全文获取类型
收费全文 | 1781篇 |
免费 | 52篇 |
国内免费 | 3篇 |
专业分类
化学 | 1144篇 |
晶体学 | 15篇 |
力学 | 53篇 |
数学 | 245篇 |
物理学 | 379篇 |
出版年
2022年 | 14篇 |
2021年 | 16篇 |
2020年 | 22篇 |
2019年 | 24篇 |
2018年 | 15篇 |
2017年 | 15篇 |
2016年 | 37篇 |
2015年 | 24篇 |
2014年 | 33篇 |
2013年 | 82篇 |
2012年 | 105篇 |
2011年 | 103篇 |
2010年 | 52篇 |
2009年 | 60篇 |
2008年 | 80篇 |
2007年 | 101篇 |
2006年 | 96篇 |
2005年 | 85篇 |
2004年 | 60篇 |
2003年 | 62篇 |
2002年 | 54篇 |
2001年 | 44篇 |
2000年 | 22篇 |
1999年 | 15篇 |
1998年 | 20篇 |
1997年 | 15篇 |
1996年 | 20篇 |
1995年 | 25篇 |
1994年 | 41篇 |
1993年 | 20篇 |
1992年 | 28篇 |
1991年 | 17篇 |
1990年 | 20篇 |
1989年 | 15篇 |
1988年 | 14篇 |
1987年 | 13篇 |
1986年 | 24篇 |
1985年 | 21篇 |
1984年 | 17篇 |
1983年 | 16篇 |
1982年 | 15篇 |
1981年 | 17篇 |
1980年 | 17篇 |
1979年 | 19篇 |
1978年 | 27篇 |
1977年 | 21篇 |
1976年 | 20篇 |
1975年 | 23篇 |
1973年 | 18篇 |
1972年 | 14篇 |
排序方式: 共有1836条查询结果,搜索用时 15 毫秒
1.
Andrey V. Lunchev Dr. Samuel A. Morris Dr. Rakesh Ganguly Prof. Andrew C. Grimsdale 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(7):1819-1823
A route to the synthesis of novel 5,7-diazapentacenes and some preliminary studies on their properties is reported. A single crystal X-ray diffraction study of the dihexyl derivative showed it had formed a dimer during the analysis. The materials possess lower lying frontier orbitals than pentacene and may have potential applications in organic electronic devices. This synthetic method may be applicable to the synthesis of other azaacenes. 相似文献
2.
3.
Joy Ann Panis Prof. Marine Louis Arnaud Brosseau Shouhei Katao Florencio de los Reyes Prof. Takuya Nakashima Dr. Rémi Métivier Dr. Clémence Allain Prof. Tsuyoshi Kawai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(44):e202201012
We synthesized two bichromophoric difluoroboron-β-diketonates (DFB) connected in para and meta positions by using cyclohexane diamine as a chiral bridge ( para and meta (R/S)-CyDFB ). TD-DFT calculations revealed that the variation in connectivity of the DFB units leads to different spatial arrangements and a chirality inversion of the bichromophoric DFB. Higher gabs values were obtained in (R/S)-CyDFB connected in para as compared to meta position. Aggregation of para (R/S)-CyDFB in mixture of solvents increase the glum values as compared to its monomeric form. Ultrasonication and heating induced the formation of highly ordered nano-helical wires of para (R/S)-CyDFB that increased the glum values to 0.015. On the other hand, meta (R/S)-CyDFB failed to form highly ordered self-assembled wires due to hindered H-binding sites. These observations indicate that the chiroptical properties of DFB bi-chromophore system can be modulated with self-assembly and spatial arrangement of the chromophores. 相似文献
4.
Manas Mahapatra Arnab Dutta Joy Sankar Deb Roy Ujjal Das Dr. Snehasis Banerjee Prof. Sanjit Dey Dr. Pijush Kanti Chattopadhyay Prof. Dilip K. Maiti Dr. Nayan Ranjan Singha 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(2):502-516
To circumvent costly fluorescent labeling, five nonconventional, multifunctional, intrinsically fluorescent aliphatic terpolymers ( 1 – 5 ) have been synthesized by C−C/C−N-coupled, solution polymerization of two non-emissive monomers with protrusions of fluorophore monomers generated in situ. These scalable terpolymers were suitable for sensing and high-performance exclusion of CuII, logic function, and bioimaging. The structures of the terpolymers, in situ attachment of fluorescent monomers, aggregation-induced enhanced emission, bioimaging ability, and super adsorption were investigated by 1H and 13C NMR, EPR, FTIR, X-ray photoelectron, UV/Vis, and atomic absorption spectroscopy, thermogravimetric analysis, high-resolution transmission electron microscopy, dynamic light scattering, solid-state fluorescence, fluorescence imaging, and fluorescence lifetime measurements, as well as by isotherm, kinetics, and thermodynamic studies. The geometries and electronic structures of the fluorophores and the absorption and emission properties of the terpolymers were examined by DFT, time-dependent DFT, and natural transition orbital analyses. For 1 , 2 , and 5 , the limits of detection were determined to be 1.03×10−7, 1.65×10−7, and 1.77×10−7 m , respectively, and the maximum adsorption capacities are 1575.21, 1433.70, and 1472.21 mg g−1, respectively. 相似文献
5.
