- Aggregated Structures of Two-Dimensional Covalent Organic Frameworks
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Covalent organic frameworks (COFs) have found wide applications due to their crystalline structures. However, it is still challenging to quantify crystalline phases in a COF sample. This is because COFs, especially 2D ones, are usually obtained as mixtures of polycrystalline powders. Therefore, the understanding of the aggregated structures of 2D COFs is of significant importance for their efficient utilization. Here we report the study of the aggregated structures of 2D COFs using 13C solid-state nuclear magnetic resonance (13C SSNMR). We find that 13C SSNMR can distinguish different aggregated structures in a 2D COF because COF layer stacking creates confined spaces that enable intimate interactions between atoms/groups from adjacent layers. Subsequently, the chemical environments of these atoms/groups are changed compared with those of the nonstacking structures. Such a change in the chemical environment is significant enough to be captured by 13C SSNMR. After analyzing four 2D COFs, we find it particularly useful for 13C SSNMR to quantitatively distinguish the AA stacking structure from other aggregated structures. Additionally, 13C SSNMR data suggest the existence of offset stacking structures in 2D COFs. These offset stacking structures are not long-range-ordered and are eluded from X-ray-based detections, and thus they have not been reported before. In addition to the dried state, the aggregated structures of solvated 2D COFs are also studied by 13C SSNMR, showing that 2D COFs have different aggregated structures in dried versus solvated states. These results represent the first quantitative study on the aggregated structures of 2D COFs, deepen our understanding of the structures of 2D COFs, and further their applications.
- Baugh, Lisa Saunders,Calabro, David C.,Kang, Chengjun,Usadi, Adam K.,Wang, Yuxiang,Yu, Kexin,Zhang, Zhaoqiang,Zhao, Dan
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supporting information
p. 3192 - 3199
(2022/03/02)
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- Synthesis of a novel chiral DA-TD covalent organic framework for open-tubular capillary electrochromatography enantioseparation
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Herein, a novel chiral covalent organic framework, DA-TD COF, with good chemical/thermal stability was synthesized and used as a chiral stationary phase for open-tubular capillary electrochromatography enantioseparation. The DA-TD COF coated capillary exh
- Chen, Hongli,Chen, Xingguo,Lv, Wenjuan,Pan, Congjie,Wang, Guoxiu
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supporting information
p. 403 - 406
(2022/01/19)
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- Rational Fabrication of Crystalline Smart Materials for Rapid Detection and Efficient Removal of Ozone
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Traditional ozone sensing and removal materials still suffer from high energy consumption and low efficiency. Thus, seeking new ozone-responsive materials with high efficiency and broad working conditions is of great significance. Herein, we first develop
- Yan, Dong,Wang, Zhifang,Cheng, Peng,Chen, Yao,Zhang, Zhenjie
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supporting information
p. 6055 - 6060
(2021/02/01)
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- A novel bifunctional-group salamo-like multi-purpose dye probe based on ESIPT and RAHB effect: Distinction of cyanide and hydrazine through optical signal differential protocol
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A novel bifunctional-group multi-purpose dye probe p-TNS has been designed and synthesized. The probe p-TNS has unique excited-state intramolecular proton transfer (ESIPT) and resonance-assisted hydrogen bonding (RAHB) coupled system, was confirmed to detect cyanide and hydrazine by blocking the ESIPT effect. Cyanide can change the fluorescence of the solution from bright green to orange-red (116 nm Stokes shift), while hydrazine causes the bright green fluorescence to be quenched. The recognition mechanism of the probe p-TNS to CN? and N2H4 was proposed reasonably through spectral characterizations and theoretical calculations. Combined with theoretical calculations, it was speculated that the solvent dependence may be caused by the ICT effect in the molecule. The probe p-TNS could be prepared into test strips for the detection of cyanide and hydrazine. In addition, the probe molecule can also be used to detect trace amounts of cyanide in agricultural products, and respond to gaseous hydrazine by direct contact, indicating that the probe p-TNS has good practical application prospects. Therefore, this molecular framework provides a new way of thinking about detecting multiple target substances.
- Chen, Zhuang-Zhuang,Deng, Yun-Hu,Zhang, Ting,Dong, Wen-Kui
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supporting information
(2021/06/29)
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- Metalloporphyrin and Ionic Liquid-Functionalized Covalent Organic Frameworks for Catalytic CO2Cycloaddition via Visible-Light-Induced Photothermal Conversion
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We report the construction of a porphyrin and imidazolium-ionic liquid (IL)-decorated and quinoline-linked covalent organic framework (COF, abbreviated as COF-P1-1) via a three-component one-pot Povarov reaction. After post-synthetic metallization of COF-P1-1 with Co(II) ions, the metallized COF-PI-2 is generated. COF-PI-2 is chemically stable and displays highly selective CO2 adsorption and good visible-light-induced photothermal conversion ability (ΔT = 26 °C). Furthermore, the coexistence of Co(II)-porphyrin and imidazolium-IL within COF-PI-2 has guaranteed its highly efficient activity for CO2 cycloaddition. Of note, the needed thermal energy for the reactions is derived from the photothermal conversion of the Co(II)-porphyrin COF upon visible-light irradiation. More importantly, the CO2 cycloaddition herein is a "window ledge"reaction, and it can proceed smoothly upon natural sunlight irradiation. In addition, a scaled-up CO2 cycloaddition can be readily achieved using a COF-PI-2@chitosan aerogel-based fixed-bed model reactor. Our research provides a new avenue for COF-based greenhouse gas disposal in an eco-friendly and energy- and source-saving way.
