全文获取类型
收费全文 | 320篇 |
免费 | 10篇 |
国内免费 | 88篇 |
专业分类
化学 | 367篇 |
晶体学 | 3篇 |
力学 | 6篇 |
综合类 | 3篇 |
数学 | 1篇 |
物理学 | 38篇 |
出版年
2023年 | 17篇 |
2022年 | 14篇 |
2021年 | 15篇 |
2020年 | 21篇 |
2019年 | 16篇 |
2018年 | 10篇 |
2017年 | 16篇 |
2016年 | 9篇 |
2015年 | 11篇 |
2014年 | 17篇 |
2013年 | 20篇 |
2012年 | 29篇 |
2011年 | 27篇 |
2010年 | 25篇 |
2009年 | 33篇 |
2008年 | 22篇 |
2007年 | 20篇 |
2006年 | 18篇 |
2005年 | 29篇 |
2004年 | 6篇 |
2003年 | 7篇 |
2002年 | 7篇 |
2001年 | 2篇 |
2000年 | 9篇 |
1999年 | 2篇 |
1998年 | 3篇 |
1997年 | 1篇 |
1996年 | 2篇 |
1995年 | 4篇 |
1993年 | 1篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1984年 | 1篇 |
1976年 | 1篇 |
排序方式: 共有418条查询结果,搜索用时 31 毫秒
1.
Chanjuan Zhang Dr. Philipp Gotico Dr. Regis Guillot Dr. Diana Dragoe Dr. Winfried Leibl Dr. Zakaria Halime Prof. Ally Aukauloo 《Angewandte Chemie (International ed. in English)》2023,62(8):e202300926
At the core of carbon monoxide dehydrogenase (CODH) active site two metal ions together with hydrogen bonding scheme from amino acids orchestrate the interconversion between CO2 and CO. We have designed a molecular catalyst implementing a bimetallic iron complex with an embarked second coordination sphere with multi-point hydrogen-bonding interactions. We found that, when immobilized on carbon paper electrode, the dinuclear catalyst enhances up to four fold the heterogeneous CO2 reduction to CO in water with an improved selectivity and stability compared to the mononuclear analogue. Interestingly, quasi-identical catalytic performances are obtained when one of the two iron centers was replaced by a redox inactive Zn metal, questioning the cooperative action of the two metals. Snapshots of X-ray structures indicate that the two metalloporphyrin units tethered by a urea group is a good compromise between rigidity and flexibility to accommodate CO2 capture, activation, and reduction. 相似文献
2.
Dr. Debayan Roy Dr. Beeraiah Baire 《Angewandte Chemie (International ed. in English)》2023,62(27):e202304557
The cyclodimerization (homochiral- and heterochiral−) of monomeric units for the construction of stereodefined polycyclic systems is a powerful strategy in both biosynthesis and biomimetic synthesis. Herein we have discovered and developed a CuII- catalyzed, biomimetic, diastereoselective tandem cycloisomerization-[3+2] cyclodimerization of 1-(indol-2-yl)pent-4-yn-3-ol. This novel strategy operates under very mild conditions, providing access to structurally unprecedented dimeric tetrahydrocarbazoles fused to a tetrahydrofuran unit in excellent yields of the products. Several fruitful control experiments, isolation of the monomeric-cycloisomerized products and their subsequent conversion into the corresponding cyclodimeric products supported their intermediacy and the possible mechanism as a cycloisomerization-diastereoselective [3+2] cyclodimerization cascade. The cyclodimerization involves a substituent controlled, highly diastereoselective homochiral [3+2] annulation or heterochiral [3+2] annulation of in situ generated 3-hydroxytetrahydrocarbazoles. The key and important features of this strategy are: a) construction of three new C−C bonds & one new C−O bond; b) creation of two new stereocenters, and c) construction of three new rings, in a single operation; d) low catalyst loading (1–5 mol %); e) 100 % atom economy; and f) rapid construction of structurally unprecedented natural product like polycyclic frameworks. A chiral pool version using an enantio- and diastereopure substrate was also demonstrated. 相似文献
3.
Wen-Li Zhou Hai-Bo Tan Sheng-Xiang Qiu Guang-Ying Chen Hong-Xin Liu Chao Zheng 《Tetrahedron letters》2017,58(19):1817-1821
A confirmed structure of meroterpenoid myrtucommulone K, which is vastly different from the originally reported one, is conducted. The first biomimetic total synthesis towards the assignment of its absolute configuration has been efficiently accessed in 5 steps, and key to the success was a heteroatom Diels-Alder cycloaddition. The structure of myrtucommulone K was re-elucidated and confirmed by extensive spectroscopic interpretation of 1D and 2D NMR. 相似文献
4.
Here, agar hydrogel was selected as diffusion medium and template to control the biomimetic mineralization of calcium carbonate (CaCO3). Due to three dimensional network structures and abundant functional groups (such as, hydroxyl groups), Ca2+ ions were uniformly distributed in the network and electrostatically attracted. The diffusion speed and range of CO32? ions were mediated by the concentration of hydrogel medium. Under the synergistic effect of Mg2+ ions, the crystal CaCO3 was induced by gas phase diffusion method in the hydrogel system. The results showed that the concentrations of Mg2+ ions and agar hydrogel had no obvious effect on the calcite phase of CaCO3, but the morphologies and sizes changed with concentrations of medium and Mg2+ ions. Attribute to template effect, the crystallization behavior and growth rate of CaCO3 crystals were regulated. Since Mg2+ ions were easily adsorbed on the surfaces of unit cell, the unique structure of CaCO3 was precisely controlled. This study provides a useful reference and inspiration for the understandings of the contributions of ion supply rate in bio-mineralization and hydrogel medium in biomimetic mineralization. 相似文献
5.
