全文获取类型
收费全文 | 1789篇 |
免费 | 79篇 |
国内免费 | 7篇 |
专业分类
化学 | 1373篇 |
晶体学 | 4篇 |
力学 | 58篇 |
数学 | 238篇 |
物理学 | 202篇 |
出版年
2023年 | 15篇 |
2022年 | 66篇 |
2021年 | 86篇 |
2020年 | 43篇 |
2019年 | 42篇 |
2018年 | 14篇 |
2017年 | 31篇 |
2016年 | 62篇 |
2015年 | 58篇 |
2014年 | 76篇 |
2013年 | 95篇 |
2012年 | 112篇 |
2011年 | 139篇 |
2010年 | 75篇 |
2009年 | 89篇 |
2008年 | 119篇 |
2007年 | 118篇 |
2006年 | 108篇 |
2005年 | 101篇 |
2004年 | 79篇 |
2003年 | 72篇 |
2002年 | 68篇 |
2001年 | 19篇 |
2000年 | 15篇 |
1999年 | 16篇 |
1998年 | 17篇 |
1997年 | 15篇 |
1996年 | 18篇 |
1995年 | 8篇 |
1994年 | 11篇 |
1993年 | 14篇 |
1992年 | 8篇 |
1991年 | 6篇 |
1990年 | 5篇 |
1989年 | 13篇 |
1985年 | 5篇 |
1984年 | 6篇 |
1983年 | 5篇 |
1982年 | 5篇 |
1979年 | 4篇 |
1978年 | 2篇 |
1977年 | 1篇 |
1976年 | 2篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1971年 | 1篇 |
1964年 | 1篇 |
1963年 | 1篇 |
1911年 | 1篇 |
1909年 | 2篇 |
排序方式: 共有1875条查询结果,搜索用时 15 毫秒
51.
Yanpeng Xue Eirini Maria Paschalidou Paola Rizzi Livio Battezzati Hans-Jörg Fecht 《哲学杂志》2018,98(30):2769-2781
Nanoporous gold thin films have been fabricated through chemical de-alloying of Au-based nanoglass with a nanocolumnar structure, with composition Au40Cu28Ag7Pd5Si20 (at.%), that had previously been deposited by magnetron sputtering. By varying the de-alloying conditions, gold ligaments ranging from 20 to 100?nm were obtained. The microstructure and chemical composition of the as-prepared films were characterised by various techniques. Surface-enhanced Raman scattering (SERS) of thin films was investigated using rhodamine 6G. The results indicate that the main microstructural features with interconnected ligaments and defects of nanoporous gold result in significant SERS enhancement. 相似文献
52.
Mario Jug Francesca Maestrelli Paola Mura 《Journal of inclusion phenomena and macrocyclic chemistry》2012,74(1-4):87-97
β-Cyclodextrin (βCD) and its soluble polymeric derivative (EPIβCD) were used to improve the effectiveness of chitosan-based bucco-adhesive film formulations containing bupivacaine hydrochloride and triclosan as poorly-soluble model drugs. The film formulations were characterized in terms of swelling, mucoadhesion and in vitro drug release, while possible interactions between the components were investigated by DSC and FTIR analyses. For both drugs EPIβCD showed a higher solubilizing efficiency than βCD; however cyclodextrin effectiveness in improving the release rate from film formulations was influenced by their different interactions with chitosan. Free βCD acted as a channelling agent, favouring the film swelling, while EPIβCD due to interaction with chitosan caused an opposite effect. βCD was the optimal partner for bupivacaine-loaded films in terms of film swelling, mucoadhesion and drug release. Contrariwise, EPIβCD was the best partner for triclosan-loaded films, allowing the highest drug release rate increase, due to its higher solubilizing ability with respect to βCD. Addition of the suitable cyclodextrin enabled formulation of buccal films with suitable drug release properties. 相似文献
53.
54.
55.
56.
