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1.
Visible‐light‐sensitive photoredox catalysis by iron complexes: Applications in cationic and radical polymerization reactions
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Jing Zhang Damien Campolo Frederic Dumur Pu Xiao Jean Pierre Fouassier Didier Gigmes Jacques Lalevée 《Journal of polymer science. Part A, Polymer chemistry》2016,54(14):2247-2253
The development of iron complexes for the photoredox catalysis is a huge challenge. Indeed, Iron complexes can be ideal candidates due to their potential visible light absorption and redox properties but also because they are less toxic, inexpensive and environmentally friendly compared to other catalysts. In the present paper, a series of novel iron complexes have been synthesized and utilized to initiate the free radical promoted cationic polymerization of epoxides or the free radical polymerization of acrylates through photoredox catalysis processes upon exposure to near UV (385 nm) or visible violet (405 nm) light emitting diodes (LEDs). When combined with an iodonium salt and N‐vinylcarbazole, the iron complex‐based photoinitiating systems are able to generate radicals, cations, and radical cations. The initiation efficiency is investigated through real‐time Fourier transform infrared spectroscopy and a satisfactory initiating ability is found. The mechanisms for the generation of the reactive initiating species through photoredox catalysis are studied by different methods (steady state photolysis, cyclic voltammetry and electron spin resonance spin trapping techniques) and discussed in detail. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2247–2253 相似文献
2.
In this study, molecular packing in lamellar liquid crystals in poly(oxyethylene) dodecyl ether(C(12)EO(n)) pure systems and the two surfactant mixtures of C(12)EO(8)/1-dodecanol(C(12)EO(0)), C(12)EO(8)/lipophilic sucrose laurate (L-595), hydrophilic sucrose laurate (L-1695)/C(12)EO(2) is investigated in terms of mean molecular area and partial molecular area (PMA). Lamellar liquid crystals formed in the C(12)EO(8)/C(12)EO(0) mixed system show higher melting temperatures than those in the C(12)EO(n) pure systems, even though the average number of EO units in the mixed surfactant system is the same as in the pure system. We compared the mean molecular area at the interface between hydrophilic and lipophilic moieties in the lamellar liquid crystals in each system. In the mixed system, the molecules are packed more tightly than in the pure system. Among the C(12)EO(n) and sucrose laurate mixtures, the L-1695/C(12)EO(2) mixed system showed a smaller mean molecular area per lipophilic chain than the C(12)EO(8)/L-595 mixed system. We investigated the effect of mixing two surfactants with different head group geometry on molecular packing by comparing the PMA of each surfactant. 相似文献
3.
A new push-pull type compound trans-4-dimesitylboryl-4′-(1,4,7,10-tetraoxa-13-aza-cyclopentadecyl) stilbene (DBTS) with aza-15-crown-5 as a donor and a three-coordinate organoboron as an acceptor was designed and synthesized. DBTS shows intense fluorescence in a wide spectra range in different solvents. Furthermore, DBTS can recognize fluoride anions with a high selectivity for the special Lewis acid-base interaction between a trivalent boron atom and a fluoride anion. As a typical alkaline earth cations receptor, DBTS also showed spectral changes upon their addition. 相似文献
4.
Qilong Zhou Ting Chen Jintao Zhang Lijun Wan Charles C. Han Rongben Zhang 《Tetrahedron letters》2008,49(38):5522-5526
As water is gradually added, a p-terphenyl derivative with dumbbell-like amphiphilic and rod-coil characteristics can hierarchically self-assemble to metastable rectangle columns architecting sheets first and then to stable quasi-hexagonal columns architecting rolled sheets, and finally to rod-like nanostructures in MeOH/H2O solution. Interestingly, the formed sheet, rolled sheet, and nanorod possess blue-light emitting property. 相似文献
5.
