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991.
In this paper, we described the synthesis and characterization of new diphenylethylene bearing imino group. We concentrated particularly on the investigation of the possibility of the excited state intramolecular charge transfer (ESIPT) of the new dyes experimentally and theoretically. The absorption and fluorescence spectroscopy of the dyes were determined in various solvents. The results showed that the maximal absorption wavelength of 2‐[(4′‐N,N‐dimethylamino‐diphenylethylene‐4‐ylimino)methyl]phenol ( C1 ) and 4‐[(4′‐N,N‐dimethylamino‐diphenylethylene‐4‐ylimino)methyl]phenol ( C2 ) exhibited almost independence on the solvent polarity. While as contrast, the maximal fluorescence wavelength of the dyes showed somewhat dependence on the solvent polarity. In particular, C1 displayed well‐separated dual fluorescence spectroscopy. The second fluorescence peak was characterized with an "abnormal" fluorescence emission wavelength in aprotic solvents with large Stokes shift (ca. 140 nm in THF), which was much more than normal Stokes shift (ca. 30 nm in THF). This emission spectroscopy could be assigned to ESIPT emission. On the other hand, the ESIPT fluorescence of C1 was much reduced or lost in the protic solvents. While, only normal fluorescence emission was detected in various solvents. Although the absorption maxima of C1 exhibited about 10 nm red‐shift with respect to those of C2 , the normal fluorescence maxima of C1 and C2 were almost identical in various solvents. These results suggested that C1 could undergo ESIPT, but C2 was not able to proceed ESIPT. The molecular geometry optimization of phototautomers in the ground electronic state (S0) was carried out with HF method (Hartree‐Fock) and at DFT level (Density Functional Theory) using B3LYP both, while the CIS was employed to optimize the geometries of the first singlet excited state (S1) of the phototautomers of C1 and C2 respectively. The properties of the ground state and the excited state of the phototautomers of C1 and C2 , including the geometrical parameter, the energy, the frontier orbits, the Mulliken charge and the dipole moment change were performed and compared completely. The data were analyzed further based on our experimental results. Furthermore, the absorption and fluorescence spectra were calculated in theory and compared with the measured ones. The rate constant of internal proton transfer (9.831×1011 s?1) of C1 was much lower than that of salicylidene methylamine ( C3 , 2.045×1015 s?1), which was a typical Schiff base compound and was well demonstrated to undergo ESIPT easily under photoexcitation. 相似文献
992.
Yang Liu Dr. Yong Yu Jacky W. Y. Lam Dr. Yuning Hong Mahtab Faisal Wang Zhang Yuan Dr. Ben Zhong Tang Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(28):8433-8438
A handy, specific, sensitive bioprobe has been developed. Tetraphenylethene (TPE) was functionalized by a maleimide (MI) group, giving a TPE‐MI adduct that was nonemissive in both solution and the solid state. It was readily transformed into a fluorogen showing an aggregation‐induced emission (AIE) property by the click addition of thiol to its MI pendant. The click reaction and the AIE effect enabled TPE‐MI to function as a thiol‐specific bioprobe in the solid state. Thus, the spot of TPE‐MI on a TLC plate became emissive when it had been exposed to L ‐cysteine, an amino acid containing a thiol group, but remained nonemissive when exposed to other amino acids that lack free thiol units. The thiol‐activated emission was rapid and strong, readily detected by the naked eye at an analyte concentration as low as approximately 1 ppb, thanks to the “lighting up” nature of the bioprobing process. Similarly, the emission of TPE‐MI was turned on only by the proteins containing free thiol units, such as glutathione. Clear fluorescence images were taken when living cells were stained by using TPE‐MI as a visualization agent, affording a facile fluorescent maker for mapping the distribution of thiol species in cellular systems. 相似文献
993.
