全文获取类型
收费全文 | 1555篇 |
免费 | 77篇 |
国内免费 | 31篇 |
专业分类
化学 | 1081篇 |
晶体学 | 14篇 |
力学 | 68篇 |
综合类 | 1篇 |
数学 | 105篇 |
物理学 | 394篇 |
出版年
2024年 | 3篇 |
2023年 | 12篇 |
2022年 | 14篇 |
2021年 | 23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 | 68篇 |
2008年 | 108篇 |
2007年 | 76篇 |
2006年 | 68篇 |
2005年 | 90篇 |
2004年 | 64篇 |
2003年 | 51篇 |
2002年 | 46篇 |
2001年 | 43篇 |
2000年 | 33篇 |
1999年 | 21篇 |
1998年 | 13篇 |
1997年 | 20篇 |
1996年 | 30篇 |
1995年 | 15篇 |
1994年 | 24篇 |
1993年 | 31篇 |
1992年 | 28篇 |
1991年 | 17篇 |
1990年 | 12篇 |
1989年 | 15篇 |
1988年 | 15篇 |
1987年 | 13篇 |
1986年 | 8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 |
排序方式: 共有1663条查询结果,搜索用时 0 毫秒
41.
42.
A new series of quinolinolate osmium carbonyl complexes were synthesized and characterized by spectroscopic methods. Single-crystal X-ray diffraction studies indicate that these complexes consist of an octahedral ligand arrangement with one chelating quinolinolate, one tfa or halide ligand, and three mutually orthogonal terminal CO ligands. Variation of the substituents on quinolinolate ligands imposes obvious electronic or structural effects, while changing the tfa ligand to an electron-donating iodide slightly increases the charge density on the central osmium atom. These Os(II) complexes show salient dual emissions consisting of fluorescence and phosphorescence, the spectral properties and relaxation dynamics of which have been studied comprehensively. The results, in combination with the theoretical approaches, lead us to propose that the emission mainly originates from the quinolinolate pi pi* state. Both experimental and theoretical approaches generalize various types of intersystem crossing versus those of the tris(quinolinolate) iridium Ir(Q)3, and their relative efficiencies were accessed on the basis of the associated frontier orbital configurations. Our results suggest that [1d(pi)pi* absolute value(H(so))3 pi pi*] (or [3d(pi)pi* absolute value(H(so))1 pi pi*]) in combination with a smaller deltaE(S1-T1) gap (i.e., increasing the MLCT (d(pi)pi*) character) is the main driving force to induce the ultrafast S1 --> T1 intersystem crossing in the third-row transition metal complexes, giving the strong phosphorescent emission. 相似文献
43.
A simple method is described for the speciation of metalions in biological extracts with a short desalting gel-filtration column. The system was optimized for the eluent and gel type to provide accurate free metal ion levels and minimum processing times. The four separation media studied were Sephadex G25, Bio-Gel P-6DG, controlled pore glass CPG40, and Fractogel HW40F. The best medium was the Fractogel HW40F because it was not compressible and allowed a pump to be used to obtain uniform flow rates. The eluent was 0.10 M ammonium acetate/0.01 M citric acid adjusted to pH 7.0. This eluent minimized ion/gel interactions and gave a lower salt content relative to other possible eluents. The separation time was 10 min per sample per metal ion of interest. The detection limits relative to the mass of wet tissue for the column/flame spectrometer system were 0.80 μg g?1, 0.80 μg g?1, and 1.6 μg g?1 for zinc, cadmium and copper, respectively. The method is evaluated for a lobster digestive gland extract; the methodology should be applicable to other systems containing nonlabile metal species. 相似文献
44.