Souguir Z Roudesli S About-Jaudet E Le Cerf D Picton L 《Journal of colloid and interface science》2007,313(1):108-116
Pullulan derivative was synthesized by coupling carboxymethylpullulan (degree of substitution DS(0)(in)=0.7) and dimethylaminopropylamine (DMAPA), activated by a hydrosoluble carbodiimide N(')-(3-dimethylaminopropyl)-N-ethylcarbodiimide hydrochloride (EDAC). FTIR and (13)C and (1)H NMR spectroscopic analyses have evidenced that the polysaccharide has been successfully modified. (1)H NMR, nitrogen analysis, and conductimetric measurements allow determination of the degree of substitution in both carboxylic acid and amine functions. We have found that both functions present a similar DS of 0.35, which is characteristic of an ampholytic polymer with possible zwitterionic-type properties. Solution properties have been studied by flow field flow fractionation (F4) coupled on-line with multiangle laser light scattering (MALLS) and quasi elastic light scattering (QELS), surface tension, and viscosity measurements. The behavior has been found largely pH dependent and an amphiphilic behavior has been evidenced in alkaline media. 相似文献
6.
The aggregation behavior and interaction of an amphiphilic antidepressant drug imipramine (IMP) hydrochloride with the cationic surfactant cetyltrimethylammonium bromide (CTAB) have been studied using light scattering (both static and dynamic) techniques. Due to rigid tricyclic hydrophobic moiety present in the molecule, the drug shows interesting association behavior. The static light scattering measurements show that the self-association of IMP commenced above a well-defined critical micellar concentration (CMC), which decreases with increasing the mole fraction of the CTAB surfactant. Both the excess Gibbs energy (ΔG(ex)) and the Gibbs energy of micellization (ΔG(M)°) are negative, and decrease with increasing mole fraction of the surfactant. The hydrodynamic diameters (d(h)) of the micellar aggregates were also evaluated using the dynamic light scattering measurements. The data indicate formation of larger aggregates by IMP and CTAB due to mixed micellization and subsequent micellar growth. The results have been analyzed using different models (viz., Clint, Motomura, Rosen, Rubingh, etc.) for mixed micelle formation. 相似文献
7.
Mazzaglia A Angelini N Darcy R Donohue R Lombardo D Micali N Sciortino MT Villari V Scolaro LM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(23):5762-5769
The entanglement process between water-soluble 5,10,15,20-tetrakis(4-sulfonatophenyl)-21H,23H-porphine and the amphiphilic cyclodextrin (CD) heptakis(2-omega-amino-O-oligo(ethylene oxide)-6-hexylthio)-beta-CD and the occurrence of various species at different porphyrin:CD ratios were studied by a combination of UV/Vis absorption, fluorescence anisotropy, time-resolved fluorescence, resonance light scattering, and circular dichroism. The effect of the entanglement process on the mean vesicle diameter was investigated over a wide concentration range by quasielastic light-scattering techniques. The experimental results indicate that the presence of porphyrins in this colloidal system promotes some structural rearrangements, essentially driven by charge interaction, which are responsible for a sensitive change of vesicle dimensions. In the range of porphyrin:CD molar ratios between 1:10 and 1:50, the porphyrin is solubilized in monomeric form (tau(1)=11.5 ns) and photosensitizes the production of singlet oxygen ((1)O(2)). At the same molar ratio the ability of this amphiphilic cyclodextrin to transport porphyrins into tumor cells indicates specificity at the nuclear-compartment level. These findings may be of potential interest for the of development agents for photodynamic therapy of tumors. 相似文献
8.
A new acridine derivative was synthesized as a fluorescent chemosensor for Zn2+ in an 100% aqueous solution. Compound 1 displayed a selective CHEF (chelation enhanced fluorescence) effect with Zn2+, on the other hand, a similar anthracene derivative 2 did not display any significant change with the metal ions examined. 相似文献
9.
Yan-Li Leng Jian-Hui Zhang Qiao Li You-Ming Zhang Qi Lin Hong Yao 《Phosphorus, sulfur, and silicon and the related elements》2016,191(10):1318-1323
A colorimetric and fluorescent cyanide probe bearing naphthol and sulfahydrazone groups has been designed and synthesized. This structurally simple probe displays a rapid response and high selectivity for cyanide in DMSO/EtOH (v/v = 2:8) solution. The addition of CN? to the sensor p-toluenesulfonyl-2-hydroxy-1-naphthylhydrazone (L3) induced a remarkable color change from pale-yellow to yellow, and green fluorescence changed to yellow. The 1H NMR titration and DFT calculations suggested that the selective sensing process is based on a nucleophilic addition reaction of cyanide to imine. Test strips based on sensor L3 were fabricated, which could act as a convenient and efficient test kit to detect CN? for “in-the-field” measurements. 相似文献
10.
