全文获取类型
收费全文 | 10590篇 |
免费 | 2792篇 |
国内免费 | 1381篇 |
专业分类
化学 | 12493篇 |
晶体学 | 205篇 |
力学 | 87篇 |
综合类 | 45篇 |
数学 | 99篇 |
物理学 | 1834篇 |
出版年
2024年 | 18篇 |
2023年 | 197篇 |
2022年 | 418篇 |
2021年 | 583篇 |
2020年 | 1094篇 |
2019年 | 739篇 |
2018年 | 572篇 |
2017年 | 463篇 |
2016年 | 970篇 |
2015年 | 911篇 |
2014年 | 928篇 |
2013年 | 1137篇 |
2012年 | 945篇 |
2011年 | 758篇 |
2010年 | 561篇 |
2009年 | 542篇 |
2008年 | 494篇 |
2007年 | 514篇 |
2006年 | 428篇 |
2005年 | 381篇 |
2004年 | 373篇 |
2003年 | 312篇 |
2002年 | 204篇 |
2001年 | 146篇 |
2000年 | 150篇 |
1999年 | 103篇 |
1998年 | 128篇 |
1997年 | 99篇 |
1996年 | 92篇 |
1995年 | 80篇 |
1994年 | 77篇 |
1993年 | 38篇 |
1992年 | 52篇 |
1991年 | 44篇 |
1990年 | 46篇 |
1989年 | 35篇 |
1988年 | 16篇 |
1987年 | 11篇 |
1986年 | 22篇 |
1985年 | 17篇 |
1984年 | 20篇 |
1983年 | 9篇 |
1982年 | 12篇 |
1981年 | 9篇 |
1979年 | 5篇 |
1978年 | 2篇 |
1977年 | 3篇 |
1970年 | 1篇 |
1969年 | 1篇 |
1957年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
51.
Rahul S. Patil Dr. Debasis Banerjee Cory M. Simon Prof. Jerry L. Atwood Dr. Praveen K. Thallapally 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(36):12618-12623
Separation of xenon and krypton is of industrial and environmental concern; the existing technologies use cryogenic distillation. Thus, a cost‐effective, alternative technology for the separation of Xe and Kr and their capture from air is of significant importance. Herein, we report the selective Xe uptake in a crystalline porous organic oligomeric molecule, noria, and its structural analogue, PgC‐noria, under ambient conditions. The selectivity of noria towards Xe arises from its tailored pore size and small cavities, which allows a directed non‐bonding interaction of Xe atoms with a large number of carbon atoms of the noria molecular wheel in a confined space. 相似文献
52.
Generation of Oxazolidine‐2,4‐diones Bearing Sulfur‐Substituted Quaternary Carbon Atoms by Oxothiolation/Cyclization of Ynamides 下载免费PDF全文
Hai Huang Junzhen Fan Dr. Guangke He Zhimin Yang Xiaodong Jin Qi Liu Prof. Dr. Hongjun Zhu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(7):2532-2538
A novel method for metal‐free oxothiolation of ynamides to construct oxazolidine‐2,4‐diones bearing sulfur‐substituted quaternary carbon atoms has been developed. It represents a rare C?O bond cleavage of ynamides, as well as a facile and tandem approach for the formation of C?O, C?S, and C?Cl bonds. This redox‐neutral protocol can be applied to the synthesis of multisubstituted oxazolidine‐2,4‐diones with good chemoselectivity and good yields of isolated products under mild conditions. 相似文献
53.