- Ding, Luo-Gang,Yao, Bing-Jian,Wu, Wen-Xiu,Yu, Zhi-Gao,Wang, Xiao-Yu,Kan, Jing-Lan,Dong, Yu-Bin
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supporting information
p. 12591 - 12601
(2021/08/24)
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- RED FLUORESCENT HIGHLY HYDROSOLUBLE COMPOUND AND FLUORESCENT DYE USING THE SAME
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PROBLEM TO BE SOLVED: To provide a hydrosoluble fluorescent probe having property of localizing in a mitochondrion and having light emission in the near infrared. SOLUTION: A fluorescent dye including compound represented by the following formula (1) is u
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- Interlayer Shifting in Two-Dimensional Covalent Organic Frameworks
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Layer-stacking structures are very common in two-dimensional covalent organic frameworks (2D COFs). While their structures are normally determined under solvent-free conditions, the structures of solvated 2D COFs are largely unexplored. We report herein t
- Kang, Chengjun,Zhang, Zhaoqiang,Wee, Vanessa,Usadi, Adam K.,Calabro, David C.,Baugh, Lisa Saunders,Wang, Shun,Wang, Yuxiang,Zhao, Dan
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supporting information
p. 12995 - 13002
(2020/09/01)
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- Photocatalytic Molecular Oxygen Activation by Regulating Excitonic Effects in Covalent Organic Frameworks
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Excitonic effects caused by Coulomb interactions between electrons and holes play subtle and significant roles on photocatalysis, yet have been long ignored. Herein, porphyrinic covalent organic frameworks (COFs, specifically DhaTph-M), in the absence or presence of different metals in porphyrin centers, have been shown as ideal models to regulate excitonic effects. Remarkably, the incorporation of Zn2+ in the COF facilitates the conversion of singlet to triplet excitons, whereas the Ni2+ introduction promotes the dissociation of excitons to hot carriers under photoexcitation. Accordingly, the discriminative excitonic behavior of DhaTph-Zn and DhaTph-Ni enables the activation of O2 to 1O2 and O2?-, respectively, under visible light irradiation, resulting in distinctly different activity and selectivity in photocatalytic terpinene oxidation. Benefiting from these results, DhaTph-Ni exhibits excellent photocatalytic activity in O2?-engaged hydroxylation of boronic acid, while DhaTph-Zn possesses superior performance in 1O2-mediated selective oxidation of organic sulfides. This work provides in-depth insights into molecular oxygen activation and opens an avenue to the regulation of excitonic effects based on COFs.
- Qian, Yunyang,Li, Dandan,Han, Yulan,Jiang, Hai-Long
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supporting information
p. 20763 - 20771
(2020/12/23)
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- Efficient synthesis of NIR emitting bis[2-(2′-hydroxylphenyl)benzoxazole] derivative and its potential for imaging applications
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Unassymetric bis[2-(2′-hydroxyphenylbenzoxole)] bis(HBO) derivatives with a DPA functionality for zinc binding have been developed with an efficient synthetic route, using the retrosynthetic analysis. Comparison of bis(HBO) derivatives with different substitution patterns allows us to verify and optimize their unique fluorescence properties. Upon binding zinc cation, bis(HBO) derivatives give a large fluorescence turn-on in both visible (λem ≈ 536 nm) and near-infrared (NIR) window (λem ≈ 746 nm). The probes are readily excitable by a 488 nm laser, making this series of compounds a suitable imaging tool for in vitro and in vivo study on a confocal microscope. The application of zinc binding-induced fluorescence turn-on is successfully demonstrated in cellular environments and thrombus imaging.
- Wang, Junfeng,Baumann, Hannah,Bi, Xiaoman,Shriver, Leah P.,Zhang, Zhaoda,Pang, Yi
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supporting information
(2020/01/25)
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- Synthesis, electronic structure, linear and nonlinear photophysical properties of novel asymmetric branched compounds
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A series of novel asymmetric branched compounds that utilize a 1,3,5-triazine core and feature D-π-A-(π-D′-π-A′)0-2 configurations (D = donor, A = acceptor, π = conjugated bridge) were designed, successfully synthesized, and fully characterized by 1H NMR, 13C NMR, FT-IR, and HRMS. Their photophysical properties including linear absorption, one-photon excited fluorescence, two-photon absorption, and frequency up-converted fluorescence, were systematically investigated in different solvents. With a rise in the polarity of solvents, the peak positions of the one-photon excited fluorescence are red-shifted and the Stokes shifts increase, while the linear absorption wavelengths change slightly. In addition, the target compounds except CZ show the positive solvatokinetic effect. With a rise in the number of branches, the red shifts of the absorption and emission maxima, the hyperchromicity of the molar absorption coefficients, and the decrease of the Stokes shifts are observed. The peripheral electron donors (carbazole, phenothiazine) and acceptors (pyridine, benzimidazole) also exert an important influence on the photophysical properties. Under excitation of 690–930 nm fs laser pulses, all the target compounds emit frequency up-converted fluorescence with the maximal peaks at 471–575 nm, and the two-photon absorption cross-sections in THF are 132 (PTZ), 182 (CZ), 453 (CZ-Py1), 844 (CZ-Py2), 1244 (CZ-BI1), and 2072 (CZ-BI2) GM, respectively. Their two-photon response is found to be nearly additive with respect to the number of branches. The time-dependent density functional theory calculations were conducted to gain an insight into their electronic structures and to better understand the structure-photophysical property relationships. The results clearly indicate the importance of appropriate structural units on the enhancement of two-photon absorption properties.
