全文获取类型
收费全文 | 1567篇 |
免费 | 86篇 |
国内免费 | 31篇 |
专业分类
化学 | 1084篇 |
晶体学 | 14篇 |
力学 | 68篇 |
综合类 | 1篇 |
数学 | 109篇 |
物理学 | 408篇 |
出版年
2023年 | 11篇 |
2022年 | 8篇 |
2021年 | 22篇 |
2020年 | 27篇 |
2019年 | 36篇 |
2018年 | 17篇 |
2017年 | 10篇 |
2016年 | 35篇 |
2015年 | 33篇 |
2014年 | 46篇 |
2013年 | 61篇 |
2012年 | 111篇 |
2011年 | 138篇 |
2010年 | 70篇 |
2009年 | 67篇 |
2008年 | 108篇 |
2007年 | 76篇 |
2006年 | 69篇 |
2005年 | 91篇 |
2004年 | 64篇 |
2003年 | 51篇 |
2002年 | 46篇 |
2001年 | 44篇 |
2000年 | 43篇 |
1999年 | 22篇 |
1998年 | 14篇 |
1997年 | 20篇 |
1996年 | 34篇 |
1995年 | 15篇 |
1994年 | 30篇 |
1993年 | 35篇 |
1992年 | 27篇 |
1991年 | 18篇 |
1990年 | 13篇 |
1989年 | 15篇 |
1988年 | 15篇 |
1987年 | 13篇 |
1986年 | 9篇 |
1985年 | 18篇 |
1984年 | 17篇 |
1983年 | 9篇 |
1982年 | 6篇 |
1981年 | 10篇 |
1979年 | 7篇 |
1978年 | 13篇 |
1977年 | 3篇 |
1975年 | 6篇 |
1974年 | 6篇 |
1973年 | 5篇 |
1939年 | 2篇 |
排序方式: 共有1684条查询结果,搜索用时 250 毫秒
71.
Yi Chen Deng-Gao Chen Yi-An Chen Cheng-Ham Wu Kai-Hsin Chang Fan-Yi Meng Meng-Chi Chen Jia-An Lin Chun-Ying Huang Jianhua Su He Tian Prof. Pi-Tai Chou 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(72):16755-16764
With the aim of generalizing the structure–properties relationship of bending heterocyclic molecules that undergo prominent photoinduced structural planarization (PISP), a series of new dihydrodibenzo[ac]phenazine derivatives in which one nitrogen atom is replaced by oxygen ( PNO ), sulfur ( PNS ), selenium ( PNSe ), or dimethylmethanediyl ( PNC ) was strategically designed and synthesized. Compounds PNO , PNS , and PNSe have significantly nonplanar geometries in the ground state, which undergo PISP to give a planarlike conformer and hence a large emission Stokes shift. A combination of femtosecond early relaxation dynamics and computational approaches established an R*→I* (intermediate)→P* sequential kinetic pattern for PNS and PNSe , whereas PNO undergoes R*→P* one-step kinetics. The polarization ability of the substituted heteroatoms, which is in the order O<S<Se, correlates with their increase in π conjugation, and hence the Stokes shift of the emission is in the order PNO < PNS < PNSe . Compound PNSe with the largest PISP barrier was shown to be a highly sensitive viscosity probe. Further evidence for heteroatom-harnessing PISP is given by PNC , in which the dimethylmethanediyl substituent lacks lone pair electrons for π extension, showing the normal emission of the bent structure. The results led to the conclusion that PISP is ubiquitous in dihydrodibenzo[ac]phenazines, for which the driving force is elongation of the π delocalization to gain stabilization in the excited state. 相似文献
72.
Ming-Tsz Chen Yu-Yang Chen Guan-Lin Li Kai-Wen Chou Ching-Han Hu Guo-Cyuan Huang Chi-Tien Chen 《应用有机金属化学》2020,34(4):e5464
This paper describes the effect of solvent-induced synthetic routes of aluminium pendant oxazoline-amido-phenolate complexes. Treatment of ligand precursor L with AlMe3 in a 1:1 ratio in diethyl ether yielded the four-coordinated complex (LAlMe)2. Reaction of ligand precursor L with AlMe3 in a 1:2 ratio in hexane generated the four-coordinated complex L(AlMe2)2. A novel transformation mode occurred from L(AlMe2)2 to (LAlMe)2 when using diethyl ether or tetrahydrofuran as solvent. A density functional theory computational study also supports a plausible mechanism. All results were supported by spectroscopic data and in agreement with single-crystal X-ray diffraction structural analysis. 相似文献
73.