Synchronizing Substrate Activation Rates in Multicomponent Reactions with Metal–Organic Framework Catalysts 下载免费PDF全文
Dr. Lina María Aguirre‐Díaz Dr. Marta Iglesias Dr. Natalia Snejko Prof. Enrique Gutiérrez‐Puebla Prof. M. Ángeles Monge 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(19):6654-6665
A study on the influence of the cation coordination number, number of Lewis acid centers, concurrent existence of Lewis base sites, and structure topology on the catalytic activity of six new indium MOFs, has been carried out for multicomponent reactions (MCRs). The new indium polymeric frameworks, namely [In8(OH)6(popha)6(H2O)4]?3 H2O ( InPF‐16 ), [In(popha)(2,2′‐bipy)]?3 H2O ( InPF‐17 ), [In3(OH)3(popha)2(4,4′‐bipy)]?4 H2O ( InPF‐18 ), [In2(popha)2(4,4′‐bipy)2]?3 H2O ( InPF‐19 ), [In(OH)(Hpopha)]?0.5 (1,7‐phen) ( InPF‐20 ), and [In(popha)(1,10‐phen)]?4 H2O ( InPF‐21 ) (InPF=indium polymeric framework, H3popha=5‐(4‐carboxy‐2‐nitrophenoxy)isophthalic acid, phen=phenanthroline, bipy=bipyridine), have been hydrothermally obtained by using both conventional heating (CH) and microwave (MW) procedures. These indium frameworks show efficient Lewis acid behavior for the solvent‐free cyanosilylation of carbonyl compounds, the one pot Passerini 3‐component (P‐3CR) and the Ugi 4‐component (U‐4CR) reactions. In addition, InPF‐17 was found to be a highly reactive, recyclable, and environmentally benign catalyst, which allows the efficient synthesis of α‐aminoacyl amides. The relationship between the Lewis base/acid active site and the catalytic performance is explained by the 2D seven‐coordinated indium framework of the catalyst InPF‐17 . This study is an attempt to highlight the main structural and synthetic factors that have to be taken into account when planning a new, effective MOF‐based heterogeneous catalyst for multicomponent reactions. 相似文献
54.
Dr. Antonio M. Rodríguez Dr. Pilar Prieto Prof. Antonio de la Hoz Prof. Ángel Díaz-Ortiz D. Raúl Martín Prof. José I. García 《ChemistryOpen》2015,4(3):308-317
The aim of this work was to determine the parameters that have decisive roles in microwave-assisted reactions and to develop a model, using computational chemistry, to predict a priori the type of reactions that can be improved under microwaves. For this purpose, a computational study was carried out on a variety of reactions, which have been reported to be improved under microwave irradiation. This comprises six types of reactions. The outcomes obtained in this study indicate that the most influential parameters are activation energy, enthalpy, and the polarity of all the species that participate. In addition to this, in most cases, slower reacting systems observe a much greater improvement under microwave irradiation. Furthermore, for these reactions, the presence of a polar component in the reaction (solvent, reagent, susceptor, etc.) is necessary for strong coupling with the electromagnetic radiation. We also quantified that an activation energy of 20–30 kcal mol−1 and a polarity (μ) between 7–20 D of the species involved in the process is required to obtain significant improvements under microwave irradiation. 相似文献
55.
Dr. Xiao‐Ye Wang Dr. Jie‐Yu Wang Prof. Jian Pei 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(9):3528-3539
Replacement of C?C unit with its isoelectronic B?N unit in aromatics provides a new class of molecules with appealing properties, which have attracted great attention recently. In this Concept, we focus on BN‐substituted polycyclic aromatics with fused structures, and review their synthesis, photophysical, and redox properties, as well as their applications in organic electronics. We also present challenging synthetic targets, large BN‐ substituted polycyclic aromatics, such as regioregular BN heterosuperbenzenes, which can be viewed as BN‐doped nanographenes. Finally, we propose an atomically precise bottom‐up synthesis of structurally well‐defined BN‐doped graphenes. 相似文献
56.
Enantioselective Template‐Directed [2+2] Photocycloadditions of Isoquinolones: Scope,Mechanism and Synthetic Applications 下载免费PDF全文
Dr. Susannah C. Coote Dr. Alexander Pöthig Prof. Dr. Thorsten Bach 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(18):6906-6912
A strategy for the enantioselective [2+2] photocycloaddition of isoquinolones with alkenes is presented, in which the formation of a supramolecular complex between a chiral template and the substrate ensures high enantioface differentiation by shielding one face of the substrate. Fifteen different electron‐deficient alkenes and ten different substituted isoquinolones undergo efficient photocycloaddition, yielding the cyclobutane products in excellent yields and with outstanding regio‐, diastereo‐ and enantioselectivities (up to 99 % ee). The mechanism of the reaction is investigated by means of triplet sensitization/quenching and radical clock experiments, the results of which are consistent with the involvement of a triplet excited state and a 1,4‐biradical intermediate. The variety of functionalized cyclobutanes obtained using this approach can be further increased by straightforward synthetic transformations of the photoadducts, allowing rapid access to libraries of compounds for various applications. 相似文献
57.