- Cai, Zhi-Bin,Chen, Li-Jun,Li, Sheng-Li,Ye, Qing,Tian, Yu-Peng
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- Water-soluble red-fluorescent dyes for two-photon deep-tissue imaging
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To realize in vivo deep two-photon fluorescence microscopy (TPFM), a probe is required that can undergo two-photon excitation and emit in the optical window of tissues (6501100 nm). In addition, the probe should have high water solubility to avoid harmful
- Ano, Hikari,Kawamata, Jun,Onishi, Shozo,Suzuki, Yasutaka
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p. 1226 - 1233
(2020/11/17)
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- Reaction Environment Modification in Covalent Organic Frameworks for Catalytic Performance Enhancement
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Herein, we show how the spatial environment in the functional pores of covalent organic frameworks (COFs) can be manipulated in order to exert control in catalysis. The underlying mechanism of this strategy relies on the placement of linear polymers in the pore channels that are anchored with catalytic species, analogous to outer-sphere residue cooperativity within the active sites of enzymes. This approach benefits from the flexibility and enriched concentration of the functional moieties on the linear polymers, enabling the desired reaction environment in close proximity to the active sites, thereby impacting the reaction outcomes. Specifically, in the representative dehydration of fructose to produce 5-hydroxymethylfurfural, dramatic activity and selectivity improvements have been achieved for the active center of sulfonic acid groups in COFs after encapsulation of polymeric solvent analogues 1-methyl-2-pyrrolidinone and ionic liquid.
- Sun, Qi,Tang, Yongquan,Aguila, Briana,Wang, Sai,Xiao, Feng-Shou,Thallapally, Praveen K.,Al-Enizi, Abdullah M.,Nafady, Ayman,Ma, Shengqian
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supporting information
p. 8670 - 8675
(2019/05/07)
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- Synergistic Effect of Covalent Bonding and Physical Encapsulation of Sulfur in the Pores of a Microporous COF to Improve Cycling Performance in Li-S Batteries
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Lithium-sulfur batteries stands out as a promising technology for energy storage owing to a combination of favorable characteristics including a high theoretical gravimetric capacity, energy density, inexpensive character, and environmental benignity. Covalent organic frameworks (COFs) are a rapidly developing family of functional nanostructures which combine porosity and crystallinity, and which have been already used in these kinds of batteries to build sulfur electrodes, by embedding sulfur into porous COFs in order to enhance cycle lifetimes. In this contribution, this is taken one step forward and a COF endowed with vinyl groups is used, in order to graft sulfur to the COF skeleton through inverse vulcanization. The main aim of the article is to show the synergistic effect of covalent bonding and physical encapsulation of sulfur in the pores of the COF in order to alleviate the fatal redox shuttling process, to improve the cycling performance, and to provide faster ion diffusion pathways. In addition, it is shown how the material with covalently-bound S provides better electrochemical performance under demanding and/or changeable charge conditions than a parent analogue material with sulfur physically confined, but without covalent linkage.
- Royuela, Sergio,Almarza, Joaquín,Manche?o, María J.,Pérez-Flores, Juan C.,Michel, Enrique G.,Ramos, María M.,Zamora, Félix,Ocón, Pilar,Segura, José L.
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p. 12394 - 12404
(2019/09/06)
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- Confinement of Br?nsted acidic ionic liquids into covalent organic frameworks as a catalyst for dehydrative formation of isosorbide from sorbitol
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The confinement of Br?nsted acidic 1-methyl-3-(3-sulfopropyl)-1H-imidazol-3-ium hydrosulfate ([PSMIm][HSO4]) into the channel walls of two-dimensional (2D) COFs using a one-pot self-assembly strategy was achieved by incorporating an imine-linked TPB-DMTP-COF (TPB, triphenylbenzene; DMTP, dimethoxyterephthaldehyde) as the host. An appropriate loading of [PSMIm][HSO4] is crucial for the BIL-COF hybrids to maintain proper geometry in the channel and sufficient acidic sites for the sorbitol substrate and sorbitan intermediate to enter and react. The best yield of isosorbide (97%) from sorbitol to date was obtained in the presence of BIL-COF-30 as the catalyst under optimized conditions. Besides, BIL-COF-30 can be recycled for at least five runs without activity loss.
