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971.
Highly Luminescent N‐Doped Carbon Quantum Dots as an Effective Multifunctional Fluorescence Sensing Platform 下载免费PDF全文
Dr. Zhaosheng Qian Juanjuan Ma Xiaoyue Shan Dr. Hui Feng Prof. Linxiang Shao Prof. Jianrong Chen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(8):2254-2263
The doping of carbon quantum dots with nitrogen provides a promising direction to improve fluorescence performance and broaden their applications in sensing systems. Herein we report a one‐pot solvothermal synthesis of N‐doped carbon quantum dots (NCQDs) and the synthesis of a series of NCQDs with different nitrogen contents. The as‐prepared NCQDs were compared with carbon quantum dots (CQDs); the introduction of nitrogen atoms largely increased the quantum yield of NCQDs and highest emission efficiency is up to 36.3 %. The fluorescence enhancement may originate from more polyaromatic structures induced by incorporated nitrogen atoms and protonation of nitrogen atoms on dots. It was found that NCQDs can act as a multifunctional fluorescence sensing platform because they can be used to detect pH values, AgI, and FeIII in aqueous solution. The fluorescence intensity of NCQDs is inversely proportional to pH values across a broad range from 5.0 to 13.5, which indicates that NCQDs can be devised as an effective pH indicator. Selective detection of AgI and FeIII was achieved based on their distinctive fluorescence influence because AgI can significantly enhance the fluorescence whereas FeIII can greatly quench the fluorescence. The quantitative determination of AgI can be accomplished with NCQDs by using the linear relationship between fluorescence intensity of NCQDs and concentration of AgI. The sensitive detection of H2O2 was developed by taking advantage of the distinct quenching ability of FeIII and FeII toward the fluorescence of NCQDs. Cellular toxicity test showed NCQDs still retain low toxicity to cells despite the introduction of a great deal of nitrogen atoms. Moreover, bioimaging experiments demonstrated that NCQDs have stronger resistance to photobleaching than CQDs and more excellent fluorescence labeling performance. 相似文献
972.
Tuning the Electronic Coupling in Cyclometalated Diruthenium Complexes through Substituent Effects: A Correlation between the Experimental and Calculated Results 下载免费PDF全文
Jiang‐Yang Shao Prof. Dr. Yu‐Wu Zhong 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(28):8702-8713
A common bridging ligand, 3,3′,5,5′‐tetrakis(N‐methylbenzimidazol‐2‐yl)biphenyl, and four terpyridine terminal ligands with various substituents (amine, tolyl, nitro, and ester groups) have been used to synthesize ten cyclometalated diruthenium complexes 1 2+– 10 2+. Among them, compounds 1 2+– 6 2+ are redox nonsymmetric, and others are symmetric. These complexes show two RuIII/II processes and an intervalence charge transfer (IVCT) transition in the one‐electron oxidized state. The potential separation (ΔE) of 1 2+– 10 2+ has been correlated to the energy difference ΔG0, the energy of the IVCT band Eop, and the ground‐state delocalization coefficient α2. Time‐dependent (TD)DFT calculations suggest that the absorptions in the visible region of 1 2+– 6 2+ are mainly associated with the metal‐to‐ligand charge‐transfer transitions from both ruthenium ions and to both terminal ligands and the bridging ligand. However, the energies of these transitions vary significantly. DFT calculations have been performed on 1 2+– 6 2+ and 1 3+– 6 3+ to give information on the electronic structures and spin populations of the mixed‐valent compounds. The TDDFT‐predicted IVCT excitations reproduce well the experimental trends in transition energies. In addition, three monoruthenium complexes have been synthesized for a comparison study. 相似文献
973.
