全文获取类型
收费全文 | 10788篇 |
免费 | 990篇 |
国内免费 | 2279篇 |
专业分类
化学 | 8082篇 |
晶体学 | 318篇 |
力学 | 2053篇 |
综合类 | 54篇 |
数学 | 338篇 |
物理学 | 3212篇 |
出版年
2024年 | 15篇 |
2023年 | 133篇 |
2022年 | 279篇 |
2021年 | 366篇 |
2020年 | 354篇 |
2019年 | 266篇 |
2018年 | 207篇 |
2017年 | 331篇 |
2016年 | 456篇 |
2015年 | 407篇 |
2014年 | 520篇 |
2013年 | 809篇 |
2012年 | 649篇 |
2011年 | 639篇 |
2010年 | 623篇 |
2009年 | 721篇 |
2008年 | 708篇 |
2007年 | 850篇 |
2006年 | 641篇 |
2005年 | 662篇 |
2004年 | 650篇 |
2003年 | 616篇 |
2002年 | 477篇 |
2001年 | 336篇 |
2000年 | 356篇 |
1999年 | 278篇 |
1998年 | 243篇 |
1997年 | 208篇 |
1996年 | 211篇 |
1995年 | 202篇 |
1994年 | 179篇 |
1993年 | 105篇 |
1992年 | 141篇 |
1991年 | 74篇 |
1990年 | 55篇 |
1989年 | 42篇 |
1988年 | 55篇 |
1987年 | 41篇 |
1986年 | 35篇 |
1985年 | 16篇 |
1984年 | 17篇 |
1983年 | 6篇 |
1982年 | 8篇 |
1981年 | 12篇 |
1980年 | 11篇 |
1979年 | 13篇 |
1978年 | 7篇 |
1977年 | 5篇 |
1976年 | 4篇 |
1973年 | 9篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
81.
Margherita Modesti Colleen Szeto Renata Ristic WenWen Jiang Julie Culbert Keren Bindon Cesare Catelli Fabio Mencarelli Pietro Tonutti Kerry Wilkinson 《Molecules (Basel, Switzerland)》2021,26(6)
When bushfires occur near grape growing regions, vineyards can be exposed to smoke, and depending on the timing and duration of grapevine smoke exposure, fruit can become tainted. Smoke-derived volatile compounds, including volatile phenols, can impart unpleasant smoky, ashy characters to wines made from smoke-affected grapes, leading to substantial revenue losses where wines are perceivably tainted. This study investigated the potential for post-harvest ozone treatment of smoke-affected grapes to mitigate the intensity of smoke taint in wine. Merlot grapevines were exposed to smoke at ~7 days post-veraison and at harvest grapes were treated with 1 or 3 ppm of gaseous ozone (for 24 or 12 h, respectively), prior to winemaking. The concentrations of smoke taint marker compounds (i.e., free and glycosylated volatile phenols) were measured in grapes and wines to determine to what extent ozonation could mitigate the effects of grapevine exposure to smoke. The 24 h 1 ppm ozone treatment not only gave significantly lower volatile phenol and volatile phenol glycoside concentrations but also diminished the sensory perception of smoke taint in wine. Post-harvest smoke and ozone treatment of grapes suggests that ozone works more effectively when smoke-derived volatile phenols are in their free (aglycone) form, rather than glycosylated forms. Nevertheless, the collective results demonstrate the efficacy of post-harvest ozone treatment as a strategy for mitigation of smoke taint in wine. 相似文献
82.
采用甘氨酸-硝酸盐法合成了固体氧化物燃料电池阴极材料La2-xBixCuO4(x=0、0.05、0.10),并利用X射线衍射(XRD)对材料的物相进行分析。结果表明,La2-xBixCuO4形成单一的类钙钛矿结构氧化物,且晶胞体积随着铋掺杂量的增加而增大。在950℃烧结24 h过程中,La2-xBixCuO4不与电解质Sm0.2Ce0.8O1.9(SDC)发生反应,表明这种电解质材料具有良好的高温化学相容性。电导率测试结果表明Bi的掺入显著提高了材料电导率。程序升温脱附测试结果表明,铋的掺杂显著增强了材料的表面氧吸附能力。不同氧分压下的交流阻抗谱测试结果表明,La1.9Bi0.1CuO4阴极在700℃空气中的极化电阻为0.26 Ω·cm2,以电解质SDC支撑的单电池NiO-SDC/SDC/La1.90Bi0.10O4在700℃的最大输出功率密度为308 mW·cm-2,电极反应的速控步骤为氧分子的扩散与表面吸附过程。 相似文献
83.
以镍钴氢氧化物、异丙醇铝为原料,采用水解法合成三元前驱体Ni_(0.88)Co_(0.07)Al_(0.05)O_2,再与锂盐混合烧结得到正极材料(TEM)、X射线光电子能谱(XPS)、能量色散X射线谱(EDS)和恒电流充放电测试等对样品的晶体结构、微观形貌、元素价态以及电化学性能进行表征。研究表明,料液比1∶25、水洗3次、600℃回烧2 h合成的LiNi_(0.88)Co_(0.07)Al_(0.05)O_2具有较优的综合电化学性能,其在0.2C的放电比容量达207.6 mAh·g~(-1),首次充放电效率为84.8%,1C放电比容量为192.0 mAh·g~(-1),循环100周后,材料的放电比容量仍有148.0 mAh·g~(-1),容量保持率达到77.1%。 相似文献
84.
