
1999年 | 15篇 |
1998年 | 10篇 |
1997年 | 6篇 |
1996年 | 16篇 |
1995年 | 19篇 |
1994年 | 17篇 |
1993年 | 9篇 |
1992年 | 7篇 |
1991年 | 5篇 |
1990年 | 5篇 |
1989年 | 6篇 |
1986年 | 2篇 |
1985年 | 2篇 |
1982年 | 3篇 |
1981年 | 6篇 |
1980年 | 7篇 |
1979年 | 5篇 |
1978年 | 2篇 |
1977年 | 4篇 |
1976年 | 4篇 |
1975年 | 4篇 |
1969年 | 3篇 |
1968年 | 2篇 |
1905年 | 3篇 |
1904年 | 2篇 |
排序方式: 共有1679条查询结果,搜索用时 15 毫秒
91.
Ahmad Bachir Fabiana Ciocchetti Daniel P. Couto Dr. Simone Di Noja Dr. Cristian Pezzato Dr. Giulio Ragazzon 《European journal of organic chemistry》2023,26(29):e202300498
Cyclobis(paraquat-p-phenylene), also known as “blue box”, is a highly electron-deficient macrocycle, widely used as a molecular receptor for small electron-rich molecules. Inserting a reactive functional group onto the molecular structure of this cyclophane is paramount for its inclusion into complex architectures. To this aim, including an alkyne moiety would be ideal, because it can participate in click reactions. However, the synthesis of such alkyne-functionalized cyclophane suffers from several drawbacks: the use of toxic and expensive CCl4, the need for high-pressure reactors, and overall low yield. We have revised the existing synthesis of this cyclophane derivative bearing an alkyne moiety, to overcome all these limitations. In particular, photochemical radical bromination is adopted to obtain a sensitive intermediate. We demonstrated that the synthesized host molecule can be functionalized via click reactions and take part in radical-radical interactions. Our work makes a key functionalized paraquat macrocycle more accessible, facilitating the development of novel redox-responsive systems. 相似文献
92.
Dr. Patrick Eiring Dr. Teresa Klein Dr. Simone Backes Marcel Streit Marvin Jungblut Dr. Sören Doose Dr. Gerti Beliu Prof. Dr. Markus Sauer 《Angewandte Chemie (International ed. in English)》2023,62(30):e202300821
The angiotensin-converting enzyme 2 (ACE2) has been identified as entry receptor on cells enabling binding and infection with the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) via trimeric spike (S) proteins protruding from the viral surface. It has been suggested that trimeric S proteins preferably bind to plasma membrane areas with high concentrations of possibly multimeric ACE2 receptors to achieve a higher binding and infection efficiency. Here we used direct stochastic optical reconstruction microscopy (dSTORM) in combination with different labeling approaches to visualize the distribution and quantify the expression of ACE2 on different cells. Our results reveal that endogenous ACE2 receptors are present as monomers in the plasma membrane with densities of only 1–2 receptors μm−2. In addition, binding of trimeric S proteins does not induce the formation of ACE2 oligomers in the plasma membrane. Supported by infection studies using vesicular stomatitis virus (VSV) particles bearing S proteins our data demonstrate that a single S protein interaction per virus particle with a monomeric ACE2 receptor is sufficient for infection, which provides SARS-CoV-2 a high infectivity. 相似文献
93.
Electrochemiluminescence Bioassays with a Water‐Soluble Luminol Derivative Can Outperform Fluorescence Assays 下载免费PDF全文
Michael Mayer Prof. Dr. Shigehiko Takegami Michael Neumeier Simone Rink Prof. Dr. Axel Jacobi von Wangelin Silja Schulte Moritz Vollmer Prof. Dr. Axel G. Griesbeck PD Dr. Axel Duerkop Prof. Dr. Antje J. Baeumner 《Angewandte Chemie (International ed. in English)》2018,57(2):408-411
The most efficient and commonly used electrochemiluminescence (ECL) emitters are luminol, [Ru(bpy)3]2+, and derivatives thereof. Luminol stands out due to its low excitation potential, but applications are limited by its insolubility under physiological conditions. The water‐soluble m‐carboxy luminol was synthesized in 15 % yield and exhibited high solubility under physiological conditions and afforded a four‐fold ECL signal increase (vs. luminol). Entrapment in DNA‐tagged liposomes enabled a DNA assay with a detection limit of 3.2 pmol L?1, which is 150 times lower than the corresponding fluorescence approach. This remarkable sensitivity gain and the low excitation potential establish m‐carboxy luminol as a superior ECL probe with direct relevance to chemiluminescence and enzymatic bioanalytical approaches. 相似文献
94.