- Du, Yi-Ran,Xu, Bao-Hua,Pan, Jia-Sheng,Wu, Yi-Wei,Peng, Xiao-Ming,Wang, Yao-Feng,Zhang, Suo-Jiang
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p. 4792 - 4799
(2019/09/09)
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- Microcrystal induced emission enhancement of a small molecule probe and its use for highly efficient detection of 2,4,6-trinitrophenol in water
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In this contribution, we reported a very simple and small molecule material, 2,5-dimethoxyterephthalaldehyde (DMA). It exhibited a relatively weak fluorescence in solution, while showed a steadily increased green fluorescence with typical aggregation- ind
- Liu, Huan,Fu, Yanyan,Xu, Wei,He, Qingguo,Cao, Huimin,Liu, Guohua,Cheng, Jiangong
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p. 857 - 862
(2018/05/03)
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- Pore Environment Control and Enhanced Performance of Enzymes Infiltrated in Covalent Organic Frameworks
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In the drive toward green and sustainable methodologies for chemicals manufacturing, biocatalysts are predicted to have much to offer in the years to come. That being said, their practical applications are often hampered by a lack of long-term operational stability, limited operating range, and a low recyclability for the enzymes utilized. Herein, we show how covalent organic frameworks (COFs) possess all the necessary requirements needed to serve as ideal host materials for enzymes. The resultant biocomposites of this study have shown the ability boost the stability and robustness of the enzyme in question, namely lipase PS, while also displaying activities far outperforming the free enzyme and biocomposites made from other types of porous materials, such as mesoporous silica and metal-organic frameworks, exemplified in the kinetic resolution of the alcohol assays performed. The ability to easily tune the pore environment of a COF using monomers bearing specific functional groups can improve its compatibility with a given enzyme. As a result, the orientation of the enzyme active site can be modulated through designed interactions between both components, thus improving the enzymatic activity of the biocomposites. Moreover, in comparison with their amorphous analogues, the well-defined COF pore channels not only make the accommodated enzymes more accessible to the reagents but also serve as stronger shields to safeguard the enzymes from deactivation, as evidenced by superior activities and tolerance to harsh environments. The amenability of COFs, along with our increasing understanding of the design rules for stabilizing enzymes in an accessible fashion, gives great promise for providing "off the shelf" biocatalysts for synthetic transformations.
- Sun, Qi,Fu, Chung-Wei,Aguila, Briana,Perman, Jason,Wang, Sai,Huang, Hsi-Ya,Xiao, Feng-Shou,Ma, Shengqian
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supporting information
p. 984 - 992
(2018/02/07)
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- Covalent organic frameworks: Efficient, metal-free, heterogeneous organocatalysts for chemical fixation of CO2 under mild conditions
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The cycloaddition of CO2 to epoxides to form cyclic carbonates is very promising and does not generate any side products. Metal-free, heterogeneous organocatalysts offer an environmentally friendly alternative to traditional metal-based catalysts. Herein two triazine-based covalent organic frameworks (COF-JLU6 and COF-JLU7) were successfully synthesized under solvothermal conditions. The structural and chemical properties of COFs were fully characterized by using powder X-ray diffraction analysis, structural simulation, Fourier transform infrared spectroscopy, 13C solid-state NMR spectroscopy, electron microscopy, thermogravimetric analysis and nitrogen adsorption. The two COF materials combine mesopores, high crystallinity and good stability, as well as a large number of hydroxy groups in the pore walls. They possess a high Brunauer-Emmett-Teller (BET) specific surface area up to 1390 m2 g-1 and a large pore volume of 1.78 cm3 g-1. The COF-JLU7 displays a high CO2 uptake of 151 mg g-1 at 273 K and 1 bar. Importantly, COF-JLU7 was found to be a highly effective catalyst to convert CO2 into cyclic carbonate through the cycloaddition reaction with epoxides under mild conditions. The effect of reaction parameters, such as reaction temperature, reaction time and CO2 pressure, on the catalytic performance was also investigated in detail. Moreover, the new framework-based catalyst can be recovered and reused five times without a significant loss of catalytic efficiency.
- Zhi, Yongfeng,Shao, Pengpeng,Feng, Xiao,Xia, Hong,Zhang, Yumin,Shi, Zhan,Mu, Ying,Liu, Xiaoming
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p. 374 - 382
(2018/01/12)
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- Synthesis, photophysical properties, and DNA-binding of novel A-π-D-π-A’ two-photon absorption chromophores
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Three novel two-photon absorption chromophores (1BI, 2TAZ, and 3PyB), which have trans-1,4-divinylbenzene π-bridge, methoxy donors, and different acceptors, were synthesized. Their structures were elucidated by means of hydrogen-1 nuclear magnetic resonan
- Ma, Fei-Fei,Cai, Zhi-Bin,Li, Sheng-Li,Tian, Yu-Peng
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p. 705 - 714
(2018/07/23)
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- Stack the Bowls: Tailoring the Electronic Structure of Corannulene-Integrated Crystalline Materials
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We report the first examples of purely organic donor–acceptor materials with integrated π-bowls (πBs) that combine not only crystallinity and high surface areas but also exhibit tunable electronic properties, resulting in a four-orders-of-magnitude conductivity enhancement in comparison with the parent framework. In addition to the first report of alkyne–azide cycloaddition utilized for corannulene immobilization in the solid state, we also probed the charge transfer rate within the Marcus theory as a function of mutual πB orientation for the first time, as well as shed light on the density of states near the Fermi edge. These studies could foreshadow new avenues for πB utilization for the development of optoelectronic devices or a route for highly efficient porous electrodes.