Martin Pomerantz Whe-Narn Chou 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4)
Abstract A series of N-phenyl-P,P,P-triarylphospha-λ5-azenes (1) as well as their l5N labeled analogs was synthesized. The 13C, 31P, and 15N NMR spectra of this series and those of two other series of related compounds, namely triarylphosphines (2) and triarylphosphine oxides (3), were measured and are reported. Many satisfactory correlations using the mono-substituent parameter (MSP) and the Taft dual-substituent parameter (DSP) treatments with the 13C substituent chemical shifts (SCS), 31P SCS, 15N SCS and the one bond P-N, P-C and C-N coupling constants were observed and will be discussed. Thus, for example, the 31P and 15N chemical shifts in 1 correlated with [sgrave]?with negative slopes while the 31P chemical shifts in 3 correlated with those in 1 with a slope of 2.0. The 13C chemical shifts in 1 correlated excellently with the corresponding ones in 3 with slopes very close to unity. The substituent effects on the chemical shifts of the various nuclei were shown to be mainly due to changes in the charge distribution on those nuclei. In 1 the one bond P-N and P-C coupling constants correlated with [sgrave]p and [sgrave]R respectively. The one bond P-C coupling constants of 1 correlated quite well with those of 3 with a slope of 0.93 while the corresponding correlation of 1 with 2 was quite poor. Taft DSP treatment of 1JPCin 1 and 3 were quite similar, ρI and ρR were both negative and ρR was much larger than ρI. Series 2 showed behavior which was different from that shown by 1 and 3 but similar to that shown by other systems with a lone electron pair on the atom bound to the phenyl ring. The substituent effects on the one bond P-N, P-C and C-N coupling constants will be discussed in terms of bonding and hybridization changes between the directly bonded nuclei. 相似文献
74.
75.
76.
Der‐Lii M. Tzou Lin‐Kai Ni Mei‐Man Chen Min‐Chuan Chiou Li‐Chou Chen Shan‐Te Hsu Kuo‐Lung Ku Chien‐Chung Cheng 《中国化学会会志》2013,60(9):1107-1112
Solid‐state Nuclear Magnetic Resonance (ss‐NMR) 13C single‐pulse excitation spectroscopy in combination with the magic‐angle spinning (MAS) technique was applied to a series of Phalaenopsis tissues, including the leaf, sheath, stem, and root, at different growth and spiking periods. Compared with{1H}/13C cross‐polarization MAS spectra, the 13C single‐pulse excitation MAS spectra displayed very distinct spectral patterns, recognizable as fingerprints of the tissues studied. 1Here, we demonstrate that solid‐state 13C single‐pulse excitation NMR spectroscopy provides a direct and robust analytical tool for studying the various tissues of Phalaenopsis in different growth and spiking induction periods. 相似文献
77.
Sulfur‐substituted 4‐quinolizidinones, previously prepared by aza‐Diels‐Alder reactions and ring‐closing metathesis, are now subjected to further synthetic transformations. Formal synthesis of cermizine C and 5‐epi‐cermizine C, and some other useful reactions have been achieved. 相似文献
78.
Ya‐Chu Hsieh Hau‐Yu Fang Yi‐Ting Chen Rong Yang Chen‐I Yang Pi‐Tai Chou Ming‐Yu Kuo Yao‐Ting Wu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(10):3112-3116
The syntheses, structures, and physical properties of dibenzozethrenes were explored. The results thus obtained were compared with those for zethrenes. Dibenzozethrenes were synthesized by the nickel‐catalyzed cyclodimerization of 9‐ethynyl‐1‐iodoanthracenes. The substituents in zethrene and dibenzozethrene twisted their backbones, and remarkably influenced their properties. Unlike closed‐shell disubstituted derivatives, the parent zethrene and dibenzozethrene are singlet open‐shell biradicals, which were studied by variable‐temperature 1H NMR, ESR, SQUID and computational methods. Since substituents were observed to affect significantly the biradical properties, the relevant mechanisms were analyzed. The nonlinear optical performance of each of these compounds depends on its π‐conjugation and biradical properties. Dibenzozethrenes have larger two‐photon absorption cross‐sections than zethrenes, as most strongly evidenced by the parent dibenzothrene [σmax=4323 GM at 530 nm]. 相似文献
79.
80.
Yi-Chun Lin Yuan-Yung Lin Hsin-Chien Chen Chao-Yin Kuo Ai-Ho Liao Ying-Liang Chou Chia-Lien Hung Cheng-Ping Shih Chih-Hung Wang 《Molecules (Basel, Switzerland)》2021,26(12)
The application of insulin-like growth factor 1 (IGF-1) to the round window membrane (RWM) is an emerging treatment for inner ear diseases. RWM permeability is the key factor for efficient IGF-1 delivery. Ultrasound microbubbles (USMBs) can increase drug permeation through the RWM. In the present study, the enhancing effect of USMBs on the efficacy of IGF-1 application and the treatment effect of USMB-mediated IGF-1 delivery for noise-induced hearing loss (NIHL) were investigated. Forty-seven guinea pigs were assigned to three groups: the USM group, which received local application of recombinant human IGF-1 (rhIGF-1, 10 µg/µL) following application of USMBs to the RWM; the RWS group, which received IGF-1 application alone; and the saline-treated group. The perilymphatic concentration of rhIGF-1 in the USM group was 1.95- and 1.67- fold of that in the RWS group, 2 and 24 h after treatment, respectively. After 5 h of 118 dB SPL noise exposure, the USM group had the lowest threshold shift in auditory brainstem response, least loss of cochlear outer hair cells, and least reduction in the number of synaptic ribbons on postexposure day 28 among the three groups. The combination of USMB and IGF-1 led to a better therapeutic response to NIHL. Two hours after treatment, the USM group had significantly higher levels of Akt1 and Mapk3 gene expression than the other two groups. The most intense immunostaining for phosphor-AKT and phospho-ERK1/2 was detected in the cochlea in the USM group. These results suggested that USMB can be applied to enhance the efficacy of IGF-1 therapy in the treatment of inner ear diseases. 相似文献