Chih-Hsin Yeh Chia-Yi Chou Chin-Sheng Wu Lee-Ping Chu Wei-Juan Huang Hsin-Chun Chen 《Molecules (Basel, Switzerland)》2022,27(14)
To establish the analytic conditions for examining the aroma quality of vanilla pods, we compared different extraction methods and identified a suitable option. We utilized headspace solid-phase microextraction (HS-SPME), steam distillation (SD), simultaneous steam distillation (SDE) and alcoholic extraction combined with gas chromatography (GC) and gas chromatography–mass spectrometry (GC-MS) to identify volatile components of vanilla pods. A total of 84 volatile compounds were identified in this experiment, of which SDE could identify the most volatile compounds, with a total of 51 species, followed by HS-SPME, with a total of 28 species. Ten volatile compounds were identified by extraction with a minimum of 35% alcohol. HS-SPME extraction provided the highest total aroma peak areas, and the peak areas of aldehydes, furans, alcohols, monoterpenes and phenols compounds were several times higher than those of the other extraction methods. The results showed that the two technologies, SDE and HS-SPME, could be used together to facilitate analysis of vanilla pod aroma. 相似文献
45.
46.
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
47.
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
48.
Shin-Hun Juang Min-Tsang Hsieh Pei-Ling Hsu Ju-Ling Chen Hui-Kang Liu Fong-Pin Liang Sheng-Chu Kuo Chen-Yuan Chiu Shing-Hwa Liu Chen-Hsi Chou Tian-Shung Wu Hsin-Yi Hung 《Molecules (Basel, Switzerland)》2021,26(1)
Constitutive androstane receptor (CAR) activation has found to ameliorate diabetes in animal models. However, no CAR agonists are available clinically. Therefore, a safe and effective CAR activator would be an alternative option. In this study, sixty courmarin derivatives either synthesized or purified from Artemisia capillaris were screened for CAR activation activity. Chemical modifications were on position 5,6,7,8 with mono-, di-, tri-, or tetra-substitutions. Among all the compounds subjected for in vitro CAR activation screening, 6,7-diprenoxycoumarin was the most effective and was selected for further preclinical studies. Chemical modification on the 6 position and unsaturated chains were generally beneficial. Electron-withdrawn groups as well as long unsaturated chains were hazardous to the activity. Mechanism of action studies showed that CAR activation of 6,7-diprenoxycoumarin might be through the inhibition of EGFR signaling and upregulating PP2Ac methylation. To sum up, modification mimicking natural occurring coumarins shed light on CAR studies and the established screening system provides a rapid method for the discovery and development of CAR activators. In addition, one CAR activator, scoparone, did showed anti-diabetes effect in db/db mice without elevation of insulin levels. 相似文献
49.
Dr. Andrey Belyaev Prof. Pi-Tai Chou Prof. Igor O. Koshevoy 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(2):537-552
Tunable electron-accepting properties of the cationic phosphorus center, its geometry and unique preparative chemistry that allows combining this unit with diversity of π-conjugated motifs, define the appealing photophysical and electrochemical characteristics of organophosphorus ionic chromophores. This Minireview summarizes the achievements in the synthesis of the π-extended molecules functionalized with P-cationic fragments, modulation of their properties by means of structural modification, and emphasizes the important effect of cation-anion interactions, which can drastically change physical behavior of these two-component systems. 相似文献
50.
Dr. Cheng‐Chung Lee Dr. Manuel Maestre‐Reyna Dr. Kai‐Cheng Hsu Prof. Dr. Hao‐Ching Wang Prof. Dr. Chia‐I Liu Prof. Dr. Wen‐Yih Jeng Li‐Ling Lin Richard Wood Dr. Chia‐Cheng Chou Prof. Dr. Jinn‐Moon Yang Prof. Dr. Andrew H.‐J. Wang 《Angewandte Chemie (International ed. in English)》2014,53(48):13054-13058
Crown ethers are small, cyclic polyethers that have found wide‐spread use in phase‐transfer catalysis and, to a certain degree, in protein chemistry. Crown ethers readily bind metallic and organic cations, including positively charged amino acid side chains. We elucidated the crystal structures of several protein‐crown ether co‐crystals grown in the presence of 18‐crown‐6. We then employed biophysical methods and molecular dynamics simulations to compare these complexes with the corresponding apoproteins and with similar complexes with ring‐shaped low‐molecular‐weight polyethylene glycols. Our studies show that crown ethers can modify protein surface behavior dramatically by stabilizing either intra‐ or intermolecular interactions. Consequently, we propose that crown ethers can be used to modulate a wide variety of protein surface behaviors, such as oligomerization, domain–domain interactions, stabilization in organic solvents, and crystallization. 相似文献