- Rice, Allison M.,Dolgopolova, Ekaterina A.,Yarbrough, Brandon J.,Leith, Gabrielle A.,Martin, Corey R.,Stephenson, Kenneth S.,Heugh, Rebecca A.,Brandt, Amy J.,Chen, Donna A.,Karakalos, Stavros G.,Smith, Mark D.,Hatzell, Kelsey B.,Pellechia, Perry J.,Garashchuk, Sophya,Shustova, Natalia B.
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p. 11310 - 11315
(2018/08/11)
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- METHODS FOR IDENTIFYING PROTEINS BY USING SYNTHETIC RECEPTORS
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The invention relates to oligomeric macrocycles and to uses thereof as receptors for recognition of protein post-translational modifications (PTM) or specific motifs in proteins.
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Page/Page column 35; 36
(2018/01/19)
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- Green synthesis and photophysical properties of novel 1H-imidazo[4,5-f][1,10]phenanthroline derivatives with blue/cyan two-photon excited fluorescence
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A simple, rapid, and highly efficient method has been developed for the synthesis of a series of novel 1H-imidazo[4,5-f][1,10]phenanthroline derivatives (1BN, 2Py, 3BI, 4BT, and 5MOBI) via a three–component, one–pot reaction under solvent–free conditions.
- Pan, Yu-Lu,Cai, Zhi-Bin,Bai, Li,Ma, Fei-Fei,Li, Sheng-Li,Tian, Yu-Peng
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p. 2886 - 2893
(2017/04/26)
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- Multipolar symmetric and asymmetric N–heterocyclic compounds with efficient two?photon absorption
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A series of novel multipolar symmetric and asymmetric N–heterocyclic compounds with different configurations were designed and synthesized. Their structures were characterized by Fourier transform infrared spectroscopy, hydrogen?1 nuclear magnetic resonan
- Cai, Zhi-Bin,Bai, Li,Pan, Yu-Lu,Ma, Fei-Fei,Li, Sheng-Li,Tian, Yu-Peng
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p. 194 - 205
(2017/06/20)
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- Probe for detecting a variety of ions and application thereof
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The invention discloses a probe for detecting a variety of ions and application thereof. The probe takes tris (2-aminoethyl)amine, O-aminothiophenol and hydroquinone dimethyl as raw materials and is obtained by reaction. The probe disclosed by the invention can realize the single-probe multi-target detection and is low in detection cost and high in detection efficiency. The analysis on a complex microscopic system is facilitated.
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Paragraph 0008; 0081; 0087; 0088
(2018/03/28)
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- Covalent organic frameworks as metal-free heterogeneous photocatalysts for organic transformations
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Two-dimensional covalent organic frameworks (2D-COFs) are excellent candidates for photocatalytic organic transformations due to their periodic columnar π-arrays and ordered nanochannels. Here, we present a novel 2D-COF that features permanent porosity wi
- Zhi, Yongfeng,Li, Ziping,Feng, Xiao,Xia, Hong,Zhang, Yumin,Shi, Zhan,Mu, Ying,Liu, Xiaoming
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supporting information
p. 22933 - 22938
(2017/11/22)
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- Structural and spectroscopic investigation on a new potentially bioactive di-hydrazone containing thiophene heterocyclic rings
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Hydrazones and several substituted hydrazones are associated with a broad spectrum of biological activities, as well as compounds containing the thiophene ring. In this context, a novel di-hydrazone derived from 2-thiophenecarboxylic acid hydrazide was sy
- Nogueira, Vanessa De S.,Ramalho Freitas, Maria Clara,Cruz, Wellington S.,Ribeiro, Tatiana S.,Resende, Jackson A.L.C.,Rey, Nicolás A.
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p. 121 - 129
(2015/11/17)
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- 2,4 and 2,5-bis(benzooxazol-2′-yl)hydroquinone (DHBO) and their borate complexes: Synthesis and optical properties
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This article describes the multistep synthesis and the solution/solid-state optical properties of a series of highly fluorescent dyes based on either a 2,4 or a 2,5-bis(benzooxazol-2′-yl)hydroquinone (DHBO) scaffold. Their fluorescence emission stems from
- Benelhadj, Karima,Massue, Julien,Ulrich, Gilles
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supporting information
p. 5877 - 5884
(2016/07/19)
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- POLYMERS AND OLIGOMERS WITH AGGREGATION-INDUCED EMISSION CHARACTERISTICS FOR IMAGING AND IMAGE-GUIDED THERAPY
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A fluorophore or conjugated polymer with aggregation-induced emission characteristics useful for drug tracking and delivery, identification and labeling of biological subjects, such as cells or parts of a cell, as well as for imaging, and image-guided pho
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- POLYMERIZABLE COMPOUND, POLYMERIZABLE COMPOSITION, POLYMER, AND OPTICALLY ANISOTROPIC SUBSTANCE
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The present invention relates to: a polymerizable compound represented by a formula (I); a polymerizable composition comprising the polymerizable compound and an initiator; a polymer obtained by polymerizing the polymerizable compound or the polymerizable composition; and an optically anisotropic article comprising the polymer [in the formula, Y1 to Y8 are a chemical single bond, —O—, —O—C(═O)—, —C(═O)—O—, or the like; G1 and G2 are a divalent aliphatic group having 1 to 20 carbon atoms, or the like; Z1 and Z2 are an alkenyl group having 2 to 10 carbon atoms, or the like; A1 is a tetravalent aromatic group, or the like; A2 and A3 are a divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms, or the like; A4 and A5 are a divalent aromatic group having 4 to 30 carbon atoms, or the like; Ax1 and Ax2 are an organic group having 2 to 30 carbon atoms that includes an aromatic ring, or the like; Ay1 and Ay2 are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or the like; Q1 and Q2 are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or the like; and m and n are 0 or 1]. According to the present invention, a polymerizable compound, a polymerizable composition, and a polymer that have a practical low melting point, exhibit excellent solubility in a general-purpose solvent, can be produced at low cost, and can produce an optical film that achieves uniform conversion of polarized light over a wide wavelength band, and also provide an optically anisotropic article.