The morphological changes of ABA amphiphilic triblock copolymer micelles in dilute solution were systematically studied by tuning the solvent property using self-consistent field simulation. The solvent property was tuned by changing the Flory-Huggins interaction parameters between each type of blocks and solvent, respectively. The simulation results show that by changing the solvent properties, a series of micelle morphologies such as vesicle, cage-like, ring-shaped, rod-like and spherical micelle morphologies can be obtained. Variations of the free energy of the solution system and the surface area of micelles with the Flory-Huggins interaction parameters were calculated to better understand the effect of solvent property on micelle morphologies. In addition, a phase diagram showing the morphological changes of micelles with the Flory-Huggins interaction parameters is provided. 相似文献
11.
It was established that many crystalline molecular complexes composed of cationic surfactants such as CTAB and several phenolic derivatives were obtained from an appropriate concentrated solution system in which a remarkable viscoelasticity was developed. It is revealed that the molecular complexes have an unambiguous composition of 1:1 molar ratio of surfactants to phenolic additives. The molecular complexes also showed characteristic endothermicity of a degree that suggests the specimens to be single and a pure species. However, through repeated runs the thermal stability of the complexes seemed to be rather poor, as exhibited by a profile change in thermograms of DSC. 相似文献
12.
Properties of the amphiphilic films in mixed cationic/anionic vesicles: a comprehensive view from a literature analysis 总被引:3,自引:0,他引:3
The so-called 'catanionic' vesicles are made from mixtures of cationic and anionic surfactants. They are attracting much interest because they form spontaneously and they can be obtained from a variety of surfactants, either commercially available or issued from original synthesis. A distinction can be made between the properties of simple surfactant mixtures and of ion pair amphiphiles (IPA), in which the counterions have been removed. We have drawn up in this paper, an inventory of the different vesicular systems which have been described in the literature, insisting on the specific features associated with these two categories of systems. We have collected here especially, information concerning the phase behaviors, the microscopic composition of the vesicular particles, their structural and size determinations, the dynamic aspects (including the micelle-vesicle transition), the theoretical predictions from thermodynamic models and the entrapment of probe molecules. We discuss the potential of catanionic vesicles as delivery systems and we show that a full understanding of their entrapment/release properties will call for much more experimental work with well defined protocols. We also point out some unsolved questions concerning the role of the excess surfactant in the stabilization of the particles and the conditions required to obtain a favourable curvature of the surfactant film. 相似文献
13.
Yamamura H Akasaki A Yamada Y Kano K Katsuhara T Araki S Kawai M Tsuda T 《Electrophoresis》2001,22(3):478-483
A positively charged beta-cyclodextrin possessing a trimethylammonio group, 6-trimethylammonio-6-deoxy-beta-cyclodextrin chloride 1 was prepared by the reaction of an amino derivative 3 with methyl iodide under very mild conditions. The cyclodextrin derivative discriminated between enantiomers of acetylphenylalanine 2 on capillary zone electrophoresis (CZE) analysis, which was possibly due to an electrostatic interaction between the trimethylammonio group of 1 and the carboxylate group of 2, and also due to the inclusion of 2 in a hydrophobic molecular cavity of 1. Double data normalization based on relative electrophoretic velocity of peaks due to indirect response of 1 and also water in an injected sample may be effective for elimination of variation and fluctuation of physical parameters of medium, such as viscosity and ionic strength, in order to determine intrinsic association constants and velocity of the complexes. 相似文献
14.