Rationally Investigating the Influence of T1 Location on Electroluminescence Performance of Aryl Amine Modified Phosphine Oxide Materials 下载免费PDF全文
Chunmiao Han Liping Zhu Jing Li Fangchao Zhao Dr. Hui Xu Prof. Dongge Ma Prof. Pengfei Yan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(49):16350-16359
The correspondence between triplet location effect and host‐localized triplet–triplet annihilation and triplet–polaron quenching effects was performed on the basis of a series of naphthyldiphenylamine (DPNA)‐modified phosphine oxide hosts. The number and ratio of DPNA and diphenylphosphine oxide was adjusted to afford symmetrical and unsymmetrical molecular structures and different electronic environments. As designed, the first triplet (T1) states were successfully localized on the specific DPNA chromophores. Owing to the meso‐ and multi‐insulating linkages, identical optical properties and comparable electrical performance was observed, including the same first singlet (S1) and T1 energy levels to support the similar singlet and triplet energy transfer and the close frontier molecular orbital energy levels. This established the basis of rational investigation on T1 location effect without interference from other optoelectronic factors. 相似文献
974.
Reactivity of Oxygen Radical Anions Bound to Scandia Nanoparticles in the Gas Phase: CH Bond Activation 下载免费PDF全文
Li‐Hua Tian Jing‐Heng Meng Dr. Xiao‐Nan Wu Dr. Yan‐Xia Zhao Dr. Xun‐Lei Ding Prof. Dr. Sheng‐Gui He Dr. Tong‐Mei Ma 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(4):1167-1175
The activation of C?H bonds in alkanes is currently a hot research topic in chemistry. The atomic oxygen radical anion (O?.) is an important species in C?H activation. The mechanistic details of C?H activation by O?. radicals can be well understood by studying the reactions between O?. containing transition metal oxide clusters and alkanes. Here the reactivity of scandium oxide cluster anions toward n‐butane was studied by using a high‐resolution time‐of‐flight mass spectrometer coupled with a fast flow reactor. Hydrogen atom abstraction (HAA) from n‐butane by (Sc2O3)NO? (N=1–18) clusters was observed. The reactivity of (Sc2O3)NO? (N=1–18) clusters is significantly sizedependent and the highest reactivity was observed for N=4 (Sc8O13?) and 12 (Sc24O37?). Larger (Sc2O3)NO? clusters generally have higher reactivity than the smaller ones. Density functional theory calculations were performed to interpret the reactivity of (Sc2O3)NO? (N=1–5) clusters, which were found to contain the O?. radicals as the active sites. The local charge environment around the O?. radicals was demonstrated to control the experimentally observed size‐dependent reactivity. This work is among the first to report HAA reactivity of cluster anions with dimensions up to nanosize toward alkane molecules. The anionic O?. containing scandium oxide clusters are found to be more reactive than the corresponding cationic ones in the C?H bond activation. 相似文献
975.
Cerium‐Based M4L4 Tetrahedra as Molecular Flasks for Selective Reaction Prompting and Luminescent Reaction Tracing 下载免费PDF全文
Yang Jiao Dr. Jian Wang Dr. Pengyan Wu Liang Zhao Dr. Cheng He Jing Zhang Prof. Chunying Duan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(8):2224-2231
The application of metal–organic polyhedra as “molecular flasks” has precipitated a surge of interest in the reactivity and property of molecules within well‐defined spaces. Inspired by the structures of the natural enzymatic pockets, three metal–organic neutral molecular tetrahedral, Ce‐TTS, Ce‐TNS and Ce‐TBS (H6TTS: N′,N′′,N′′′‐nitrilotris‐4,4′,4′′‐(2‐hydroxybenzylidene)‐benzohydrazide; H6TNS: N′,N′′,N′′′‐nitrilotris‐6,6′,6′′‐(2‐hydroxybenzylidene)‐2‐naphthohydrazide; H6TBS: 1,3,5‐ phenyltris ‐4,4′,4′′‐(2‐hydroxybenzylidene)benzohydrazide), which exhibit different size of the edges and cavities, were achieved through self‐assembly by incorporating robust amide‐containing tridentate chelating sites into the fragments of the ligands. They acted as molecular flasks to prompt the cyanosilylation of aldehydes with excellent selectivity towards the substrates size. The amide groups worked as trigger sites and catalytic driven forces to achieve efficient guest interactions, enforcing the substrates proximity within the cavity. Experiments on catalysts with the different cavity radii and substrates with the different molecular size demonstrated that the catalytic performance exhibited enzymatical catalytic mechanism and occurred in the molecular flask. These amides were also able to amplify guest‐bonding events into the measurable outputs for the detection of concentration variations of the substrates, providing the possibility for metal–organic hosts to work as smart molecular flasks for the luminescent tracing of catalytic reactions. 相似文献
976.