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Paragraph 0223-0226
(2015/12/23)
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- Fullerene dimer derivatives and organic electronic devices containing them
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The present invention relates to a fullerene dimer derivative and to an organic electronic device containing the same. More particularly, the fullerene dimer derivative having a pyrrolidine group according to the present invention can provide an organic electronic device having improved energy conversion efficiency as the fullerene dimer derivative has excellent miscibility with polymeric materials that are electron donors, and an organic electronic device adopting the same can realize a higher open circuit voltage.
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Paragraph 0107-0109
(2016/10/17)
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- Investigation of two-photon absorption properties in new A-D-A compounds emitting blue and yellow fluorescence
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Three new acceptor-donor-acceptor compounds (LBQ, DBQ, BYQ) were synthesized and characterized by infrared, hydrogen nuclear magnetic resonance, mass spectrometry and elemental analysis. Their photophysical properties were investigated including linear ab
- Jin, Fan,Cai, Zhi-Bin,Huang, Jiu-Qiang,Li, Sheng-Li,Tian, Yu-Peng
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- Investigation of photophysical properties of new branched compounds with triazine and benzimidazole units
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Three new acceptor-donor-acceptor branched compounds with triazine and benzimidazole units (M1, M2, and M3) were synthesized and characterized by infrared, hydrogen-1 nuclear magnetic resonance, carbon-13 nuclear magnetic resonance, mass spectrometry, and elemental analysis. Their photophysical properties were investigated including linear absorption, single-photon excited fluorescence, fluorescence quantum yield, two-photon absorption, and frequency up-converted fluorescence. When the number of branches increases, the spectral positions of the linear absorption and the single-photon excited fluorescence show red shifts, while the fluorescence quantum yields decrease. When the polarity of solvents increases, the spectral positions of the single-photon excited fluorescence and the Stokes shifts also show red shifts, while the fluorescence quantum yields of the two-branched compound (M2) and three-branched compound (M3) decrease. Under the excitation of an 800 nm laser with a pulse width of 80 fs, all these compounds emit intense green frequency up-converted fluorescence, and the two-photon absorption cross-sections are 210, 968, and 1613 GM for M1, M2, and M3, respectively. This result shows that significant enhancement of the two-photon absorption cross-section can be achieved by sufficient electronic coupling between the strong charge transfer acceptor-donor-acceptor quadrupolar branches through the s-triazine core. the Partner Organisations 2014.
- Cai, Zhibin,Zhou, Mao,Li, Bo,Chen, Ye,Jin, Fan,Huang, Jiuqiang
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p. 3042 - 3049
(2014/07/07)
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- Liquid crystalline bis(N-salicylideneaniline)s: Synthesis and thermal behavior of constitutional isomers
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The first examples of mesogenic bis(N-salicylideneaniline)s (BSANs), wherein two lipophilic (half-disk shaped) entities are interlinked through the dihydroxydiformylbenzene core, were synthesized and characterized. In particular, three constitutional (positional) isomeric BSANs were prepared by the facile twofold condensation of 3,4,5-tris(alkoxy)anilines with 2,3-dihydroxyterephthalaldehyde, 4,6-dihydroxyisophthalaldehyde, and 2,5-dihydroxyterephthalaldehyde and their structures were established by elemental analyses, FT-IR, 1H NMR, and 13C NMR. Proton NMR experiments demonstrated their existence in enol-imine (OH) form solely. Polarizing optical microscopic, differential scanning calorimetric, and powder X-ray diffraction studies evidenced the occurrence of columnar mesomorphism in two sets of isomers.
- Hiremath, Uma S.