Natural cellulose substances have been proven to be ideal structural templates and scaffolds for the fabrication of artificial functional materials with designed structures, psychochemical properties and functionalities. They possess unique hierarchically porous network structures with flexible, biocompatible, and environmental characteristics, exhibiting great potentials in the preparation of energy-related materials. This minireview summarizes natural cellulose-based materials that are used in batteries, supercapacitors, photocatalytic hydrogen generation, photoelectrochemical cells, and solar cells. When natural cellulose substances are employed as the structural template or carbon sources of energy materials, the three-dimensional porous interwoven structures are perfectly replicated, leading to the enhanced performances of the resultant materials. Benefiting from the mechanical strengths of natural cellulose substances, wearable, portable, free-standing, and flexible materials for energy storage and conversion are easily obtained by using natural cellulose substances as the substrates. 相似文献
6.
A new family of organocatalysts based on aminoquinoline and pyrrolidine have been developed and shown to catalyze the direct and highly enantioselective cyclization of 2′-hydroxychalcones in imitation of the natural process of chalcone cyclization. The straightforward synthetic process occurs under mild reaction conditions, tolerates moisture and air, and gives an enantiomeric excess up to 99%. This approach provides a facile and efficient access to chiral flavanones. 相似文献
7.
《Helvetica chimica acta》2017,100(9)
Here we report the direct chemical synthesis of coenzyme B12 (AdoCbl) from Coβ ‐5′‐deoxyadenosylcobyric acid (AdoCby) and the preparation of the latter from crystalline CN ,H2O‐cobyric acid (CN ,H2OC by). AdoCby is a suggested common key intermediate in the biosynthesis of AdoCbl and of other cobamides in microorganisms. AdoCby was thoroughly characterized by spectroscopic means, including homo‐nuclear and hetero‐nuclear NMR , as such data are not available in published work. AdoCbl was prepared from AdoCby in one‐step in over 85% yield, by covalent attachment in aqueous solution of the integral B12‐nucleotide moiety using 1‐ethyl‐3‐(3‐dimethylaminopropyl)‐carbodiimide (EDC ·HC l) and N‐hydroxybenzotriazole (HOB t) as coupling reagents. By the same procedure crystalline vitamin B12 (CNC bl) was also prepared in 92% yield from CN ,H2OC by. Coordination of the B12‐nucleotide base at the Coα ‐face of AdoCby or of CN ,H2OC by was indicated to assist in the efficient covalent coupling at the activated f‐side chain function to furnish the complete corrinoids AdoCbl and CNC bl. 相似文献
8.
In living organisms, many biological processes are inextricably linked with light, such as the photosynthesis systems and rhodopsin. Hence, construction of light-sensitive biomimetic-nanochannels, which can realize the functions of cells and other membrane structures with high degree of spatial and temporal control, is particularly attractive and challenging. As a cornerstone of light-sensitive nanochannels, the photoresponsive materials are a big family and at their mature stage after several decades of development, which can provide different strategies to construct biomimetic photoresponsive nanochannels. In this review, we mainly summarize the construction and applications of photoresponsive nanochannels on the basis of various photoresponsive materials. The construction of photoresponsive nanochannels can be classified into four categories: photoresponsive inorganic nanochannels based on inorganic-compound-based photonic sensitive materials; photoresponsive organic nanochannels based on organic-compound-based photonic sensitive materials; photoresponsive polymers nanochannel based on photoresponsive polymers materials and potential photoresponsive nanochannels based on other photoresponsive materials. After introducing the construction of photoresponsive nanochannels, the review highlights some of the most recent applications of photoresponsive nanochannels in separation, energy conversion and storage, drug delivery and so on. 相似文献
9.
10.
在细胞和分子水平上,研究了稀土化合物氯化铽(TbCl3)对成骨细胞MC3T3-E1增殖、分化及矿化功能的影响。结果表明,细胞水平上,浓度为0.0001、0.001、0.01、0.1、1和10 μmol·L-1的TbCl3均促进MC3T3-E1细胞的增殖、分化及其矿化功能,然而,当浓度升至为100和1000 μmol·L-1时,TbCl3表现出抑制作用。分子水平上,浓度为0.0001和0.1 μmol·L-1的TbCl3明显上调成骨分化相关基因骨形成蛋白2(BMP-2),碱性磷酸酶(ALP),骨涎蛋白(BSP),Ⅰ型胶原蛋白(Col Ⅰ),骨钙素(OCN)和runt 相关转录因子2(Runx2)的表达。浓度为1 000 μmol·L-1的TbCl3则抑制上述成骨分化相关基因的表达。浓度为0.000 1、0.1和1 μmol·L-1的TbCl3促进成骨分化相关蛋白Runx2,BMP-2和OCN的表达;结果显示,低浓度的TbCl3促进MC3T3-E1细胞的成骨分化及矿化功能,而高浓度TbCl3则呈现出抑制作用。TbCl3通过调控Runx2的表达刺激早期成骨分化相关基因BMP-2、Col Ⅰ和晚期成骨分化相关基因ALP、OCN的表达,从而诱导MC3T3-E1成骨分化。 相似文献