Simon Muench René Burges Alexandra Lex-Balducci Johannes C. Brendel Michael Jäger Christian Friebe Andreas Wild Ulrich S. Schubert 《Journal of polymer science. Part A, Polymer chemistry》2021,59(6):494-501
Despite intensive scientific efforts on the development of organic batteries, their full potential is still not being realized. The individual components, such as electrode materials and electrolytes, are in most cases developed independently and are not adjusted to each other. In this context, we report on the performance optimization of a full-organic solid-state battery system by the mutual adaptation of the electrode materials and an ionic liquid (IL)-based gel polymer electrolyte (GPE). The formulation of the latter was designed for a one-step manufacturing approach and can be applied directly to the electrode surface, where it is UV-cured to yield the GPE without further post-treatment steps. Herein, a special focus was placed on the applicability in industrial processes. A first significant capacity increase was achieved by the incorporation of the IL into the electrode composite. Furthermore, the GPE composition was adapted applying acrylate- and methacrylate-based monomers and combinations thereof with the premise of a fast curing step. Furthermore, the amount of IL was varied, and all combinations were evaluated for their final performance in cells. The latter variation revealed that a high ionic conductivity is not the only determining factor for a good cell performance. Next to a sufficient conductivity, the interaction between electrode and electrolyte plays a key role for the cell performance as it enhances the accessibility of the counter ions to the redox-active sites. 相似文献
85.
Gene Senges Dr. Lin Li Dr. Artur Wodyński Dr. Helmut Beckers Dr. Robert Müller Prof. Dr. Martin Kaupp Prof. Dr. Sebastian Riedel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(54):13642-13650
Molecular platinum fluorides PtFn, n=1–6, are prepared by two different routes, photo-initiated fluorine elimination from PtF6 embedded in solid noble-gas matrices, and the reaction of elemental fluorine with laser-ablated platinum atoms. IR spectra of the reaction products isolated in rare-gas matrices under cryogenic conditions provide, for the first time, experimental vibrational frequencies of molecular PtF3, PtF4 and PtF5. Photolysis of PtF6 enabled a highly efficient and almost quantitative formation of molecular PtF4, whereas both PtF5 and PtF3 were formed simultaneously by subsequent UV irradiation of PtF4. The vibrational spectra of these molecular platinum fluorides were assigned with the help of one- and two-component quasirelativistic DFT computation to account for scalar relativistic and spin–orbit coupling effects. Competing Jahn-Teller and spin–orbit coupling effects result in a magnetic bistability of PtF4, for which a spin-triplet (3B2g, D2h) coexists with an electronic singlet state (1A1g, D4h) in solid neon matrices. 相似文献
86.
Guohai Deng Dr. Sudip Pan Dr. Jiaye Jin Prof. Dr. Guanjun Wang Prof. Lili Zhao Prof. Dr. Mingfei Zhou Prof. Gernot Frenking 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(1):412-418
Two structural isomers containing five second-row element atoms with 24 valence electrons were generated and identified by matrix-isolation IR spectroscopy and quantum chemical calculations. The OCBNO complex, which is produced by the reaction of boron atoms with mixtures of carbon monoxide and nitric oxide in solid neon, rearranges to the more stable OBNCO isomer on UV excitation. Bonding analysis indicates that the OCBNO complex is best described by the bonding interactions between a triplet-state boron cation with an electron configuration of (2s)0(2pσ)0(2pπ)2 and the CO/NO− ligands in the triplet state forming two degenerate electron-sharing π bonds and two ligand-to-boron dative σ bonds. 相似文献
87.
Developing ideal IR probes is essential to understand the structure and dynamics of biomolecules with time-resolved IR spectroscopies and imaging techniques. Especially, nitrile (CN) group has recently been proposed to serve as IR probes of the local environment of proteins. Herein, we investigated the effect of a substituent on the vibrational properties of the benzonitrile. The electron-donating and withdrawing character of p-substituent on benzonitrile are expected to modulate the vibrational frequency, molar extinction coefficient, and vibrational lifetime of CN probe. FT-IR revealed the positive correlation between electron-donating character and the molar extinction coefficient of CN stretch mode. Infrared pump-probe (IR-PP) measurements showed that the vibrational lifetime of CN stretch mode exhibits a relatively weak correlation with the electron-donating strength. Among the investigated samples, 4-dimethylamino benzonitrile with the strongest electron-donating strength shows enhanced absorption and extended vibrational lifetime. Utilizing substituent effects will be a practical strategy to improve the performance of the IR probe. 相似文献
88.
89.
Sulfonated carbon dots (SCDs) were synthesized from plant leaves via continuously hydrothermal treatment by hydrogen peroxide and sulfuric acid, used as catalyst for converting fructose to 5-hydroxymethylfurfural (HMF). Owing to nanosize effect and moderate acidic intensity, SCDs could thoroughly distribute in the solvent with an improved interfacial compatibility and selectively convert fructose to HMF. Under the optimal condition, the yield of HMF was 92.6% along with a fructose conversion of 100%, benefiting from a low activation energy of 52.9 kJ/mol when dimethylsulfoxide was used as solvent. The SCDs catalyst can be recovered, after six recycles, the fructose conversion and HMF yield were remained 66.1% and 56.2% under condition with incompletely conversion of fructose, respectively. This work provides a sustainable route to prepare carbon dots with a superior catalytic performance for converting biomass to important biobased platform chemicals. 相似文献
90.
Recent studies on electropolymerization methods toward one-dimensional conducting polymer structures are summarized in this review. In particular, advanced techniques for templated electropolymerization of aromatic monomers, in which migration of monomers into nanopores of the template is highly enhanced by using electrophoretic effect, are described. For templateless approach, electric field–driven bipolar electropolymerization of 3,4-ethylenedioxythiophene monomer is introduced as a strong tool to fabricate the corresponding conducting polymer fibers and films grown in the direction of an applied electric field. 相似文献