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111.
Tingting Zhang Dr. Jiaying Yan Yuanyuan Hu Dr. Xiang Liu Liu Wen Dr. Kaibo Zheng Dr. Nuonuo Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(39):9266-9271
A two-step, one-flask synthesis of central seven-membered borondifluoride-3,3-dimethyl-2-[2-(2-pyrrolyl)ethenyl] indole (BOPYIN) ligands has been developed by using the unexplored 3,3-dimethyl-2-[2-(2-pyrrolyl)ethenyl] indole. The simple synthetic approach has enabled modification of the electronic structure by changing the substituents on the indole unit. X-ray analysis indicated that conformations of the seven-membered BF2 complex including BOPYIN and diazaborepin differ from that of the five- and six-membered organoboron complexes. Interestingly, the bond angle of the N⋅⋅⋅B−N bond increases with the number of atoms in the core ring, based on Baeyer strain theory. These unsymmetric BOPYIN derivatives have excellent photophysical properties, including high fluorescence quantum yields, except for BOPYIN- 4 in the solution state, large Stokes shifts, and good molar absorptivity. The dipole moment of BOPYIN- 3 in the first excited singlet state and ground state was demonstrated by a linear Lippert–Mataga plot. The absorption and emission spectra were not mirror images for BOPYIN- 1 – 3 and 5 , in contradiction to Kasha's rule, as determined by TDDFT. The synthesized BOPYINs have been shown to be biocompatible fluorophores in cell bioimaging. 相似文献
112.
The spectral properties of fluorescent proteins (FPs) depend on the protein environment of the chromophore (CRO). A deeper understanding of the CRO – environment interactions in terms of FPs’ spectral characteristics will allow for a rational design of novel markers with desired properties. Here, we are taking a step towards achieving this important goal. With the time-dependent density functional theory (TDDFT), we calculate one- and two-photon absorption (OPA and TPA) spectra for 5 green FPs (GFPs) and 3 yellow FPs (YFPs) differing in amino acid sequence. The goal is to reveal the roles of: (i) electrostatic interactions, (ii) hydrogen-bonds (h-bonds) and (iii) h-bonds together with distant electrostatic field in absorption spectra tuning. Our results point to design hypothesis towards FPs optimised for TPA-based applications. Both h-bonds and electrostatic interactions co-operate in enhancing TPA cross-section ( ) for the transition in GFPs. Furthermore, it seems that details of h-bonds network in the CRO's vicinity influences response to CRO – environment electrostatic interactions in YFPs. We postulate that engineering FPs with more hydrophilic CRO's environment can lead to greater . We also find that removing h-bonds formed with the CRO's phenolate leads to TPA enhancement for transition to higher excited states than S1. Particularly Y145 and T203 residues are important in this regard. 相似文献
113.
Review on recent and advanced applications of monoliths and related porous polymer gels in micro-fluidic devices 总被引:1,自引:0,他引:1
Mercedes Vázquez 《Analytica chimica acta》2010,668(2):100-8248
This review critically summarises recent novel and advanced achievements in the application of monolithic materials and related porous polymer gels in micro-fluidic devices appearing within the literature over the period of the last 5 years (2005-2010). The range of monolithic materials has developed rapidly over the past decade, with a diverse and highly versatile class of materials now available, with each exhibiting distinct porosities, pore sizes, and a wide variety of surface functionalities. A major advantage of these materials is their ease of preparation in micro-fluidic channels by in situ polymerisation, leading to monolithic materials being increasingly utilised for a larger variety of purposes in micro-fluidic platforms. Applications of porous polymer monoliths, silica-based monoliths and related homogeneous porous polymer gels in the preparation of separation columns, ion-permeable membranes, preconcentrators, extractors, electrospray emitters, micro-valves, electrokinetic pumps, micro-reactors and micro-mixers in micro-fluidic devices are discussed herein. Procedures used in the preparation of monolithic materials in micro-channels, as well as some practical aspects of the micro-fluidic chip fabrication are addressed. Recent analytical/bioanalytical and catalytic applications of the final micro-fluidic devices incorporating monolithic materials are also reviewed. 相似文献
114.
C. Baumstark-Khan M. Palm J. Wehner M. Okabe M. Ikawa G. Horneck 《Journal of fluorescence》1999,9(1):37-43
Generation of Chinese Hamster Ovary (CHO) cell lines stably expressing green fluorescent protein (GFP) was achieved using a plasmid vector that encoded the red-shifted pCX-xGFP under the control of a strong hybrid promoter composed of a CMV enhancer and a -actin/-globin gene promoter. Cotransfection of the promoter-less pSV2-Neo helper plasmid transmitting neomycin resistance was followed by selection with the antibiotic G418. Constitutive GFP expression could be visualized in living and fixed cells using fluorescence spectroscopy, fluorescence microscopy, and flow cytometry. DNA repair-proficient (AA8) and deficient (UV5) CHO strains were used for survival tests after UVC irradiation. Cells carrying the GFP construct (AA8-pGFP, UV5-pGFP) show the same response to UV irradiation (colony forming ability) as their nontransformed parental cell lines (AA8, UV5). Using GFP as a marker for cell viability, cells were harvested after certain postirradiation growth periods and the numbers of GFP expressing cells and fluorescence intensities were determined by FACS analysis. Generally, GFP fluorescence in irradiated cells is not seen when cell membranes are damaged (leak-out of the soluble GFP). Irradiated cells without membrane damage express GFP continuously (leading to a dose-dependent increase in GFP contents). 相似文献
115.
