全文获取类型
收费全文 | 19801篇 |
免费 | 3738篇 |
国内免费 | 2506篇 |
专业分类
化学 | 15824篇 |
晶体学 | 210篇 |
力学 | 753篇 |
综合类 | 311篇 |
数学 | 2208篇 |
物理学 | 6739篇 |
出版年
2024年 | 39篇 |
2023年 | 272篇 |
2022年 | 515篇 |
2021年 | 989篇 |
2020年 | 1029篇 |
2019年 | 777篇 |
2018年 | 623篇 |
2017年 | 776篇 |
2016年 | 1069篇 |
2015年 | 921篇 |
2014年 | 1175篇 |
2013年 | 1879篇 |
2012年 | 1353篇 |
2011年 | 1183篇 |
2010年 | 1076篇 |
2009年 | 1190篇 |
2008年 | 1231篇 |
2007年 | 1304篇 |
2006年 | 1160篇 |
2005年 | 1007篇 |
2004年 | 963篇 |
2003年 | 919篇 |
2002年 | 693篇 |
2001年 | 541篇 |
2000年 | 503篇 |
1999年 | 423篇 |
1998年 | 372篇 |
1997年 | 291篇 |
1996年 | 272篇 |
1995年 | 274篇 |
1994年 | 252篇 |
1993年 | 180篇 |
1992年 | 152篇 |
1991年 | 92篇 |
1990年 | 78篇 |
1989年 | 76篇 |
1988年 | 57篇 |
1987年 | 42篇 |
1986年 | 52篇 |
1985年 | 56篇 |
1984年 | 37篇 |
1983年 | 9篇 |
1982年 | 18篇 |
1981年 | 29篇 |
1980年 | 23篇 |
1979年 | 16篇 |
1978年 | 9篇 |
1977年 | 13篇 |
1976年 | 6篇 |
1975年 | 11篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
81.
Yuto Kurasaki Yasuhito Suzuki Akikazu Matsumoto 《Journal of polymer science. Part A, Polymer chemistry》2020,58(7):923-931
We carried out the thermal curing of the copolymers of N-allylmaleimide (AMI) and 2-ethylhexyl acrylate (2EHA) using 1,3,4,6-tetra(2-mercaproethyl)glycoluril ( G1 ), 1,3,4,6-tetra(3-mercaptopropyl)glycoluril ( G2 ), 1,3,4,6-tetraallylglycoluril ( G3 ), triallylisocyanurate (TAIC), and pentaerythritol tetrakis(3-mercaptobutyrate) (PEMB) as the crosslinkers. Based on the results for the analysis of thiol–ene reactions monitored by IR spectroscopy, it was confirmed that the curing rate significantly depended on the combination of the used crosslinkers. The insoluble fraction after curing was more than 90% for the systems using the glycoluril crosslinkers, while the conversion of the allyl groups was suppressed due to the rigid structure of these crosslinkers. The heat resistance and the mechanical properties of the crosslinked polymers were investigated by thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis, and mechanical tensile tests. For the products cured using the glycoluril crosslinkers, the glass transition temperature (Tg) and the maximum temperature of thermal decomposition (Tmax) were 54–59 °C and 395–409 °C, respectively, being higher than those for the cured product prepared with PEMB and TAIC as the conventional crosslinkers. The elasticity (75–139 MPa), the maximum strength (3.0–4.1 MPa), and the adhesion strength (6.7–10.7 MPa) for the polymers cured with the glycoluril crosslinkers, determined by the mechanical tensile and single lap-shear adhesion tests, were higher than those for cured materials produced with PEMB. Thus, the thermal and mechanical properties of the maleimide copolymers were efficiently enhanced by crosslinking using the rigid glycoluril compounds. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 923–931 相似文献
82.
Ali Pourjavadi Maryam Tavakolizadeh Seyed Hassan Hosseini Navid Rabiee Mojtaba Bagherzadeh 《Journal of polymer science. Part A, Polymer chemistry》2020,58(15):2062-2073
A number of synthetic hydrogels suffer from low mechanical strength. Despite of the recent advances in the fabrication of tough hydrogels, it is still a great challenge to simultaneously construct high stretchability, and self-adhesive and self-healing capability in a hydrogel. Herein, a new type of double network hydrogel was prepared based on irreversible cross-linking of polyacrylamide chains and Schiff-base reversible cross-linking between glycidyl methacrylate-grafted ethylenediamine and oxidized sodium alginate (OSA). The combination of both cross-linkings and their synergistic effect provided a novel hydrogel with high strength, stretchable, rapid self-healing, and self-adhesiveness to different material. Besides, the hydrogels with diverse OSA content could maintain their original shapes after loading–unloading tensile test. The resulting hydrogel has a great potential in various fields for supporting and load-bearing substance. 相似文献
83.