Zhanfeng Zheng Dr. Jaclyn Teo Xi Chen Dr. Hongwei Liu Dr. Yong Yuan Dr. Eric R. Waclawik Dr. Ziyi Zhong Dr. Huaiyong Zhu Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(4):1202-1211
Three catalytic oxidation reactions have been studied: The ultraviolet (UV) light induced photocatalytic decomposition of the synthetic dye sulforhodamine B (SRB) in the presence of TiO2 nanostructures in water, together with two reactions employing Au/TiO2 nanostructure catalysts, namely, CO oxidation in air and the decomposition of formaldehyde under visible light irradiation. Four kinds of TiO2 nanotubes and nanorods with different phases and compositions were prepared for this study, and gold nanoparticle (Au‐NP) catalysts were supported on some of these TiO2 nanostructures (to form Au/TiO2 catalysts). FTIR emission spectroscopy (IES) measurements provided evidence that the order of the surface OH regeneration ability of the four types of TiO2 nanostructures studied gave the same trend as the catalytic activities of the TiO2 nanostructures or their respective Au/TiO2 catalysts for the three oxidation reactions. Both IES and X‐ray photoelectron spectroscopy (XPS) proved that anatase TiO2 had the strongest OH regeneration ability among the four types of TiO2 phases or compositions. Based on these results, a model for the surface OH group generation, absorption, and activation of molecular oxygen has been proposed: The oxygen vacancies at the bridging O2? sites on TiO2 surfaces dissociatively absorb water molecules to form OH groups that facilitate adsorption and activation of O2 molecules in nearby oxygen vacancies by lowering the absorption energy of molecular O2. A new mechanism for the photocatalytic formaldehyde decomposition with the Au/TiO2 catalysts is also proposed, based on the photocatalytic activity of the Au‐NPs under visible light. The Au‐NPs absorb the light owing to the surface plasmon resonance effect and mediate the electron transfers that the reaction needs. 相似文献
994.
Ming‐Zhong Wang Cong‐Ying Zhou Man‐Kin Wong Dr. Chi‐Ming Che Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(19):5723-5735
Ruthenium porphyrins (particularly [Ru(2,6‐Cl2tpp)CO]; tpp=tetraphenylporphinato) and RuCl3 can act as oxidation and/or Lewis acid catalysts for direct C‐3 alkylation of indoles, giving the desired products in high yields (up to 82 % based on 60–95 % substrate conversions). These ruthenium compounds catalyze oxidative coupling reactions of a wide variety of anilines and indoles bearing electron‐withdrawing or electron‐donating substituents with high regioselectivity when using tBuOOH as an oxidant, resulting in the alkylation of N‐arylindoles to 3‐{[(N‐aryl‐N‐alkyl)amino]methyl}indoles (yield: up to 82 %, conversion: up to 95 %) and the alkylation of N‐alkyl or N‐H indoles to 3‐[p‐(dialkylamino)benzyl]indoles (yield: up to 73 %, conversion: up to 92 %). A tentative reaction mechanism involving two pathways is proposed: an iminium ion intermediate may be generated by oxidation of an sp3 C? H bond of the alkylated aniline by an oxoruthenium species; this iminium ion could then either be trapped by an N‐arylindole (pathway A) or converted to formaldehyde, allowing a subsequent three‐component coupling reaction of the in situ generated formaldehyde with an N‐alkylindole and an aniline in the presence of a Lewis acid catalyst (pathway B). The results of deuterium‐labeling experiments are consistent with the alkylation of N‐alkylindoles via pathway B. The relative reaction rates of [Ru(2,6‐Cl2tpp)CO]‐catalyzed oxidative coupling reactions of 4‐X‐substituted N,N‐dimethylanilines with N‐phenylindole (using tBuOOH as oxidant), determined through competition experiments, correlate linearly with the substituent constants σ (R2=0.989), giving a ρ value of ?1.09. This ρ value and the magnitudes of the intra‐ and intermolecular deuterium isotope effects (kH/kD) suggest that electron transfer most likely occurs during the initial stage of the oxidation of 4‐X‐substituted N,N‐dimethylanilines. Ruthenium‐catalyzed three‐component reaction of N‐alkyl/N‐H indoles, paraformaldehyde, and anilines gave 3‐[p‐(dialkylamino)benzyl]indoles in up to 82 % yield (conversion: up to 95 %). 相似文献
995.
Guo-Liang Dai Chuan-Feng Wang Yan-Xian Jin Jie Zhao Ai-Guo Zhong De-Man Han 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2010,84(6):971-979
The potential energy surfaces for the La+SCO and La++ SCO reactions have been theoretically investigated by using the DFT (B3LYP/ECP/6-311+G(2d)) level of theory. Both ground and excited state potential energy surfaces (PES) are discussed. The present results show
that the reaction mechanism is insertion mechanism both along the C-S and C-O bond activation branches, but the C-S bond activation
is much more favorable in energy than the C-O bond activation. The reaction of La atom with SCO was shown to occur preferentially
on the ground state (doublet) PES throughout the reaction process, and the experimentally observed species, have been explained
according to the mechanisms revealed in this work. While for the reaction between La+ cation with SCO, it involves potential energy curve-crossing which dramatically affects reaction mechanism, and the crossing
points (CPs) have been localized by the approach suggested by Yoshizawa et al. Due to the intersystem crossing existing in
the reaction process of La+ with SCO, the products SLa+(η2CO) and OLa+(η2CS) may not form. This mechanism is different from that of La + SCO system. All our theoretical results not only support the
existing conclusions inferred from early experiment, but also complement the pathway and mechanism for this reaction. 相似文献
996.
