全文获取类型
收费全文 | 1327篇 |
免费 | 81篇 |
国内免费 | 5篇 |
专业分类
化学 | 1082篇 |
晶体学 | 5篇 |
力学 | 10篇 |
数学 | 164篇 |
物理学 | 152篇 |
出版年
2023年 | 14篇 |
2022年 | 6篇 |
2021年 | 31篇 |
2020年 | 41篇 |
2019年 | 36篇 |
2018年 | 21篇 |
2017年 | 11篇 |
2016年 | 43篇 |
2015年 | 47篇 |
2014年 | 49篇 |
2013年 | 71篇 |
2012年 | 90篇 |
2011年 | 100篇 |
2010年 | 63篇 |
2009年 | 48篇 |
2008年 | 75篇 |
2007年 | 110篇 |
2006年 | 99篇 |
2005年 | 95篇 |
2004年 | 76篇 |
2003年 | 63篇 |
2002年 | 49篇 |
2001年 | 15篇 |
2000年 | 13篇 |
1999年 | 10篇 |
1998年 | 5篇 |
1997年 | 10篇 |
1996年 | 12篇 |
1995年 | 9篇 |
1994年 | 6篇 |
1993年 | 5篇 |
1992年 | 9篇 |
1991年 | 7篇 |
1990年 | 14篇 |
1989年 | 12篇 |
1988年 | 4篇 |
1987年 | 5篇 |
1986年 | 6篇 |
1985年 | 6篇 |
1984年 | 8篇 |
1983年 | 1篇 |
1982年 | 4篇 |
1981年 | 2篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 3篇 |
1974年 | 1篇 |
排序方式: 共有1413条查询结果,搜索用时 15 毫秒
1.
Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis 下载免费PDF全文
Dr. Diego Núñez‐Villanueva Dr. M. Ángeles Bonache Laura Lozano Dr. Lourdes Infantes Prof. José Elguero Prof. Ibon Alkorta Prof. M. Teresa García‐López Dr. Rosario González‐Muñiz Dr. Mercedes Martín‐Martínez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2489-2500
Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis. 相似文献
2.
3.
Maldonado-Bustamante Sara Roxana Mondaca-Fernndez Iram Gortares-Moroyoqui Pablo Berg Alex Balderas-Corts Jos de Jess Meza-Montenegro Mara Mercedes Brown-Bojrquez Francisco Arvayo-Enrquez Hctor 《Cellulose (London, England)》2022,29(13):7151-7161
Cellulose - The present study investigates the organosolv treatment of wheat straw, for the optimization of cellulose delignification, which will serve as raw material for the paper industry. The... 相似文献
4.
Shuhao Zhang Mercedes K. Taylor Lingchang Jiang Prof. Hao Ren Prof. Guangshan Zhu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(15):3205-3221
Light hydrocarbons (C1–C3) are used as basic energy feedstocks and as commodity organic compounds for the production of many industrially necessary chemicals. Due to the nature of the raw materials and production processes, light hydrocarbons are generated as mixtures, but the high-purity single-component products are of vital importance to the petrochemical industry. Consequently, the separation of these C1–C3 products is a crucial industrial procedure that comprises a significant share of the total global energy consumption per year. As a complement to traditional separation methods (distillation, partial hydrogenation, etc.), adsorptive separations using porous solids have received widespread attention due to their lower energy costs and higher efficiency. Extensive research has been devoted to the use of porous materials such as zeolites and metal-organic frameworks (MOFs) as solid adsorbents for these key separations, owing to the high porosity, tunable pore structures, and unsaturated metal sites present in these materials. Recently, porous organic framework (POF) materials composed of organic building blocks linked by covalent bonds have also shown excellent properties in light hydrocarbon adsorption and separation, sparking interest in the use of these materials as adsorbents in separation processes. This Minireview summarizes the recent advances in the use of POFs for light hydrocarbon separations, including the separation of mixtures of methane/ethane, methane/propane, ethylene/ethane, acetylene/ethylene, and propylene/propane, while highlighting the relationships between the structural features of these materials and their separation performances. Finally, the difficulties, challenges, and opportunities associated with leveraging POFs for light hydrocarbon separations are discussed to conclude the review. 相似文献
5.
Dr. Ignacio Colomer Dr. Mercedes Ureña Dr. Alma Viso Prof. Roberto Fernández de la Pradilla 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(20):4620-4632
The chemo- and stereocontrolled functionalization of conjugated sulfinyl dienes in a cascade process that involves a conjugate addition, diastereoselective protonation and a [2,3]-sigmatropic rearrangement is reported. Enantioenriched 1,4-diol and 1,4-aminoalcohol derivatives are obtained in a very straightforward manner. Further functionalization of these structures, including highly stereoselective epoxidation, dihydroxylation and the stereodivergent synthesis of several polyols in a controlled fashion is described. 相似文献
6.