Yingjian Yu Dr. Bin Meng Prof. Dr. Frieder Jäkle Prof. Jun Liu Prof. Lixiang Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(4):873-880
Triarylboranes that exhibit p–π* conjugation serve as versatile building blocks to design n-type organic/polymer semiconductors. A series of new molecular acceptors based on triarylborane is reported here. These molecules are designed with a boron atom that bears a bulky 2,4,6-tri-tert-butylphenyl (Mes*) substituent at the core and strong electron-withdrawing 2-(3-oxo-2,3-dihydroinden-1-ylidene)malononitrile (IC) units as the end-capping groups that are linked to the core by bithiophene bridges. Butyl or butoxy groups are introduced to the bithiophene units to tune the optoelectronic properties. These molecules show nearly planar backbones with highly localized steric hindrance at the core, low LUMO/HOMO energy levels, and broad absorption bands spanning the visible region, which are all very desirable characteristics for use as electron acceptors in organic solar cell (OSC) applications. The attachment of butyl groups to the bithiophene bridges brings about a slightly twisted backbone, which in turn promotes good solubility and homogeneous donor/acceptor blend morphology, whereas the introduction of butoxy groups leads to improved planarity, favorable stacking in the film state, and a greatly reduced band gap. OSC devices based on these molecules exhibit encouraging photovoltaic performances with power conversion efficiencies reaching up to 4.07 %. These results further substantiate the strong potential of triarylboranes as the core unit of small molecule acceptors for OSC applications. 相似文献
84.
Dr. David Scheerer Prof. Dr. Heng Chi Dr. Dan McElheny Prof. Dr. Timothy A. Keiderling Prof. Dr. Karin Hauser 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(16):3524-3534
Site-specific isotopic labeling of molecules is a widely used approach in IR spectroscopy to resolve local contributions to vibrational modes. The induced frequency shift of the corresponding IR band depends on the substituted masses, as well as on hydrogen bonding and vibrational coupling. The impact of these different factors was analyzed with a designed three-stranded β-sheet peptide and by use of selected 13C isotope substitutions at multiple positions in the peptide backbone. Single-strand labels give rise to isotopically shifted bands at different frequencies, depending on the specific sites; this demonstrates sensitivity to the local environment. Cross-strand double- and triple-labeled peptides exhibited two resolved bands that could be uniquely assigned to specific residues, the equilibrium IR spectra of which indicated only weak local-mode coupling. Temperature-jump IR laser spectroscopy was applied to monitor structural dynamics and revealed an impressive enhancement of the isotope sensitivity to both local positions and coupling between them, relative to that of equilibrium FTIR spectroscopy. Site-specific relaxation rates were altered upon the introduction of additional cross-strand isotopes. Likewise, the rates for the global β-sheet dynamics were affected in a manner dependent on the distinct relaxation behavior of the labeled oscillator. This study reveals that isotope labels provide not only local structural probes, but rather sense the dynamic complexity of the molecular environment. 相似文献
85.
Yusuke Tanaka Tomotaka Murayama Dr. Atsuya Muranaka Dr. Eiyu Imai Prof. Dr. Masanobu Uchiyama 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(8):1768-1771
We designed and synthesized a new type of small helical molecule exhibiting intense circularly polarized luminescence (CPL) ( 12H ) by modifying a 20π-electron hemiporphyrazine with a large transition magnetic dipole moment. The hemiporphyrazine ring was opened and one additional pyridine unit was introduced, resulting in an overlap of two pyridine rings. X-ray structure analysis confirmed that 12H and its zinc complex ( 1Zn ) adopt a helical geometry. A racemic mixture of 1Zn was resolved into two enantiomers ((P)- and (M)- 1Zn ), which exhibited CPL with a high luminescence dissymmetry factor (glum) value of ±2.1×10−2. The origin of the large glum value was rationalized by means of DFT calculations. Helical structures could be formed in a diastereoselective manner by covalently attaching chiral units to the skeleton ( 1’2H and 1’Zn ). 1Zn was found to possess chiral recognition ability for amines. 相似文献
86.
87.
