全文获取类型
收费全文 | 124159篇 |
免费 | 10165篇 |
国内免费 | 14218篇 |
专业分类
化学 | 84340篇 |
晶体学 | 2069篇 |
力学 | 3993篇 |
综合类 | 1010篇 |
数学 | 17303篇 |
物理学 | 39827篇 |
出版年
2024年 | 170篇 |
2023年 | 951篇 |
2022年 | 2209篇 |
2021年 | 2533篇 |
2020年 | 3098篇 |
2019年 | 2950篇 |
2018年 | 2697篇 |
2017年 | 3817篇 |
2016年 | 4230篇 |
2015年 | 3649篇 |
2014年 | 5182篇 |
2013年 | 9768篇 |
2012年 | 8425篇 |
2011年 | 7606篇 |
2010年 | 6141篇 |
2009年 | 8063篇 |
2008年 | 8376篇 |
2007年 | 8565篇 |
2006年 | 7549篇 |
2005年 | 6343篇 |
2004年 | 5875篇 |
2003年 | 4936篇 |
2002年 | 6079篇 |
2001年 | 3762篇 |
2000年 | 3489篇 |
1999年 | 3246篇 |
1998年 | 2807篇 |
1997年 | 2279篇 |
1996年 | 1920篇 |
1995年 | 1821篇 |
1994年 | 1609篇 |
1993年 | 1287篇 |
1992年 | 1212篇 |
1991年 | 790篇 |
1990年 | 669篇 |
1989年 | 627篇 |
1988年 | 485篇 |
1987年 | 394篇 |
1986年 | 368篇 |
1985年 | 317篇 |
1984年 | 325篇 |
1983年 | 183篇 |
1982年 | 276篇 |
1981年 | 228篇 |
1980年 | 246篇 |
1979年 | 242篇 |
1978年 | 203篇 |
1977年 | 151篇 |
1976年 | 121篇 |
1973年 | 80篇 |
排序方式: 共有10000条查询结果,搜索用时 156 毫秒
1.
《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
2.
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
3.
This paper is concerned with the Cauchy problem on the Boltzmann equation without angular cutoff assumption for hard potential in the whole space. When the initial data is a small perturbation of a global Maxwellian, the global existence of solution to this problem is proved in unweighted Sobolev spaces with . But if we want to obtain the optimal temporal decay estimates, we need to add the velocity weight function, in this case the global existence and the optimal temporal decay estimate of the Boltzmann equation are all established. Meanwhile, we further gain a more accurate energy estimate, which can guarantee the validity of the assumption in Chen et al. (0000). 相似文献
4.
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
5.
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
6.
Chemical bonding in representative astrophysically relevant neutral,cation, and anion HCnH chains
下载免费PDF全文
![点击此处可从《中国物理 B》网站下载免费的PDF全文](/ch/ext_images/free.gif)
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
7.
8.
《Arabian Journal of Chemistry》2022,15(3):103673
In this study, we designed a series of pyrene-based donor-π-donor-π-acceptor compounds (HPTC1-HPTC7) by structural tailoring the reference compound (HPTC) using acceptor units. Nonlinear optical (NLO) properties, frontier molecular orbitals (FMOs), natural bonding orbital (NBO), transition density matric (TDM) analysis, and absorption spectra of reference and proposed derivatives were calculated at M06/6-31G(d,p) functional. All the designed compounds have smaller energy bandgaps than the HPTC compound. Moreover, the designed compounds exhibited larger global softness values than the reference. The absorption maxima of HPTC2, HPTC3, and HPTC7 are blue shifted with respect to HPTC. NBO analysis revealed that prolonged hyper conjugative associations and strong interactions between the donor (π) and acceptor (π*) moieties play a crucial part in their stabilization. The FMO and NBO findings supported the NLO responses of entitled compounds, and consequently, the linear and nonlinear properties of designed derivatives elevate compared to the reference molecule. Promisingly, the NLO response for HPTC7 comprises of highest values of <α>, βtotal and < γ > as 1.92 × 10?22 esu, 1.95 × 10?27 esu, and 4.69 × 107 (a.u). This NLO behavior shows push–pull NLO chromophores for HPTC7 predicting its role in pursuing NLO materials for optoelectronic applications. 相似文献
9.
10.