全文获取类型
收费全文 | 137840篇 |
免费 | 11573篇 |
国内免费 | 16797篇 |
专业分类
化学 | 103569篇 |
晶体学 | 2073篇 |
力学 | 5394篇 |
综合类 | 1165篇 |
数学 | 16733篇 |
物理学 | 37276篇 |
出版年
2024年 | 257篇 |
2023年 | 1157篇 |
2022年 | 3143篇 |
2021年 | 3175篇 |
2020年 | 3880篇 |
2019年 | 3617篇 |
2018年 | 3205篇 |
2017年 | 4335篇 |
2016年 | 4962篇 |
2015年 | 4337篇 |
2014年 | 5883篇 |
2013年 | 11004篇 |
2012年 | 9058篇 |
2011年 | 8468篇 |
2010年 | 6891篇 |
2009年 | 8784篇 |
2008年 | 8924篇 |
2007年 | 9357篇 |
2006年 | 8340篇 |
2005年 | 7100篇 |
2004年 | 6570篇 |
2003年 | 5530篇 |
2002年 | 6620篇 |
2001年 | 4081篇 |
2000年 | 3783篇 |
1999年 | 3513篇 |
1998年 | 2966篇 |
1997年 | 2446篇 |
1996年 | 2083篇 |
1995年 | 1950篇 |
1994年 | 1716篇 |
1993年 | 1439篇 |
1992年 | 1372篇 |
1991年 | 896篇 |
1990年 | 740篇 |
1989年 | 685篇 |
1988年 | 550篇 |
1987年 | 407篇 |
1986年 | 380篇 |
1985年 | 329篇 |
1984年 | 330篇 |
1983年 | 181篇 |
1982年 | 306篇 |
1981年 | 222篇 |
1980年 | 235篇 |
1979年 | 230篇 |
1978年 | 197篇 |
1977年 | 142篇 |
1976年 | 133篇 |
1973年 | 90篇 |
排序方式: 共有10000条查询结果,搜索用时 47 毫秒
1.
Patrick Imrie Jianyong Jin 《Journal of polymer science. Part A, Polymer chemistry》2022,60(2):149-174
4D printing is an exciting branch of additive manufacturing. It relies on established 3D printing techniques to fabricate objects in much the same way. However, structures which fall into the 4D printed category have the ability to change with time, hence the “extra dimension.” The common perception of 4D printed objects is that of macroscopic single-material structures limited to point-to-point shape change only, in response to either heat or water. However, in the area of polymer 4D printing, recent advancements challenge this understanding. A host of new polymeric materials have been designed which display a variety of wonderful effects brought about by unconventional stimuli, and advanced additive manufacturing techniques have been developed to accommodate them. As a result, the horizons of polymer 4D printing have been broadened beyond what was initially thought possible. In this review, we showcase the many studies which evolve the very definition of polymer 4D printing, and reveal emerging areas of research integral to its advancement. 相似文献
2.
《Mendeleev Communications》2022,32(6):777-779
The reactions of aryllithium reagents o-LiC6H4CH2NR2 with (MeO)2CO afford two new tris(aryl)carbinols bearing pendant-NR2 donor groups in the side chain [o-R NCH C H ] COH [R = Me, R + R = (CH) ]. These alcohols feature helical chirality due to differently inclined aromatic fragments and are presented in a crystalline cell as two M and P enantiomers. Carbinol (R = Me) readily reacts with (Me3SiCH2)3Sc(THF)2 to give a scandium bis(alkyl) complex [(o-C6H4CH2NMe2)3CO]Sc(CH2SiMe3)2 featuring rigid binding of the alkoxy anion through a κ1-O, κ2-N chelating coordination mode 相似文献
3.
Dr. Jordan Donat Mr. Patrick Dubourdeaux Dr. Martin Clémancey Dr. Julia Rendon Clara Gervasoni Mr. Morgan Barbier Jessica Barilone Dr. Jacques Pécaut Prof. Dr. Serge Gambarelli Prof. Dr. Pascale Maldivi Prof. Dr. Jean-Marc Latour 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(70):e202201875
Nitrene transfer reactions have emerged as one of the most powerful and versatile ways to insert an amine function to various kinds of hydrocarbon substrates. However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from FeII and FeIII precursors where the metal is embedded in a tetracarbene macrocycle. Catalytic nitrene transfer to reference substrates (thioanisole, styrene, ethylbenzene and cyclohexane) revealed that the same active species was at play, irrespective of the ferrous versus ferric nature of the precursor. Through combination of spectroscopic (UV-visible, Mössbauer), ESI-MS and DFT studies, an FeIV tosylimido species was identified as the catalytically active species and was characterized spectroscopically and computationally. Whereas its formation from the FeII precursor was expected by a two-electron oxidative addition, its formation from an FeIII precursor was unprecedented. Thanks to a combination of spectroscopic (UV-visible, EPR, Hyscore and Mössbauer), ESI-MS and DFT studies, we found that, when starting from the FeIII precursor, an FeIII tosyliodinane adduct was formed and decomposed into an FeV tosylimido species which generated the catalytically active FeIV tosylimide through a comproportionation process with the FeIII precursor. 相似文献
4.