Grinberg S Linder C Kolot V Waner T Wiesman Z Shaubi E Heldman E 《Langmuir : the ACS journal of surfaces and colloids》2005,21(17):7638-7645
Self-assembling nanostructures were prepared from novel cationic amphiphilic compounds synthesized from vernonia oil, a natural epoxydized triglyceride. The presence of a 12,13-epoxy group on the C18 unsaturated fatty acid, vernolic acid, which is the main constituent of vernonia oil, permitted the synthesis of novel amphiphilic derivatives with a hydrogen-bonding hydroxyl and a cationic headgroup moiety on adjacent carbon atoms. The amphiphiles were prepared in a two-stage synthesis that comprised opening of the epoxy groups with a haloacetic acid, followed by quaternization of the halo group with a tertiary amine containing a C12 aliphatic chain. Intact vernonia oil as the starting material gave a triple-headed cationic amphiphile, containing three vernolic acid derived moieties connected through a glycerol backbone. A single-headed amphiphile with two alkyl chains and a single quaternary ammonium headgroup was synthesized from the methyl ester of vernolic acid as the starting material. The triple-headed derivative could form nonencapsulating structures. Cholesterol was required in the formulation (1:1) to make spherical vesicles that could encapsulate a water-soluble marker. The single-headed derivative, however, formed spherical encapsulating vesicles without cholesterol. TEM, NMR, and FT-IR were used to characterize the vesicles, and molecular structure vs morphology relationships were postulated on the basis of these data. The triple-headed amphiphile also formed a DNA complex that was highly resistant to hydrolysis by DNase. This amphiphile-DNA complex was used as vector for gene transfer in cell culture demonstrating efficient DNA transfection. 相似文献
15.
A rhodamine spirolactam derivative (1) is developed as a colormetric and fluorescent probe for trivalent aluminum ions (Al3+). It exhibits a highly sensitive “turn-on” fluorescent response toward Al3+ with a 70-fold fluorescence intensity enhancement under 2 equiv. of Al3+ added. The probe can be applied to the quantification of Al3+ with a linear range covering from 5.0 × 10−7 to 2.0 × 10−5 M and a detection limit of 4.0 × 10−8 M. Most importantly, the fluorescence changes of the probe are remarkably specific for Al3+ in the presence of other metal ions, which meet the selective requirements for practical application. Moreover, the experiment results show that the response behavior of 1 towards Al3+ is pH independent in neutral condition (pH 6.0–8.0) and the response of the probe is fast (response time less than 3 min). In addition, the proposed probe has been used to detect Al3+ in water samples and image Al3+ in living cells with satisfying results. 相似文献
16.
Lermer L Roupioz Y Ting R Perrin DM 《Journal of the American Chemical Society》2002,124(34):9960-9961
Site-specific RNA cleavage has received considerable attention over the years. Directed synthesis to append imidazoles or amines or both to oligonucleotides to target specific RNA cleavage represents an exciting avenue of research. However, to date catalysis by such synthetic constructs, particularly in terms of turnover, has been difficult to observe. This is the first report of a truly catalytic M2+-independent DNAzyme synthetically modified with imidazoles and cationic amines that would seem to mimic RNaseA. This work now demonstrates how synthetic organic chemistry, when merged with combinatorial selection, can result in a new class of DNAzymes that meets the ongoing synthetic challenges for developing relatively small biomimetic catalysts. 相似文献
17.
Lei Jia Jun Zhang Lin Du 《Acta Crystallographica. Section C, Structural Chemistry》2019,75(8):1060-1064
The novel tetraphenylethylene derivative 4‐methyl‐N‐[3‐(1,2,2‐triphenylethenyl)phenyl]benzenesulfonamide (abbreviated as MTBF), C33H27NO2S, was synthesized successfully and characterized by single‐crystal X‐ray diffraction, high‐resolution mass spectroscopy and 1H NMR spectroscopy. MTBF crystallizes in the centrosymmetric monoclinic space group P21/c. In the crystal structure, the MTBF molecules are connected into a one‐dimensional band and then a two‐dimensional sheet by hydrogen bonds of the N—H…O and C—H…O types. The sheets are further linked to produce a three‐dimensional network via C—H…π interactions. The molecules aggregate via these intermolecular forces, which restrain the intramolecular motions (RIM) and decrease the energy loss in the aggregation state, so as to open the radiative channels, and thus MTBF exhibits excellent fluorescence by aggregation‐induced emission (AIE) enhancement. 相似文献
18.