Liangqia Guo Jianhai Zhong Jinmei Wu FengFu Fu Guonan Chen Xiaoyan Zheng 《Talanta》2010,82(5):1654-12011
A simple, rapid, field-portable colorimetric method for the detection of melamine based on melamine-induced color change of label-free gold nanoparticles (Au NPs) was developed in this study. Melamine can induced the aggregation of Au NPs and results in the color change from wine-red to purple, which provided a platform for rapid and field-portable colorimetric detection of melamine. The proposed method can be used to detect melamine in liquid milk and infant formula with a detection limit of 1.0 and 4.2 ppm, respectively, within 30 min by naked eyes observation without the aid of any advanced instrument and the need of any complex pretreatment, and detect as low as 0.15 ppm of melamine in liquid milk and 2.5 ppm of melamine in infant formula with UV-vis-spectroscopy. The proposed method is promising for on-site screening of melamine adulterant in milk products. 相似文献
997.
It is well known that the ferroelectric performance of poly (vinylidene fluoride) (PVDF) is caused by its β-crystal structure, which can be efficiently induced through a stretching process applied to the PVDF. Though numerous PVDF nanocomposites have been reported on, there is still a lack of studies on how the stretching process affects the phase transformation in PVDF nanocomposites. In this study, the effects of stretching on the crystalline structures and alternating current (AC) conductivity of PVDF nanocomposites with different concentrations (up to 5.0 wt.%) of CNFs were investigated. Results revealed that the stretching process is not only an effective approach to produce β-crystal from pure PVDF, but also for CNF/PVDF composites. The extremely high phase transformation from α- to β-crystal (?96%) is maintained for the nanocomposites with above 1.0 wt.% CNFs. The AC conductivity of CNF/PVDF composites remarkably decreases when the resultant percolation threshold is raised from 1.0 to 4.2 wt.% CNFs after stretching. This is attributed to the reduced crystallinity induced by the phase transformation from α- to β-PVDF as well as the CNF re-orientation. 相似文献
998.
Wen‐Zuo Li Jian‐Bo Cheng Qing‐ Zhong Li Bao‐An Gong Jia‐Zhong Sun 《International journal of quantum chemistry》2010,110(10):1857-1862
The HBeN? and HNBe? anions have been investigated for the first time using the CASSCF, CASPT2, and DFT/B3LYP methods with the contracted atomic natural orbital (ANO) and cc‐pVTZ basis sets. The geometries of all stationary points along the potential energy surfaces were optimized at the CASSCF/ANO and B3LYP/cc‐pVTZ levels. The ground and the first excited states of HBeN? are predicted to be X2Π and A2Σ+ states, respectively. It was predicted that the ground state of HNBe? is X2Σ+ state. The A2Π state of HNBe? has unique imaginary frequency. A bend local minimum M1 was found along the 12A″ potential energy surface and the A2Π state of HNBe? should be the transition state of the isomerization reactions for M1 ? M1. The CASPT2/ANO potential energy curves of isomerization reactions were calculated as a function of HBeN bond angle. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 相似文献
999.
1000.
Bai Sun Minqiang Li Fang Zhang Yu Zhong Nansheng Kang Wei Lu Jinhuai Liu 《Microchemical Journal》2010,95(2):293-297
A prototype setup for detecting illicit materials by energy-dispersive X-ray diffraction (EDXRD) has been developed. The obtained results of NaCl by the equipment suggest that the total measurement system is reliable and can be used to detect different kinds of materials. The tests of TNT, methamphetamine and heroin are also performed on this equipment and the related EDXRD spectra are obviously influenced by the detecting angle and the X-ray sources. The detecting angle of 10° is more suitable for detecting TNT and methamphetamine, while 12° is better for heroin. Moreover, the curves of TNT, methamphetamine and heroin emitted by W target have more diffraction peaks than those emitted by Cu or Mo target, while the peak intensities of TNT and methamphetamine emitted by Mo are stronger than those emitted by Cu or W target. The curve of methamphetamine emitted by Mo target shows a special characteristic and exhibits a super strong diffraction peak located at 1.62 Å− 1, which can be attributed to the effect arising from Mo kα and kβ. 相似文献