Dr. Thais F. Abelha Dr. Graeme Morris Dr. Sandro M. Lima Dr. Luis H. C. Andrade Dr. Andrew J. McLean Prof. Cameron Alexander Dr. Jesus Calvo-Castro Dr. Callum J. McHugh 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(14):3173-3180
Development of novel bioimaging materials that exhibit organelle specific accumulation continues to be at the forefront of research interests and efforts. Among the various subcellular organelles, mitochondria, which are found in the cytoplasm of eukaryotic cells, are of particular interest in relation to their vital function. To date, most molecular probes that target mitochondria utilise delocalised lipophilic cations such as triphenylphosphonium and pyridinium. However, the use of such charged motifs is known to be detrimental to the working function of the mitochondrial transmembrane potential and there remains a strong case for development of neutral mitochondrial fluorescent probes. Herein, we demonstrate for the first time the exploitation of diketopyrrolopyrrole-based chemistries for the realisation of a neutral fluorescent probe that exhibits organelle specific accumulation within the mitochondria at the nanomolar level. The synthesised probe, which bears a neutral triphenylphosphine oxide moiety, exhibits a large Stokes shift and high fluorescence quantum yield in water, both highly sought-after properties in the development of bioimaging agents. In vitro studies reveal no interference with cell metabolism when tested for the human MCF7 breast cancer cell and nanomolar subcellular organelle colocalisation with commercially available mitochondrial staining agent Mitotracker Red. In light of its novelty, neutral structure and the preferential accumulation at nanomolar concentrations we anticipate this work to be of significant interest for the increasingly larger community devoted to the realisation of neutral mitochondrial selective systems and more widely to those engaged in the rational development of superior organic architectures in the biological field. 相似文献
6.
Back Cover: Spontaneous Stepwise Self‐Assembly of a Polyoxometalate–Organic Hybrid into Catalytically Active One‐Dimensional Anisotropic Structures (Chem. Eur. J. 31/2014) 下载免费PDF全文
7.
Raman spectroscopy provides information on bone chemical composition and structure via widely used metrics including mineral to matrix ratio, mineral crystallinity and carbonate content, collagen crosslinking ratio and depolarization ratios. These metrics are correlated with bone material properties, such as hardness, plasticity and Young''s modulus. We review application of Raman spectroscopy to two important irradiated animalmodels: the mouse tibia, amodel for damage to cortical bone sites including the rib (breast cancer) and to healthy tissue adjacent to extremity sarcomas, and the rat mandible, a model for radiation damage in head and neck cancer radiotherapy. Longitudinal studies of irradiated mouse tibia demonstrate that radiation-induced matrix abnormalities can persist even 26 weeks postradiation. Polarized Raman spectroscopy shows formation of more ordered orientation of both mineral and collagen. At 8 weeks post-radiation, irradiated rat hemimandible exhibits transient hypermineralization, increased collagen cross-linking and decreased depolarization ratios of mineral and collagen. A standard radioprotectant, amifostine, mitigates rat mandible radiation damage, with none remaining detectable 18 weeks post-radiation. Already a powerful tool to monitor radiation damage, Raman spectroscopy may be important in development of new radiotherapy protocols and radioprotective agents. Further in vivo studies of radiation effects on the rodent models are underway, as are development of methodologies for eventual use in human subjects. 相似文献
8.
9.
Dr. Caroline T. Saouma Wesley D. Morris Julia W. Darcy Prof. James M. Mayer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(25):9256-9260
Biological [Fe‐S] clusters are increasingly recognized to undergo proton‐coupled electron transfer (PCET), but the site of protonation, mechanism, and role for PCET remains largely unknown. Here we explore this reactivity with synthetic model clusters. Protonation of the arylthiolate‐ligated [4Fe‐4S] cluster [Fe4S4(SAr)4]2? ( 1 , SAr=S‐2,4‐6‐(iPr)3C6H2) leads to thiol dissociation, reversibly forming [Fe4S4(SAr)3L]1? ( 2 ) and ArSH (L=solvent, and/or conjugate base). Solutions of 2 +ArSH react with the nitroxyl radical TEMPO to give [Fe4S4(SAr)4]1? ( 1ox ) and TEMPOH. This reaction involves PCET coupled to thiolate association and may proceed via the unobserved protonated cluster [Fe4S4(SAr)3(HSAr)]1? ( 1‐H ). Similar reactions with this and related clusters proceed comparably. An understanding of the PCET thermochemistry of this cluster system has been developed, encompassing three different redox levels and two protonation states. 相似文献
10.
Prof. Polly L. Arnold Dr. Alessandro Prescimone Dr. Joy H. Farnaby Dr. Stephen M. Mansell Prof. Simon Parsons Prof. Nikolas Kaltsoyannis 《Angewandte Chemie (International ed. in English)》2015,54(23):6735-6739
The diuranium(III) compound [UN′′2]2(μ‐η6:η6‐C6H6) (N′′=N(SiMe3)2) has been studied using variable, high‐pressure single‐crystal X‐ray crystallography, and density functional theory . In this compound, the low‐coordinate metal cations are coupled through π‐ and δ‐symmetric arene overlap and show close metal? CH contacts with the flexible methyl CH groups of the sterically encumbered amido ligands. The metal–metal separation decreases with increasing pressure, but the most significant structural changes are to the close contacts between ligand CH bonds and the U centers. Although the interatomic distances are suggestive of agostic‐type interactions between the U and ligand peripheral CH groups, QTAIM (quantum theory of atoms‐in‐molecules) computational analysis suggests that there is no such interaction at ambient pressure. However, QTAIM and NBO analyses indicate that the interaction becomes agostic at 3.2 GPa. 相似文献