Oligotriarylamines with a Pyrene Core: A Multicenter Strategy for Enhancing Radical Cation and Dication Stability and Tuning Spin Distribution 下载免费PDF全文
Hai‐Jing Nie Chang‐Jiang Yao Jiang‐Yang Shao Prof. Dr. Jiannian Yao Prof. Dr. Yu‐Wu Zhong 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(52):17454-17465
Monoamine 1 , diamines 2 – 4 , triamine 5 , and tetraamine 6 have been synthesized by substituting dianisylamino groups at the 1‐, 3‐, 6‐, and/or 8‐positions of pyrene. Diamines 2 – 4 differ in the positions of the amine substituents. No pyrene–pyrene interactions are evident in the single‐crystal packing of 3 , 4 , and 6 . With increasing numbers of amine substituents, the first oxidation potential decreases progressively from the mono‐ to the tetraamine. These compounds show intense charge‐transfer (CT) emission in CH2Cl2 at around 530 nm with quantum yields of 48–68 %. Upon stepwise oxidation by electrolysis or chemical oxidation, these compounds were transformed into radical cations 1 ?+– 6 ?+ and dications 2 2+– 6 2+, which feature strong visible and near‐infrared absorptions. Time‐dependent density functional theory studies suggested the presence of localized transitions from the pyrene radical cation and aminium radical cation, intervalence CT, and CT between the pyrene and amine moieties. Spectroscopic studies indicated that these radical cations and dications have good stability. Triamine 5 and tetraamine 6 formed efficient CT complexes with tetracyanoquinodimethane in solution. The results of EPR spectroscopy and density functional theory calculations suggested that the dications 2 2+– 4 2+ have a triplet ground state, whereas 5 2+ and 6 2+ have a singlet ground state. The dication of 1,3‐disubstituted diamine 4 exhibits a strong EPR signal. 相似文献
977.
α‐Fe2O3 Cubes with High Visible‐Light‐Activated Photoelectrochemical Activity towards Glucose: Hydrothermal Synthesis Assisted by a Hydrophobic Ionic Liquid 下载免费PDF全文
Dr. Li Xu Dr. Jiexiang Xia Prof. Leigang Wang Dr. Jing Qian Prof. Huaming Li Prof. Kun Wang Dr. Kaiyong Sun Prof. Minqiang He 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(8):2244-2253
A liquid/liquid interfacial reaction system was designed to fabricate α‐Fe2O3 cubes. The reaction system uses a hydrophobic ionic liquid containing iron ions ([(C8H17)2(CH3)2N]FeCl4) for manufacturing α‐Fe2O3 cubes by a novel and environmentally friendly hydrothermal method under low‐temperature conditions (140 °C). The iron‐containing ionic liquid is hydrophobic and can form a liquid/liquid interface with water, which is vital for fabrication of the α‐Fe2O3 cubes. Nanomaterials synthesized from hydrophobic iron‐containing ionic liquids show good crystallinity, well‐developed morphology, and uniform size. The effect of different ionic liquids on the morphology of α‐Fe2O3 was investigated in detail. [(C8H17)2(CH3)2N]FeCl4 is assumed to perform the triple role of forming a liquid/liquid interface with water and acting as reactant and template at the same time. The effect of the reaction temperature on the formation of the α‐Fe2O3 cubes was also studied. Temperatures lower or higher than 140 °C are not conducive to formation of the α‐Fe2O3 cubes. Their photoelectrochemical properties were tested by means of the transient photocurrent response of electrodes modified with as‐prepared α‐Fe2O3 cubes. The photocurrent response of an α‐Fe2O3 cubes/indium tin oxide electrode is high and stable, and it shows great promise as a photoelectrochemical glucose sensor with high sensitivity and fast response, which are beneficial to practical applications of nanosensors. 相似文献
978.