116.
Vincent Lemaur Jérôme Cornil Delphine Didier Aline Mujawase Sergey Sergeyev 《Helvetica chimica acta》2007,90(11):2087-2095
We report on the synthesis and electronic spectra of the chiral, donor‐acceptor (push‐pull) chromophores (±)‐ 4 and (±)‐ 5 with a 6H,12H‐5,11‐methanodibenzo[b,f][1,5]diazocine scaffold (Scheme 1 and Fig. 2). The electronic structures of these compounds were investigated at a quantum‐chemical level (Figs. 2 and 3). The chemical reactivity of 6H,12H‐5,11‐methanodibenzo[b,f][1,5]diazocine ((±)‐ 11 ) towards aromatic electrophilic substitution (Scheme 2 and Table) provided additional information about its electronic structure and confirmed nonnegligible delocalization of the lone pair of the bridge‐head N‐atoms in this heterocyclic system. 相似文献
117.
M. Ya. Goikhman L. I. Subbotina I. V. Gofman A. V. Yakimanskii A. E. Bursian V. A. Lukoshkin G. N. Fedorova A. V. Sidorovich O. E. Praslova N. N. Smirnov I. V. Abalov V. V. Kudryavtsev 《Russian Chemical Bulletin》2005,54(6):1481-1487
A new method was elaborated for the introduction of chromophores into the side chains of polymers by esterification of polyamidoimides
containing side carboxy groups with glycidyl ethers of dyes, 4-(4-nitrophenylazo)phenol and 4-(6-nitrobenzothiazol-2-ylazo)phenol.
The optimum modification conditions were found that made it possible to esterify 15, 30, 50, and 90% of the carboxy groups.
The synthesized polymers possess valuable physicomechanical properties (E = 2.8–3.3 GPa, σu = 69–90 MPa, εu = 38–77%) and glass transition temperatures of 115–125 °C, depending on the degree of esterification. After chromophore orientation
in the corona discharge, all the polymers demonstrate nonlinear optical properties of the second order.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1438–1444, June, 2005. 相似文献
118.
Wei‐Yu Lin Hsian‐Wen Wang Zhi‐Chang Liu Jun Xu Chih‐Wei Chen Yun‐Chin Yang Shou‐Ling Huang Hsiao‐Ching Yang Prof. Tien‐Yau Luh Prof. 《化学:亚洲杂志》2007,2(6):764-774
Two dimers and a series of polymers with 5,6‐endo pendant aryl groups that contain different substituents at the para positions were synthesized. The conformation and stereochemistry of the dimers and polymers were determined by nonlinear optical analysis (EFISH) as well as UV/Vis and 13C NMR spectroscopy. The chemical shifts of C7 for the polymers appeared as two peaks in the 13C NMR spectra when the substituents are electron‐withdrawing groups. The percentage decrease in the relative extinction coefficient of the polymers, εd, was linearly related to the Hammett constant σ. Polynorbornenes with electron‐withdrawing substituents may adopt isotactic stereochemistry with all pendant groups aligned in one direction. The nature of the interactions between neighboring chromophores may be one of the most important factors in directing the stereoregularity and conformation of these polymers. The corresponding polymers derived from the exo isomers appeared to be less stereoregular. 相似文献
119.
Degradation of polyamide 11 in rotational moulding 总被引:1,自引:0,他引:1
The degradation of polyamide 11 (PA 11) was studied in samples rotationally moulded using a range of processing temperatures. The chemical changes occurring in the moulded material were assessed using FTIR, UV-vis spectroscopy, 1H NMR spectroscopy, gas chromatography, rheometry and microscopy. The results showed that the degradation is complex and depends on the location of the material in the moulding. At the internal surface, the degradation is predominantly thermo-oxidative leading to the formation of carbon dioxide, carboxylic acids and conjugated unsaturated oligo-enimines (UV-vis-active chromophores). Away from the internal surface, the dominant process is through the recombination of broken chains and/or post-condensation reactions that increase the molecular weight without the formation of UV-vis-active chromophores. A degradation mechanism is proposed for PA 11 in rotational moulding. 相似文献
120.
The linear and nonlinear optical polarizabilities of donor-acceptor (D-pi-A) chromophores in confined geometries of calix[4]arenes are investigated through a model for interacting polar-polarizable molecules. Both the linear polarizability (alpha) and the first hyperpolarizability (beta) decrease with increasing the interdipolar angle, as expected in the oriented-gas picture. However, within the polar-polarizable model we predict deviations from the additive result, irrespective of the interdipolar angle. Depending on the nature of the chromophore, electrostatic intermolecular interactions between polar and polarizable chromophores lead to cooperative damping or enhancement of the optical responses. Specifically, for chromophores whose ground state is dominated by the neutral D-pi-A structure both alpha and beta are suppressed with respect to the prediction of the oriented-gas model, whereas the opposite holds true for chromophores whose ground state is dominated by the zwitterionic D(+)-pi-A(-). These results explain recent experimental data on a calix[4]arene functionalized with a donor-acceptor dye for nonlinear optical applications. Density functional theory calculations on the relevant crystal structure further support our interpretation. 相似文献