全文获取类型
收费全文 | 2497篇 |
免费 | 554篇 |
国内免费 | 92篇 |
专业分类
化学 | 2587篇 |
晶体学 | 15篇 |
力学 | 148篇 |
综合类 | 3篇 |
数学 | 31篇 |
物理学 | 359篇 |
出版年
2024年 | 5篇 |
2023年 | 35篇 |
2022年 | 86篇 |
2021年 | 86篇 |
2020年 | 184篇 |
2019年 | 104篇 |
2018年 | 103篇 |
2017年 | 67篇 |
2016年 | 226篇 |
2015年 | 196篇 |
2014年 | 180篇 |
2013年 | 190篇 |
2012年 | 152篇 |
2011年 | 159篇 |
2010年 | 118篇 |
2009年 | 167篇 |
2008年 | 156篇 |
2007年 | 148篇 |
2006年 | 141篇 |
2005年 | 86篇 |
2004年 | 102篇 |
2003年 | 85篇 |
2002年 | 39篇 |
2001年 | 34篇 |
2000年 | 46篇 |
1999年 | 29篇 |
1998年 | 32篇 |
1997年 | 25篇 |
1996年 | 21篇 |
1995年 | 16篇 |
1994年 | 13篇 |
1993年 | 16篇 |
1992年 | 10篇 |
1991年 | 12篇 |
1990年 | 8篇 |
1989年 | 5篇 |
1988年 | 14篇 |
1987年 | 5篇 |
1985年 | 10篇 |
1984年 | 2篇 |
1982年 | 4篇 |
1981年 | 2篇 |
1978年 | 2篇 |
1976年 | 2篇 |
1975年 | 3篇 |
1974年 | 3篇 |
1973年 | 2篇 |
1969年 | 2篇 |
1968年 | 1篇 |
1967年 | 2篇 |
排序方式: 共有3143条查询结果,搜索用时 15 毫秒
11.
Graphene has attracted increasing attention in multidisciplinary studies because of its unique physical and chemical properties. Herein, the adsorption of polycyclic aromatic hydrocarbons (PAHs), such as naphthalene (NAP), anthracene (ANT), and pyrene (PYR), on reduced graphene oxides (rGOs) and graphene oxides (GOs) as a function of pH, humic acid (HA), and temperature were elucidated by means of a batch technique. For comparison, nonpolar and nonporous graphite were also employed in this study. The increasing of pH from 2 to 11 did not influence the adsorption of PAHs on rGOs, whereas the suppressed adsorption of NAP on rGOs was observed both in the presence of HA and under high‐temperature conditions. Adsorption isotherms of PAHs on rGOs were in accordance with the Polanyi–Dubinin–Ashtahhov (PDA) model, providing evidence that pore filling and flat surface adsorption were involved. The saturated adsorbed capacities (in mmol g?1) of rGOs for PAHs calculated from the PDA model significantly decreased in the order of NAP>PYR>ANT, which was comparable to the results of theoretical calculations. The pore‐filling mechanism dominates the adsorption of NAP on rGOs, but the adsorption mechanisms of ANT and PYR on rGOs are flat surface adsorption. 相似文献
12.
Dr. Meiling Guo Prof. Dr. Zhaochi Feng Dr. Jan P. Hofmann Prof. Dr. Bert M. Weckhuysen Dr. Fengtao Fan Prof. Dr. Can Li 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(42):14200-14204
Microporous vanadosilicates with octahedral VO6 and tetrahedral SiO4 units, better known as AM‐6, have been hydrothermally synthesized with different morphologies by controlling the Na/K molar ratio of the initial gel mixtures. The morphology of the AM‐6 materials changed from bulky cube to nanofiber aggregates as the Na/K molar ratio decreased from 1.9 to 0.2. Raman spectroscopy revealed that the VO3? intermediate species plays an important role in the formation of the nanofiber morphology. The orientation of ‐V‐O‐V‐ chains in nanofiber aggregates was examined by confocal polarized micro‐Raman spectroscopy. It was found that these aggregates are assemblies of short ‐V‐O‐V‐ chains perpendicular to the axis of nanofibers. The obtained AM‐6 nanofibers greatly increase the exposed proportion of V? O terminals, and thus improve the catalytic performance. 相似文献
13.
Activated sludge was tested for its ability to remove Cu2+ from aqueous solution. The effects of various experimental parameters (initial pH, initial Cu2+ concentration, adsorbent dosage, and temperature) on Cu2+ adsorption were evaluated. The Langmuir isotherm model well described the adsorption of Cu2+ onto activated sludge. The pseudo-second-order kinetic equation was appropriate for describing the kinetic performance of the sorption. Furthermore, Webber–Morris models indicated that the sorption of Cu2+ was generally found to involve with the intraparticle diffusion process. Parameters of adsorption thermodynamic suggested that the interaction of Cu2+ adsorbed by sludge was spontaneous and exothermic. Activated sludge was characterized by Fourier transform infrared spectroscopy analysis and results showed that active groups such as –OH, –COOH, –NH2 were involved in Cu2+ adsorption. Zeta potential analysis demonstrated inner-sphere adsorption for Cu2+ adsorption on sludge. 相似文献
14.
15.