Molecular Size and Electronic Structure Combined Effects on the Electrogenerated Chemiluminescence of Sulfurated Pyrene‐Cored Dendrimers
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Giovanni Valenti Dr. Andrea Fiorani Dr. Simone Di Motta Dr. Giacomo Bergamini Prof. Marc Gingras Prof. Paola Ceroni Prof. Fabrizia Negri Prof. Francesco Paolucci Prof. Massimo Marcaccio 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(7):2936-2947
The electrochemistry, photophysics, and electrochemically generated chemiluminescence (ECL) of a family of polysulfurated dendrimers with a pyrene core have been thoroughly investigated and complemented by theoretical calculations. The redox and luminescence properties of dendrimers are dependent on the generation number. From low to higher generation it is both easier to reduce and oxidize them and the emission efficiency increases along the family, with respect to the polysulfurated pyrene core. The analysis of such data evidences that the formation of the singlet excited state by cation–anion annihilation is an energy‐deficient process and, thus, the ECL has been justified through the triplet–triplet annihilation pathway. The study of the dynamics of the ECL emission was achieved both experimentally and theoretically by molecular mechanics and quantum chemical calculations. It has allowed rationalization of a possible mechanism and the experimental dependence of the transient ECL on the dendrimer generation. The theoretically calculated Marcus electron‐transfer rate constant compares very well with that obtained by the finite element simulation of the whole ECL mechanism. This highlights the role played by the thioether dendrons in modulating the redox and photophysical properties, responsible for the occurrence and dynamics of the electron transfer involved in the ECL. Thus, the combination of experimental and computational results allows understanding of the dendrimer size dependence of the ECL transient signal as a result of factors affecting the annihilation electron transfer. 相似文献
57.
Dr. Marzia Dell'Aera Dr. Filippo Maria Perna Dr. Paola Vitale Dr. Angela Altomare Prof. Alessandro Palmieri Dr. Lewis C. H. Maddock Leonie J. Bole Dr. Alan R. Kennedy Prof. Eva Hevia Prof. Vito Capriati 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(40):8742-8748
We report the first transition metal catalyst- and ligand-free conjugate addition of lithium tetraorganozincates (R4ZnLi2) to nitroolefins. Displaying enhanced nucleophilicity combined with unique chemoselectivity and functional group tolerance, homoleptic aliphatic and aromatic R4ZnLi2 provide access to valuable nitroalkanes in up to 98 % yield under mild conditions (0 °C) and short reaction time (30 min). This is particularly remarkable when employing β-nitroacrylates and β-nitroenones, where despite the presence of other electrophilic groups, selective 1,4 addition to the C=C is preferred. Structural and spectroscopic studies confirmed the formation of tetraorganozincate species in solution, the nature of which has been a long debated issue, and allowed to unveil the key role played by donor additives on the aggregation and structure of these reagents. Thus, while chelating N,N,N’,N’-tetramethylethylenediamine (TMEDA) and (R,R)-N,N,N’,N’-tetramethyl-1,2-diaminocyclohexane (TMCDA) favour the formation of contacted-ion pair zincates, macrocyclic Lewis donor 12-crown-4 triggers an immediate disproportionation process of Et4ZnLi2 into equimolar amounts of solvent-separated Et3ZnLi and EtLi. 相似文献
58.
59.
60.
Marina Russo Filomena Cichello Carla Ragonese Paola Donato Francesco Cacciola Paola Dugo Luigi Mondello 《Analytical and bioanalytical chemistry》2013,405(13):4617-4626
In this work, a high-performance liquid chromatography with evaporative light scattering detection method has been developed and applied for quantification of the polar content of the lipid fraction in milk samples of different origin. From a chromatographic stand-point, a 4.6-mm I.D. hydrophilic interaction liquid chromatography column was employed to attain a baseline separation of major phospholipid classes contained in the various milk samples tested. Quantitative analysis was performed by the external calibration method using reference material solutions in the 5–100 mg/L concentration range. Analytical recoveries ranging from 57 to 100 %, and repeatability data lower than 8.04 % were obtained on a skimmed cow’s milk sample. The crude cow milk was the most abundant (0.04 %) in phospholipids and donkey milk was the poorest (0.004 %). Quantitative differences were determined in the phospholipid content of the milk samples tested. Finally, characterization of phospholipid profile and fatty acid composition of the different samples was carried out by an ion trap-time of flight mass spectrometer and gas chromatography coupled to flame ionization and mass spectrometry detection. A thorough screening of the polar lipid composition of milk samples of different origin is here outlined, for the first time. 相似文献