Kang Yang Chang-Shan Yang Xing-Xian Dong Dr. Yu-Hui Tan Prof. Yun-Zhi Tang Dr. Wen-Juan Wei 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(26):5887-5892
Smart multifunctional molecular ferroelectrics bearing high Curie temperatures and diverse excellent physical properties, such as second harmonic generation (SHG) responses, luminescence, and semiconductivity, among others, have significant applications but have seldom been documented. Herein, the rare-earth metals Nd and Pr are introduced into a simple molecular system (nBu4N )3[M(NO3)x(SCN)y] (nBu4N=tetrabutyl ammonium, M=rare-earth metal, nBu=CH3CH2CH2CH2), and two new multifunctional molecular ferroelectrics are obtained: (nBu4N )3[Nd(NO3)4(SCN)2] ( 1 ) and (nBu4N )3[Pr(NO3)4(SCN)2] ( 2 ). Their distinct heat and dielectric anomaly dependence on temperature verifies that compounds 1 and 2 experience high-temperature para-ferroelectric phase transitions at 408 and 413 K, respectively. Strikingly, both molecular ferroelectrics possess large spontaneous polarization with Ps values of 9.05 and 8.50 μC cm−2, respectively, and are further characterized by the appearance of multiple intersecting non-180° domains and polarization switching behavior. In particular, compounds 1 and 2 show good stability with only a small decrease in SHG intensity after switching cycles, suggesting that they have great potential for application in nonlinear optical (NLO) switches. Simultaneously, the rare-earth compounds 1 and 2 present bright yellow–red and bright green fluorescence, respectively, at room temperature. 相似文献
88.
Dr. Timothy A. Barendt Dr. Melissa L. Ball Dr. Qizhi Xu Dr. Boyuan Zhang Dr. Brandon Fowler Ayden Schattman Virginia Cary Ritter Prof. Michael L. Steigerwald Prof. Colin Nuckolls 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(17):3744-3748
This work presents a synergy between organic electronics and supramolecular chemistry, in which a host–guest complex is designed to function as an efficacious electronic material. Specifically, the noncovalent recognition of a fullerene, phenyl-C61-butyric acid methyl ester ( PC61BM ), by an alternating perylene diimide ( P )-bithiophene ( B ) conjugated macrocycle ( PBPB ) results in a greater than five-fold enhancement in electron mobility, relative to the macrocycle alone. Characterization and quantification of the binding of fullerenes by host PBPB is provided alongside evidence for intermolecular electronic communication within the host–guest complexes. 相似文献
89.
Metal-Free,Visible-Light-Induced Selective C−C Bond Cleavage of Cycloalkanones with Molecular Oxygen
Hong Xin Prof. Dr. Xin-Hua Duan Dr. Le Liu Prof. Dr. Li-Na Guo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(51):11690-11694
A metal-free, visible-light-induced oxidative C−C bond cleavage of cycloketones with molecular oxygen is described. Cooperative Brønsted-acid catalysis and photocatalysis enabled selective C−C bond cleavage of cycloketones to generate an array of γ-, δ- and ϵ-keto esters under very mild conditions. Mechanistic studies indicate that singlet molecular oxygen (1O2) is responsible for this transformation. 相似文献
90.
Dr. Stefano Elli Dr. Eduardo Stancanelli Dr. Zhangjie Wang Dr. Maurice Petitou Prof. Jian Liu Dr. Marco Guerrini 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(51):11814-11818
Heparin binds to and activates antithrombin (AT) through a specific pentasaccharide sequence, in which a trisaccharide subsite, containing glucuronic acid (GlcA), has been considered as the initiator in the recognition of the polysaccharide by the protein. Recently it was suggested that sulfated iduronic acid (IdoA2S) could replace this “canonical” GlcA. Indeed, a heparin octasaccharidic sequence obtained by chemoenzymatic synthesis, in which GlcA is replaced with IdoA2S, has been found to similarly bind to and activate antithrombin. By using saturation-transfer-difference (STD) NMR, NOEs, transferred NOEs (tr-NOEs) NMR and molecular dynamics, we show that, upon binding to AT, this IdoA2S unit develops comparable interactions with AT as GlcA. Interestingly, two IdoA2S units, both present in a 1C4-2S0 equilibrium in the unbound saccharide, shift to full 2S0 and full 1C4 upon binding to antithrombin, providing the best illustration of the critical role of iduronic acid conformational flexibility in biological systems. 相似文献