Copper‐Catalyzed One‐Pot Denitrogenative–Dehydrogenative–Decarboxylative Coupling of β‐Ketoacids with Trifluorodiazoethane: Facile Access to Trifluoromethylated Aldol Products 下载免费PDF全文
Dr. Heng‐Ying Xiong Zhen‐Yan Yang Zhen Chen Jun‐Liang Zeng Dr. Jing Nie Prof. Jun‐An Ma 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(27):8325-8329
A novel copper‐catalyzed one‐pot cross‐coupling of β‐ketoacids with in situ generated trifluorodiazoethane has been developed. This reaction provides a direct and efficient method, in which one C?C bond and one C?O bond were formed in a carbenoid center with concomitant denitrogenation–dehydrogenation–decarboxylation, to afford trifluoromethylated aldol products. In several preliminary experiments, good to high enantioselectivities were also obtained. 相似文献
979.
Tailoring 3,3′‐Dihydroxyisorenieratene to Hydroxystilbene: Finding a Resveratrol Analogue with Increased Antiproliferation Activity and Cell Selectivity 下载免费PDF全文
Yan‐Fei Kang Wen‐Jing Yan Ting‐Wen Zhou Dr. Fang Dai Dr. Xiu‐Zhuang Li Xia‐Zhen Bao Yu‐Ting Du Cui‐Hong Yuan Hai‐Bo Wang Xiao‐Rong Ren Dr. Qiang Liu Dr. Xiao‐Ling Jin Prof. Dr. Bo Zhou Prof. Dr. Jie Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(29):8904-8908
Four novel compounds were designed by “tailoring” 3,3′‐dihydroxyisorenieratene (a natural carotenoid) based on an isoprene unit retention truncation strategy. Among them, the smallest molecule 1 (2,3,6,2′,3′,6′‐hexamethyl‐4,4′‐dihydroxy‐trans‐stilbene) was concisely synthesized in a one‐pot Stille–Heck tandem sequence, and surfaced as a promising lead molecule in terms of its selective antiproliferative activity mediated by blocking the NCI‐H460 cell cycle in G1 phase. Additionally, theoretical calculations and cell uptake experiments indicate that the unique polymethylation pattern of compound 1 significantly induces a conformational change shift out of planarity and increases its cell uptake and metabolic stability. The observation should be helpful to rationally design resveratrol‐inspired antiproliferative agents. 相似文献
980.
Solvothermal Transformation of a Calcium Oleate Precursor into Large‐Sized Highly Ordered Arrays of Ultralong Hydroxyapatite Microtubes 下载免费PDF全文
Dr. Bing‐Qiang Lu Prof. Dr. Ying‐Jie Zhu Feng Chen Chao Qi Xin‐Yu Zhao Jing Zhao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(23):7116-7121
Hydroxyapatite (HAP), a well‐known member of the calcium phosphate family, is the major inorganic component of bones and teeth in vertebrates. The highly ordered arrays of HAP structures are of great significance for hard tissue repair and for understanding the formation mechanisms of bones and teeth. However, the synthesis of highly ordered HAP structure arrays remains a great challenge. In this work, inspired by the ordered structure of tooth enamel, we have successfully synthesized three‐dimensional bulk materials with large sizes (millimeter scale) that are made of highly ordered arrays of ultralong HAP microtubes (HOAUHMs) by solvothermal transformation of calcium oleate precursor. The core–shell‐structured oblate sphere consists of a core that is composed of HAP nanorods and a shell that consists of highly ordered HAP microtube arrays. The prepared HOAUHMs are large: 6.0 mm in diameter and up to 1.4 mm in thickness. With increasing solvothermal reaction time, the HOAUHMs grow larger; the microtubes become more uniform and more ordered. This work provides a new synthetic method for synthesizing highly ordered arrays of uniform HAP ultralong microtubes that are promising for biomedical applications. 相似文献