Triggering the Directional Selectivity of a Ring‐Closure Reaction Leads to Pyridoazacarbazoles with Anticancer Properties 下载免费PDF全文
Tamara N. Steinhauer Daniel S. Längle Dr. Christopher Meier Dr. Ulrich Girreser Dr. Lars Stenzel Prof. Dr. Dieter Heber Prof. Dr. Bernd Clement 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(18):6668-6672
We herein describe a facile and versatile synthetic route to the tetracyclic system of 6‐substituted 5,6‐dihydro‐11H‐pyrido[3,2‐i]‐1‐azacarbazoles with promising anticancer properties. These derivatives are built up by an elegant one‐step base‐catalyzed synthetic procedure from commercially available building blocks. One additional step provides the corresponding skeleton hitherto unknown in the literature. The possibility to synthesize a large library of compounds with various substitution patterns utilizing this method underlines the importance of this synthetic procedure. 相似文献
58.
Metal Oxide Assisted Preparation of Core–Shell Beads with Dense Metal–Organic Framework Coatings for the Enhanced Extraction of Organic Pollutants 下载免费PDF全文
Mateo del Rio Dr. Carlos Palomino Cabello Veronica Gonzalez Dr. Fernando Maya Dr. Jose B. Parra Dr. Victor Cerdà Dr. Gemma Turnes Palomino 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(33):11770-11777
Dense and homogeneous metal–organic framework (MOF) coatings on functional bead surfaces are easily prepared by using intermediate sacrificial metal oxide coatings containing the metal precursor of the MOF. Polystyrene (PS) beads are coated with a ZnO layer to give ZnO@PS core–shell beads. The ZnO@PS beads are reactive in the presence of 2‐methylimidazole to transform part of the ZnO coating into a porous zeolitic imidazolate framework‐8 (ZIF‐8) external shell positioned above the internal ZnO precursor shell. The obtained ZIF‐8@ZnO@PS beads can be easily packed in column format for flow‐through applications, such as the solid‐phase extraction of trace priority‐listed environmental pollutants. The prepared material shows an excellent permeance to flow when packed as a column to give high enrichment factors, facile regeneration, and excellent reusability for the extraction of the pollutant bisphenol A. It also shows an outstanding performance for the simultaneous enrichment of mixtures of endocrine disrupting chemicals (bisphenol A, 4‐tert‐octylphenol and 4‐n‐nonylphenol), facilitating their analysis when present at very low levels (<1 μg L?1) in drinking waters. For the extraction of the pollutant bisphenol A, the prepared ZIF‐8@ZnO@PS beads also show a superior extraction and preconcentration capacity to that of the PS beads used as precursors and the composite materials obtained by the direct growth of ZIF‐8 on the surface of the PS beads in the absence of metal oxide intermediate coatings. 相似文献
59.
Adrian Tlahuext‐Aca Dr. Matthew N. Hopkinson R. Aleyda Garza‐Sanchez Prof. Dr. Frank Glorius 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(17):5909-5913
Highly selective tandem nucleophilic addition/cross‐coupling reactions of alkynes have been developed using visible‐light‐promoted dual gold/photoredox catalysis. The simultaneous oxidation of AuI and coordination of the coupling partner by photo‐generated aryl radicals, and the use of catalytically inactive gold precatalysts allows for high levels of selectivity for the cross‐coupled products without competing hydrofunctionalization or homocoupling. As demonstrated in representative arylative Meyer–Schuster and hydration reactions, this work expands the scope of dual gold/photoredox catalysis to the largest class of substrates for gold catalysts and benefits from the mild and environmentally attractive nature of visible‐light activation. 相似文献
60.
Single Crystal to Single Crystal (SC‐to‐SC) Transformation from a Nonporous to Porous Metal–Organic Framework and Its Application Potential in Gas Adsorption and Suzuki Coupling Reaction through Postmodification 下载免费PDF全文
Dr. Rupam Sen Debraj Saha Dr. Subratanath Koner Dr. Paula Brandão Dr. Zhi Lin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(15):5962-5971
A new amino‐functionalized strontium–carboxylate‐based metal–organic framework (MOF) has been synthesized that undergoes single crystal to single crystal (SC‐to‐SC) transformation upon desolvation. Both structures have been characterized by single‐crystal X‐ray analysis. The desolvated structure shows an interesting 3D porous structure with pendent ?NH2 groups inside the pore wall, whereas the solvated compound possesses a nonporous structure with DMF molecules on the metal centers. The amino group was postmodified through Schiff base condensation by pyridine‐2‐carboxaldehyde and palladium was anchored on that site. The modified framework has been utilized for the Suzuki cross‐coupling reaction. The compound shows high activity towards the C?C cross‐coupling reaction with good yields and turnover frequencies. Gas adsorption studies showed that the desolvated compound had permanent porosity and was microporous in nature with a BET surface area of 2052 m2 g?1. The material also possesses good CO2 (8 wt %) and H2 (1.87 wt %) adsorption capabilities. 相似文献