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p. 3419 - 3423
(2013/07/04)
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- Synthesis and properties of bimetallic Hoveyda-Grubbs metathesis catalysts
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The catalytic activity of ruthenium Hoveyda-Grubbs complexes in olefin metathesis is a function of complex steric and electronic effects acting on initiation and propagation steps. In order to study the π-electron factors influencing the initiation process, we attempted syntheses of bimetallic complexes with common organic ligands bearing two chelate rings. While most of the studied ligand exchange reactions of the isomeric bis-chelating benzene derivatives gave mixtures of unstable complexes, a homodinuclear derivative of 1,4-dimethoxy-2,5-divinylbenzene was sparingly soluble and precipitated from the reaction mixture in a pure form. The complex was studied with spectroscopic and X-ray methods, which confirmed the symmetrical bimetallic structure. However, in model metathesis reactions the catalyst displayed activity very comparable to the related monometallic complexes. This suggests that in the bimetallic system two consecutive initiation processes of the metathesis catalyst (first, bimetallic complex + olefin → monometallic complex + propagating species; second, monometallic complex + olefin → styrene + propagating species) proceed at similar rates and, thus, no cooperativity between the two steps is displayed. Properties of the family of bimetallic complexes were probed with NMR studies, and π-electronic effects operating in the systems were discussed.
- Grudzien, Krzysztof,Malinska, Maura,Barbasiewicz, Michal
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scheme or table
p. 3636 - 3646
(2012/07/13)
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- Synthesis of isomerically pure anti-anthradithiophene derivatives
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The regiospecific total synthesis and characterization of anti-isomers of 2,8-dialkylanthradithiophenes are described. The "anti" structure of the ADT derivatives is demonstrated by 13C NMR as well as single crystal X-ray diffraction.
- Tylleman, Benoit,Velde, Christophe M.L. Vande,Balandier, Jean-Yves,Stas, Sara,Sergeyev, Sergey,Geerts, Yves Henri
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scheme or table
p. 5208 - 5211
(2011/12/04)
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- 2,5-diformylbenzene-1,4-diol: A versatile building block for the synthesis of ditopic redox-active schiff base ligands
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2,5-Diformylbenzene-1,4-diol (5) is a well-suited starting compound for the preparation of ditopic hydroquinone-based ligands. Here, we report an optimized synthesis of 5 which improves the overall yield from published 7 % to 42 %. Three new ditopic Schiff base ligands, 2,5-[iPr2N(CH 2)2N=CH]2-1,4-(OH)2-C 6H2 (8), 2,5-(pyCH2N=CH)2-1,4-(OH) 2-C6H2 (9), and 2,5-[py(CH2) 2N=CH]2-1,4-(OH)2-C6H2 (10), have been synthesized from 5 and structurally characterized by X-ray crystal structure analysis (py = 2-pyridyl).
- Kretz, Tonia,Bats, Jan Willem,Lerner, Hans-Wolfram,Wagner, Matthias
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- A convenient synthetic route to 2,5-dialkoxyterephthalaldehyde
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A convenient method for synthesizing 2,5-dialkoxyterephthalaldehyde by oxidation of 1,4-dialkoxy-2,5-bis(halogenomethyl)benzene with dimethyl sulfoxide in one step is described.
- Shao, Pin,Li, Zhen,Luo, Jianlin,Wang, Hongli,Qin, Jingui
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- Anodic Oxidation of Mono- and Disubstituted 1,4-Dimethoxybenzenes
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The electrochemical oxidation of mono- and disubstituted 1,4-dimethoxybenzene derivatives with zero, one, and two benzylic CH2X groups (X = OAc, Cl, OH) (5a-c and 6a-c) has been carried out by using both constant-current and controlled-potential techniques in methanol and in the presence of different electrolytes and working electrodes. Constant-current electrolysis in KOH-methanol solutions yielded mostly the corresponding 1,4-quinone derivatives from 5a-c and 6b, whereas the disubstituted 1,4-dimethoxybenzenes 6a,c underwent side-chain oxidation to form 2,5-dimethoxyterephthalaldehydes. Upon alteration of the medium from the commonly used basic KOH-methanol to neutral LiClO4-methanol, a new spectrum of products was achieved in most cases, involving novel coupling products from monosubstituted substrates and quinone derivatives from disubstituted ones. Controlled-potential oxidation at the glassy carbon anodes and in a neutral LiClO4-methanol medium led to more complex mixtures of products, namely, polymers and new coupling products from monosubstituted substrates and quinones and side-chain oxidation (or substitution) products from the disubstituted ones. Three new coupling products were isolated and characterized by X-ray measurements.
- Zeng, Cheng-Chu,Becker, James Y.
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p. 1053 - 1059
(2007/10/03)
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- Synthesis and photophysical studies of bis-enediynes as tunable fluorophores
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We have synthesized a family of bis-enediynes by two complementary Pd/Cu-catalyzed Sonogashira cross-coupling methods. One is a modified Sonogashira reaction between the TMS-protected tetraalkyne 20 (or 21) and various aromatic bromides to afford bis-enediynes 22a-d and 23a-d bearing different peripheral aryl units. The other, the reaction of bifunctional 1,1-dibromo-1-alkenes with phenylacetylene, afforded a series of bis-enediynes 24-32 bearing various core aryl groups. These chemical modifications to the core and periphery of bis-enediynes induce dramatic changes in absorption and emission spectra. Bis-enediynes 22 and 23 show a large Stokes shift of about 50-110 nm when compared to the less-conjugated bis-enediynes 20 and 21. Absorptions and emissions of bis-enediynes 25, 27-29, and 31 were red-shifted relative to those of enediyne 35. Substantial increases in fluorescence quantum yields are observed as a result of extending the π-conjugation. The emission wavelength of bis-enediynes was tailored from indigo blue to reddish-orange, suggesting that the color of emission can be tunable by modification of the core and/or peripheral units.