Dr. Dominikus Heift Dr. Zoltán Benkő Prof. Dr. Hansjörg Grützmacher 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(36):11326-11330
Unsaturated phosphorus compounds, such as phosphaalkenes and phosphaalkynes, show a versatile reactivity in cycloadditions. Although phosphaketenes (R?P?C?O) have been known for three decades, their chemistry has remained limited. Herein, we show that heteroatom‐substituted phosphaketenes, R3E?P?C?O (E=Si, Sn), are building blocks for silyl‐ and stannyl‐substituted five‐membered heterocycles containing three phosphorous atoms. The structure of the heterocyclic anion depends on the nature of the tetrel atom involved. Although the silyl analogue [P3C2(OSiR3)2]? is an aromatic 1,2,4‐triphospholide, the stannyl compound [P(CO)2(PSnR3)2]? is a 1,2,4‐triphosphacyclopenta‐3,5‐dionate with a delocalized OCPCO fragment. Because of their anionic character, these compounds can easily be used as building blocks, for example, in the preparation of a silyl‐functionalized hexaphosphaferrocene or the parent 1,2,4‐triphosphacyclopenta‐3,5‐dionate [P(CO)2(PH)2]?. NMR spectroscopic investigations and computations have shown that the heterocycle‐formation reactions presented herein are remarkably complex. 相似文献
16.
Combining Experimental and Computational Studies to Understand and Predict Reactivities of Relevance to Homogeneous Catalysis 下载免费PDF全文
Dr. Althea S.‐K. Tsang Italo A. Sanhueza Prof. Dr. Franziska Schoenebeck 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(50):16432-16441
This article showcases three major uses of computational chemistry in reactivity studies: the application after, in combination with, and before experiment. Following a brief introduction of suitable computational tools, challenges and opportunities in the implementation of computational chemistry in reactivity studies are discussed, exemplified with selected case studies from our and other laboratories. 相似文献
17.
Exceedingly Fast Copper(II)‐Promoted ortho CH Trifluoromethylation of Arenes using TMSCF3 下载免费PDF全文
Ming Shang Shang‐Zheng Sun Dr. Hong‐Li Wang Dr. Brian N. Laforteza Prof. Dr. Hui‐Xiong Dai Prof. Dr. Jin‐Quan Yu 《Angewandte Chemie (International ed. in English)》2014,53(39):10439-10442
The direct ortho‐trifluoromethylation of arenes, including heteroarenes, with TMSCF3 has been accomplished by a copper(II)‐promoted C? H activation reaction which completes within 30 minutes. Mechanistic investigations are consistent with the involvement of C? H activation, rather than a simple electrophilic aromatic substitution (SEAr), as the key step. 相似文献
18.
Jennifer Paola Hernández Mancera Francisco Núñez-Zarur Soledad Gutiérrez-Oliva Alejandro Toro-Labbé Ricardo Vivas-Reyes 《Journal of computational chemistry》2020,41(23):2022-2032
Quantum chemical calculations were used to study the mechanism of Diels-Alder reactions involving chiral anthracenes as dienes and a series of dienophiles. The reaction force analysis was employed to obtain a detailed scrutiny of the reaction mechanisms, it has been found that thermodynamics and kinetics of the reactions are quite consistent: the lower the activation energy, the lower the reaction energy, thus following the Bell-Evans-Polanyi principle. It has been found that activation energies are mostly due to structural rearrangements that in most cases represented more than 70% of the activation energy. Electronic activity mostly due to changes in σ and π bonding were revealed by the reaction electronic flux (REF), this property helps identify whether changes on σ or π bonding drive the reaction. Additionally, new global indexes describing the behavior of the electronic activity were introduced and then used to classify the reactions in terms of the spontaneity of their electronic activity. Local natural bond order electronic population analysis was used to check consistency with global REF through the characterization of specific changes in the electronic density that might be responsible for the activity already detected by the REF. Results show that reactions involving acetoxy lactones are driven by spontaneous electronic activity coming from bond forming/strengthening processes; in the case of maleic anhydrides and maleimides it appears that both spontaneous and non-spontaneous electronic activity are quite active in driving the reactions. 相似文献
19.
Tzu‐Yu Chen Jinfeng Chen Yijie Tang Jiahai Zhou Yisong Guo Wei‐chen Chang 《Angewandte Chemie (International ed. in English)》2020,59(19):7367-7371
N‐alkylisonitrile, a precursor to isonitrile‐containing lipopeptides, is biosynthesized by decarboxylation‐assisted ‐N≡C group (isonitrile) formation by using N‐alkylglycine as the substrate. This reaction is catalyzed by iron(II) and 2‐oxoglutarate (Fe/2OG) dependent enzymes. Distinct from typical oxygenation or halogenation reactions catalyzed by this class of enzymes, installation of the isonitrile group represents a novel reaction type for Fe/2OG enzymes that involves a four‐electron oxidative process. Reported here is a plausible mechanism of three Fe/2OG enzymes, Sav607, ScoE and SfaA, which catalyze isonitrile formation. The X‐ray structures of iron‐loaded ScoE in complex with its substrate and the intermediate, along with biochemical and biophysical data reveal that ‐N≡C bond formation involves two cycles of Fe/2OG enzyme catalysis. The reaction starts with an FeIV‐oxo‐catalyzed hydroxylation. It is likely followed by decarboxylation‐assisted desaturation to complete isonitrile installation. 相似文献
20.