Quantitative Prediction of Rate Constants for Aqueous Racemization To Avoid Pointless Stereoselective Syntheses 下载免费PDF全文
Dr. Andrew Ballard Dr. Hiwa O. Ahmad Dr. Stefania Narduolo Lucy Rosa Nikki Chand Dr. David A. Cosgrove Dr. Peter Varkonyi Dr. Nabil Asaad Dr. Simone Tomasi Dr. Niklaas J. Buurma Dr. Andrew G. Leach 《Angewandte Chemie (International ed. in English)》2018,57(4):982-985
Racemization has a large impact upon the biological properties of molecules but the chemical scope of compounds with known rate constants for racemization in aqueous conditions was hitherto limited. To address this remarkable blind spot, we have measured the kinetics for racemization of 28 compounds using circular dichroism and 1H NMR spectroscopy. We show that rate constants for racemization (measured by ourselves and others) correlate well with deprotonation energies from quantum mechanical (QM) and group contribution calculations. Such calculations thus provide predictions of the second‐order rate constants for general‐base‐catalyzed racemization that are usefully accurate. When applied to recent publications describing the stereoselective synthesis of compounds of purported biological value, the calculations reveal that racemization would be sufficiently fast to render these expensive syntheses pointless. 相似文献
95.
Simone König Martin Zeller Jasna Peter-Katalinic Johannes Roth Clemens Sorg Thomas Vogl 《Journal of the American Society for Mass Spectrometry》2001,12(11):1180-1185
In this paper, analysis strategies developed for a sequencing problem concerning the identification of an S100 protein isolated from human granulocytes are discussed. The analysis of a trypsinized lyophilized sample suggested the presence of a number of peptides which are non-tryptic in origin. During purification of proteins from cell lysates nonspecific cleavage can be observed which may reflect biological processes and can become an unavoidable analytical problem. Current mass spectrometric software is evaluated for the analysis of nonspecific digests in this context. Matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS), high-performance liquid chromatography (HPLC)-MS/MS, and selected ion monitoring (SIM)-MS/MS have been used for peptide analysis and in addition HPLC-MS was carried out for protein analysis leading to the detection of an N-terminal modification of the protein. The success of the study is mainly due to the careful investigation of nonspecific cleavage products. Data obtained from the routine mass spectrometric analysis of an in-gel-digest allowed the identification of this protein as S100 calcium-binding protein A6-calcyclin whose expression in granulocytes has not been described so far. 相似文献
96.
Aromatic azides with hindered amine light stabilizer (HALS) residues or hydrophilic groups such as glucose, sucrose and dextrine residues were synthesized and used for surface modification of polyolefins. By UV‐irradiation nitrenes were formed, which are able to react with polyolefin surfaces. By photochemical immobilization of the carbohydrates hydrophilicity of PE and PP was strongly increased (surface tensions > 44mN/m). Light stability of PP surfaces modified with HALS azides was comparable with PP, stabilised with Tinuvin 770. Bulk modification of ethylene‐propylene and ethylene‐octene copolymers was achieved by grafting nitrenes formed by thermal decomposition of azido benzoic acid. In a circulating air oven up to 1.55 wt% amino benzoic acid residues could be bonded covalently to ethylene‐propylene‐copolymers, less than half of it to ethylene‐octene‐copolymers. Reactive extrusion resulted in grafting yields of more than 50% for both types of copolymers. 相似文献
97.