- Hwang, Gil Tae,Son, Hyung Su,Ku, Ja Kang,Kim, Byeang Hyean
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p. 11241 - 11248
(2007/10/03)
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- Compositions containing aromatic aldehydes and their use in treatments
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Disclosed are pharmaceutical and cosmetic compositions containing aromatic aldehyde compounds. Some of the disclosed compositions are useful as topical therapeutics for treating inflammatory dermatologic conditions. Some of the compositions are useful in transdermal and other systemic dose forms for treating other inflammatory conditions in mammals.
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- The synthesis of trianglimines: On the scope and limitations of the [3 + 3] cyclocondensation reaction between (1R,2R)-diaminocyclohexane and aromatic dicarboxaldehydes
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The synthesis of aromatic dicarboxaldehydes, using dilithiation methodology is described along with their reactivity, in the [3 + 3] cyclocondensation reaction, with (1R,2R)-diaminocyclohexane to give trianglimine macrocycles. The scope and limitations of the cyclocondensation reaction are studied and some comments on the properties of the novel macrocycles are made such as their conformation in solution and temperature dependent dynamic NMR behaviour.
- Kuhnert, Nikolai,Rossignolo, Giulia M.,Lopez-Periago, Ana
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p. 1157 - 1170
(2007/10/03)
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- Synthesis and Topochemistry of 2,5-Bisacrylate-Substituted 1,4-Benzoquinones
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The 2,5-bisacrylate-substituted 1,4-benzoquinone bisketal 7a was synthesized by electrochemical oxidation of the corresponding dimethoxybenzene 6. The methyl ester 7a was transesterified to the corresponding ethyl, n-propyl and isopropyl esters 7b-7d by T
- Irngartinger, Hermann,Herpich, Ruediger
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p. 595 - 604
(2007/10/03)
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- Intramolecular hydrogen bonding and molecular structure of 2,5-dihydroxyterephthalaldehyde and 4,6-dihydroxyisophthalaldehyde: A gas-phase electron diffraction and ab initio molecular orbital study
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The molecular structure of 2,5-dihydroxyterephthalaldehyde has been determined from a joint electron diffraction/ab initio investigation, and the molecular structure of 4,6-dihydroxyisophthalaldehyde has been obtained from ab initio calculations at the MP2/6-31G* level. There is considerable intramolecular hydrogen bonding in these structures manifested by the O...H and O...O distances as well as by the structural changes in the rest of the molecule. These changes are consistent with the notion of resonance-assisted hydrogen bonding. The hydrogen bonding is somewhat stronger in 4,6-dihydroxyisophthalaldehyde than in 2,5-dihydroxyterephthalaldehyde, and this difference may be linked to the difference in the mutual positioning of the interacting formyl and hydroxy groups in these molecules.
- Borisenko, Konstantin B.,Zauer, Karoly,Hargittai, Istvan
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p. 19303 - 19309
(2007/10/03)
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- Synthesis of Bipyridyl-, Viologen-, and Quinone-bridged Porphyrins
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Mesoporphyrin-II has been bridged by several 2,2'-hydroxymethyl-substituted 4,4'-bipyridine compounds.N-Methylation of the bipyridine bridge groups yielded viologen-bridged porphyrins which have unusual aggregation and fluorescence properties.An improved route to quinone-bridged porphyrins is also reported.
- Leighton, Philip,Sanders, Jeremy K. M.
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p. 2385 - 2394
(2007/10/02)
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- Synthesis of Hydrocarbon-Strapped Porphyrins Containing Quinone and Phenolic Groups
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A general synthesis of strapped porphyrins is described and is illustrated for porphyrins bearing quinone and phenol groups in the bridging strap, which is exclusively a polymethylene chain.The NMR and optical spectra of the strapped porphyrins are discussed.
- Morgan, Brian,Dolphin, David
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p. 5364 - 5374
(2007/10/02)
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- Radiohalogen-Labeled Imaging Agents. 3. Compounds for Measurement of Brain Blood Flow by Emission Tomography
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The radioiodine-labeled amines currently available as brain-imaging agents, based on our previous work and that of others, are prepared either by exchange labeling or by direct iodination of a protected intermediate.The intrinsic slowness of these process
- Sargent, Thornton,Shulgin, Alexander T.,Mathis, Chester A.
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p. 1071 - 1077
(2007/10/02)
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- SYNTHESIS OF OXIRANYLQUIONOES AS NEW POTENTIAL BIOREDUCTIVE ALKYLATING AGENTS
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1,4-Benzoquinones and 1,4-naphtoquinones carrying oxiranyl substituents have been synthesized as potential bioreductive alkylating agents.The method presented here involves the syntheses of 1,4-dimethoxybenzaldehydes or 1,4-dimethoxynaphtaldehydes, and co
- Syper L.,Mlochowsky, J.,Kloc, K.
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p. 781 - 792
(2007/10/02)
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