Dr. Yolimar Gil Dr. Alejandro Castro-Alvarez Dr. Pablo Fuentealba Prof. Evgenia Spodine Dr. Daniel Aravena 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(48):e202200336
Enhancement of axial magnetic anisotropy is the central objective to push forward the performance of Single-Molecule Magnet (SMM) complexes. In the case of mononuclear lanthanide complexes, the chemical environment around the paramagnetic ion must be tuned to place strongly interacting ligands along either the axial positions or the equatorial plane, depending on the oblate or prolate preference of the selected lanthanide. One classical strategy to achieve a precise chemical environment for a metal centre is using highly structured, chelating ligands. A natural approach for axial-equatorial control is the employment of macrocycles acting in a belt conformation, providing the equatorial coordination environment, and leaving room for axial ligands. In this review, we present a survey of SMMs based on the macrocycle belt motif. Literature systems are divided in three families (crown ether, Schiff-base and metallacrown) and their general properties in terms of structural stability and SMM performance are briefly discussed. 相似文献
5.
Jiraya Kiriratnikom Xun Zhang Xiaohan Cao Bo Chu Chengjian Zhang Xinghong Zhang 《Journal of polymer science. Part A, Polymer chemistry》2022,60(15):2262-2268
Facile construction of sulfur-rich polymers using readily available raw chemicals is an area aggressively pursued but challenging. Herein we use common feedstocks of ethylene oxide (EO), propylene oxide (PO), and carbonyl sulfide (COS) to synthesize copoly(thioether)s which are traditionally produced from unpleasant and difficult to store episulfides. In this protocol, the EO/COS coupling selectively generates a pure poly(ethylene sulfide) (PES) with melting temperature (Tm) values up to 172°C and high yields up to 98%. The EO/PO/COS terpolymerization leads to the incorporation of soft poly(propylene sulfide) (PPS) and hard PES segments together, affording a random PES-co-PPS copoly(thioether) with the complete consumption of EO and PO. Additionally, by simply varying the EO/PO feeding ratio, the obtained copoly(thioether)s possess tunable thermal properties, Tm values in the range of 76–144°C, and excellent solubility. These copolymerizations are conducted in one-pot/one-step at industrially favored reaction temperatures of 100–120°C using catalysts of common organic bases, suggesting a facile and practical manner. Especially, the copoly(thioether) exhibits high refractive indices up to 1.68 owing to its high sulfur content, suggesting a broad application prospect in optical materials. 相似文献
6.
Tapasi Chand Laxmikanta Khamari Deepak Chopra Saptarshi Mukherjee Manmohan Kapur 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(43):e202200723
A one-step Rh-catalyzed site-selective ortho-C−H alkynylation of perylene as well as naphthalene mono- and diimides is reported. A single step regioselective access to ortho-C−H alkynylated derivatives of these ryleneimides not only increases the step economy of the ortho-functionalization on these dyes but also provides a quick access route towards highly functionalized dyes that have potential optoelectronic applications. Increased solubility of tetra(triisopropylsilyl)acetylenyl PDIs in organic solvents greatly enhances their utility for further derivatization. 相似文献
7.
Chemical bonding in representative astrophysically relevant neutral,cation, and anion HCnH chains 下载免费PDF全文
Ioan Baldea 《中国物理 B》2022,31(12):123101-123101
Most existing studies assign a polyynic and cumulenic character of chemical bonding in carbon-based chains relying on values of the bond lengths. Building on our recent work, in this paper we add further evidence on the limitations of such an analysis and demonstrate the significant insight gained via natural bond analysis. Presently reported results include atomic charges, natural bond order and valence indices obtained from ab initio computations for representative members of the astrophysically relevant neutral and charged HC2k/2k+1H chain family. They unravel a series of counter-intuitive aspects and/or help naive intuition in properly understanding microscopic processes, e.g., electron removal from or electron attachment to a neutral chain. Demonstrating that the Wiberg indices adequately quantify the chemical bonding structure of the HC2k/2k+1H chains—while the often heavily advertised Mayer indices do not—represents an important message conveyed by the present study. 相似文献
8.
9.
Donglei Wei Huili Li Chuanqing Yang Jianmin Fu Hou Chen Liangjiu Bai Wenxiang Wang Huawei Yang Lixia Yang Ying Liang 《Journal of polymer science. Part A, Polymer chemistry》2022,60(10):1588-1594
Acridone as a new kind of visible light photocatalyst has been developed to catalyze metal free atom transfer radical polymerization (ATRP). The photocatalyst possess low excited state potential as can undergo an oxidative quenching pathway to initiate ATRP of vinyl monomers. Kinetic study and light on/off reaction demonstrate the “living”/controlled nature of the polymerization by light. Block copolymers can be achieved by using PMMA as macroinitiator to reinitiate polymerization of other vinyl monomers, which shows highly preserved Br chain-end functionality in the synthesized polymers. Moreover, the polymerization can be conducted under air atmosphere as most photocatalysts need anaerobic condition, which may give inspiration of further application of this kind of photocatalyst. 相似文献
10.