Jochen Glaser Simone Dill Michael Marzini Hermann A. Mayer H.‐Jürgen Meyer 《无机化学与普通化学杂志》2001,627(5):1090-1094
(Meta)stable CaC2 One out of four modifications of CaC2 is the so‐called metastable Calcium Carbide, CaC2‐III, which was synthesized as pure material. It forms by heating monoclinic CaC2‐II (C2/c) above 150 °C and remains stable after cooling down to room temperature. The structure was refined from X‐ray powder patterns (C2/m, Z = 4, a = 722.6(1) pm, b = 385.26(7) pm, c = 737.6(1) pm, β = 107.345(2)°). After grinding CaC2‐III transforms back into CaC2‐II. Heating CaC2‐III induces a reversible phase transition into the cubic modification (CaC2‐IV) at 460 °C. Differences between the three different structures of CaC2 I–III, being stable at ambient conditions are also shown by 13C‐MAS‐NMR measurements, especially the presence of two distinct types of carbon atoms in the structure of the title compound. 相似文献
98.
Stefano Federico Tuhina Khan Nicola Relitti Giulia Chemi Margherita Brindisi Simone Brogi Ettore Novellino Daniela M. Zisterer Giuseppe Campiani Sandra Gemma Stefania Butini 《Tetrahedron letters》2018,59(51):4466-4470
We developed a Jocic-type protocol for the construction of the pyrrolonaphthoxazepine (PNOX) core. After an initial investigation based on the isolation of a trichloromethyl carbinol derivative, we shifted our attention towards a multicomponent single-step protocol. Screening of a variety of bases and solvents led to the identification of the optimum conditions for the preparation of the key α-aryloxy carboxylic acids to undergo intramolecular cyclization. The novel chemical route significantly improved overall yields for the preparation of PNOX-based compounds and was successfully extended to the preparation of 1,4-benzoxazinone-based templates. 相似文献
99.
Validation of Sun Exposure Reported Annually Against Interim Self‐report and Daily Sun Diaries 下载免费PDF全文
Laura King Fan Xiang Ashwin Swaminathan Keith Dear Simone L. Harrison Ingrid van der Mei Michael G. Kimlin Catherine D'Este Robyn M. Lucas 《Photochemistry and photobiology》2017,93(5):1294-1302
Data on personal sun exposure over a period exceeding the immediate past days or weeks are typically self‐reported in brief questionnaire items. The validity of such self‐reporting of longer term personal sun exposure, for example over a year, including detail on variation across seasons, has not previously been investigated. In a volunteer sample (n = 331) of Australian adults aged 18 years and over, we assessed the 12‐month reliability of sun exposure reported separately for each season, and its accuracy compared to a daily sun diary in the same season. Seasonal time outdoors displayed fair‐to‐good reliability between baseline and end of study (12 months), with responses showing higher agreement at lower levels of time outdoors. There was good agreement for ranking of individuals' time outdoors with the daily sun diary data, although the actual diary time outdoors was typically considerably lower than the self‐reported questionnaire data. Place of residence, education, being a smoker, day of the week (i.e. working day vs nonworking day) and working mainly outdoors were significant predictors of agreement. While participants overestimated their actual time outdoors, the self‐report questionnaire provided a valid ranking of long‐term sun exposure against others in the study that was reliable over time. 相似文献
100.
Polyanna Silveira Hornung Layse do Prado Cordoba Simone Rosa da Silveira Lazzarotto Egon Schnitzler Marcelo Lazzarotto Rosemary Hoffmann Ribani 《Journal of Thermal Analysis and Calorimetry》2017,127(3):1869-1877
Determination of the characteristics of native starches is crucial in order to select their best application in various industrial fields. Thus, two different types of non-traditional native starches from the Dioscoreaceas species (Dioscorea sp. and Dioscorea piperifolia Humb. var. Wild) were studied regarding their thermal, structural and rheological properties. The results were contrasted with traditional commercial starch sources (potato, cassava and corn). From the thermogravimetric results (TG/DTG), D. piperifolia starch obtained the highest thermal stability of the samples, except for potato starch. Furthermore, using differential scanning calorimetry and viscoamylograph profiles (RVA), it was found that the Dioscoreaceas starches presented a higher onset (T o) temperature and susceptibility to retrogradation. They also showed lower values in relation to relative crystallinity, which was calculated from their X-ray patterns and tendency to white (L*) colour. The shapes of the Discoreaceas starch granules were determined using electron microscopy; it was found that as the potato starch the Dioscoreaceas starches showed a wide range of particle size. 相似文献