A cationic fluorocarbon surfactant system of diethanolheptadecafluoro-2-undecanolmethylammonium chloride (DEFUMACl) and both mixed systems of DEFUMACl/cationic dodecyltrimethylammonium chloride (DTACl) and DEFUMACl/cationic Gemini copolymer was investigated by 19F NMR spectroscopy and surface tension measurements. The critical micelle concentration (cmc) of DEFUMACl by 19F NMR is about 3.40 mmol/L, which is completely consistent with that obtained by the surface tension method. The studies of salt and temperature on the cmc values of DEFUMACl suggest that both salt addition and temperature increase decrease the cmc values of DEFUMACl. 19F NMR measurements provide much richer information on both mixed systems. For the DEFUMACl-DTACl system, two break points were observed with increased total surfactant concentration. The first break point means the DEFUMACl and DTACl mixed micelles and the second one implies the individual DEFUMACl micelles. Results of 19F NMR and surface tension measurements for DEFUMACl/cationic Gemini copolymer mixtures show three peculiar break points, corresponding to the critical association concentration (cac) of DEFUMACl, the concentration where cationic Gemini copolymer molecules become saturated by DEFUMACl micelles, and the concentration where DEFUMACl micelles and cationic Gemini copolymer coexist. These peculiar points in the cationic-fluorocarbon and cationic-copolymer systems were first reported by 19F NMR and surface tension measurements. These results should broaden the useful information for a better understanding of the mechanism of interaction and the behavior of surfactant-polymer mixtures. 相似文献
19.
Dutta S Shome A Kar T Das PK 《Langmuir : the ACS journal of surfaces and colloids》2011,27(8):5000-5008
The necessity for the development of new antimicrobial agents due to the ever increasing threat from microbes is causing a rapid surge in research. In the present work, we have shown the efficient antimicrobial activity of a series of amino acid-based hydrogelating amphiphiles through alteration in their counterion. The subtle variation in the counterion from chloride to various organic carboxylates had a significant impact on the antimicrobial properties with notable improvement in biocompatibility toward mammalian cells. Incorporation of a hydrophobic moiety in the counterion augmented the antibacterial property of the amphiphilic hydrogelator as minimum inhibitory concentration (MIC) against the Gram-positive bacterial strain, Bacillus subtilis decreased up to 5-fold (with respect to the chloride) in the case of n-hexanoate. These counterion-varied amphiphilic hydrogelators were also found to be effective against fungal strains (Candida albicans and Saccharomyces cerevisiae) where they exhibited MICs in the range of 1.0-12.5 μg/mL. To widen the spectrum of antibacterial activity, particularly against Gram-negative bacteria, silver nanoparticles (AgNPs) were synthesized in situ within the supramolecular assemblies of the carboxylate hydrogelators. These AgNP-amphiphile soft-nanocomposites showed bactericidal property against both Gram-positive and Gram-negative bacteria. Encouragingly, these carboxylate hydrogelators showed superior biocompatibility toward mammalian cells, HepG2 and NIH3T3, as compared to the chloride analogue at a concentration range of 10-200 μg/mL. Importantly, the AgNP composites also showed sufficient viability to mammalian cells. Because of the intrinsic hydrogelation ability of these counterion-varied amphiphiles, the resulting soft materials and the nanocomposites could find applications in biomedicine and tissue engineering. 相似文献
20.
《Journal of Coordination Chemistry》2012,65(9):1561-1573
Two palladium(II) complexes with imidazole derivative ligands have been synthesized. The molecular structures of the complexes were determined by X-ray crystallography and their spectroscopic properties were studied. Based on the crystal structures, computational investigations were carried out to determine the electronic structures of the complexes. The electronic spectra were calculated with use of time-dependent DFT method, and the transitions were correlated with the molecular orbitals of the complexes. The emission of the complex with 1-methylimidazole was examined. 相似文献