Sara Bertuzzi Dr. Ana Gimeno Reyes Núñez-Franco Dr. Ganeko Bernardo-Seisdedos Sandra Delgado Dr. Gonzalo Jiménez-Osés Dr. Oscar Millet Prof. Dr. Jesús Jiménez-Barbero Dr. Ana Ardá 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(67):15643-15653
The interaction of human galectin-1 with a variety of oligosaccharides, from di-(N-acetyllactosamine) to tetra-saccharides (blood B type-II antigen) has been scrutinized by using a combined approach of different NMR experiments, molecular dynamics (MD) simulations, and isothermal titration calorimetry. Ligand- and receptor-based NMR experiments assisted by computational methods allowed proposing three-dimensional structures for the different complexes, which explained the lack of enthalpy gain when increasing the chemical complexity of the glycan. Interestingly, and independently of the glycan ligand, the entropy term does not oppose the binding event, a rather unusual feature for protein-sugar interactions. CLEANEX-PM and relaxation dispersion experiments revealed that sugar binding affected residues far from the binding site and described significant changes in the dynamics of the protein. In particular, motions in the microsecond-millisecond timescale in residues at the protein dimer interface were identified in the presence of high affinity ligands. The dynamic process was further explored by extensive MD simulations, which provided additional support for the existence of allostery in glycan recognition by human galectin-1. 相似文献
7.
Dr. Arianna Melillo Dr. Antonio Franconetti Prof. Dr. Mercedes Alvaro Prof. Dr. Belen Ferrer Prof. Hermenegildo Garcia 《Chemistry (Weinheim an der Bergstrasse, Germany)》2023,29(1):e202202625
Hydrogenation of multiple bonds are among the most general and important organic reactions. Typical heterogeneous catalysts are based on transition metal nanoparticles, including noble metals. Data are presented here showing that metal nodes of MIL-101(Cr) and UiO-66 in the absence of occluded metal nanoparticles can promote hydrogenation of polarized X=Y double bonds of nitro and carbonyl groups. The catalytic activity is a function of the composition of the metal node and the organic linker. It is proposed that the reaction mechanism is based on the operation of frustrated Lewis acid/base pairs. 相似文献
8.
Jorge Labella Dr. Gonzalo Durán-Sampedro Swathi Krishna Prof. M. Victoria Martínez-Díaz Prof. Dirk M. Guldi Prof. Tomás Torres 《Angewandte Chemie (International ed. in English)》2023,62(5):e202214543
Large π-conjugated systems are key in the area of molecular materials. Herein, we prepare via AuI-catalyzed cyclization a series of fully π-conjugated anthracene-fused oligo-BODIPYs. Their structural and optoelectronic properties were studied by several techniques, ranging from X-ray, UV/Vis, and cyclic voltammetry to transient absorption spectroscopy. As a complement, their electronic structures were explored by means of Density Functional Theory (DFT) calculations. Depending on the size and shape of the π-conjugated skeleton, unique features—such as face-to-face supramolecular organization, NIR absorption and fluorescence as well as strong electron accepting character—were noted. All in all, the aforementioned features render them valuable for technological applications. 相似文献
9.
Alberto Concellón Iván Marín Joaquín Barberá Mercedes Marcos José L. Serrano 《Helvetica chimica acta》2023,106(5):e202300010
We have developed a new strategy for the preparation of a light-responsive ionic liquid crystal (LC) that shows photo-switchable proton conduction. The ionic LC consists of a bowl-shaped calix[4]arene core ionically functionalized with azobenzene moieties. The non-covalent architectures were obtained by the formation of ionic salts between the carboxylic acid group of an azo-derivative and the terminal amine groups of a calixarene core. The presence of ionic salts results in a hierarchical self-assembly process that extends to the formation of a nanostructured lamellar LC arrangement (smectic A phase). In this LC phase, the ionic LC calixarene is able to display proton conductive properties, since the ionic nanosegregated areas (formed by the ionic pairs) generate the continuous channels that favor proton transport. The optical and photo-responsive properties were studied by UV-Vis spectroscopy, demonstrating that the azobenzene moieties of the ionic LC undergo reversible (E)-to-(Z) isomerization by irradiation with UV light. Interestingly, this (E)-to-(Z) photoisomerization results in a decrease of the proton conductivity values since the bent-shaped (Z)-isomer disrupts the lamellar LC phase. This isomerization process is totally reversible and leads to an ionic LC material with unique photo-switchable proton conductive properties. 相似文献
10.
Dr. Yanira Méndez Dr. Aldrin V. Vasco Galway Ivey Ana Laura Dias Dr. Peter Gierth Bárbara B. Sousa Dr. Claudio D. Navo Angel Torres-Mozas Dr. Tiago Rodrigues Dr. Gonzalo Jiménez-Osés Prof. Gonçalo J. L. Bernardes 《Angewandte Chemie (International ed. in English)》2023,62(44):e202311186
Multicomponent reactions are of utmost importance at generating a unique, wide, and complex chemical space. Herein we describe a novel multicomponent approach based on the combination of the isonitrile-tetrazine (4+1) cycloaddition and the Ugi four-component reaction to generate pyrazole amide derivatives. The scope of the reaction as well as mechanistic insights governing the 4H-pyrazol-4-imine tautomerization are provided. This multicomponent process provides access to a new chemical space of pyrazole amide derivatives and offers a tool for peptide modification and stapling. 相似文献