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971.
Wanlong Xiao Yuhao Mo Jing Guo Zhishan Su Shunxi Dong Xiaoming Feng 《Chemical science》2021,12(8):2940
New types of C2-symmetric chiral macrodiolides are readily obtained via chiral N,N′-dioxide-scandium(iii) complex-promoted asymmetric tandem Friedel–Crafts alkylation/intermolecular macrolactonization of ortho-quinone methides with C3-substituted indoles. This protocol provides an array of enantioenriched macrodiolides with 16, 18 or 20-membered rings in moderate to good yields with high diastereoselectivities and excellent enantioselectivities through adjusting the length of the tether at the C3 position of indoles. Density functional theory calculations indicate that the formation of macrocycles is more favorable than that of 9-membered-ring lactones in terms of kinetics and thermodynamics. The potential utility of these intriguing chiral macrodiolide molecules is demonstrated in the enantiomeric recognition of aminols and chemical recognition of metal ions.An asymmetric tandem Friedel–Crafts alkylation/intermolecular macrolactonization of ortho-quinone methides with C3-substituted indoles was achieved by using a chiral N,N′-dioxide-scandium(iii) complex. 相似文献
972.
Chau‐Hui Wang Ging‐Ho Hsiue 《Journal of polymer science. Part A, Polymer chemistry》2002,40(8):1112-1121
A novel series of temperature‐ and pH‐sensitive hydrogels based on poly(2‐ethyl‐2‐oxazoline) and three‐arm poly(D,L ‐lactide) were synthesized via photocopolymerization. For the creation of polymeric networks, two types of macromers terminated with methacrylate groups were prepared: poly(2‐ethyl‐2‐oxazoline) dimethacrylate and three‐arm poly(D,L ‐lactide) trimethacrylate. The chemical structures were analyzed with 1H NMR and Fourier transform infrared techniques. The thermal behaviors, morphologies, and swelling properties were measured for the characterization of the polymeric networks. All the poly(2‐ethyl‐2‐oxazoline)/three‐arm poly(D,L ‐lactide)hydrogels provided high water retention capacity and exhibited reversible swelling–shrinking behavior in response to temperature and pH variations. The hydrogels with higher poly(2‐ethyl‐2‐oxazoline) dimethacrylate contents were more effective in raising the swelling ratio and temperature and pH sensitivity. However, higher contents of three‐arm poly(D,L ‐lactide) trimethacrylate produced larger particles and pore sizes in the hydrogels. This study effectively proves that this unique combination of water swellability and biodegradability provides hydrogels with a much wider range of applications in biomedical fields. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1112–1121, 2002 相似文献
973.
Amphiphilic triblock copolymers of poly(3-hydroxybutyrate)-poly(ethylene glycol)-poly(3-hydroxybutyrate) (PHB-PEG-PHB) were directly synthesized by the ring-opening copolymerization of β-butyrolactone monomer using PEG as macroinitiator. Their structure, thermal properties and crystallization were investigated by 1H NMR, differential scanning calorimetry (DSC) and X-ray diffraction. It was found that both PHB and PEG blocks were miscible. With the increase in the PHB block length, the triblock copolymers became amorphous because amorphous PHB block remarkably depressed the crystallization of the PEG block. Biodegradable nanoparticles with core-shell structure were prepared in aqueous solution from the amphiphilic triblock copolymers, and characterized by 1H NMR, SEM and fluorescence. The hydrophobic PHB segments formed the central solid-like core, and stabilized by the hydrophilic PEG block. The nanoparticle size was close related to the initial concentrations of the nanoparticle dispersions and the compositions of the triblock copolymers. Moreover, the PHB-PEG-PHB nanoparticles also showed good drug loading properties, which suggested that they were very suitable as delivery vehicles for hydrophobic drugs. 相似文献
974.
Nicola Armaroli Gianluca Accorsi JohnN. Clifford Jean‐Franois Eckert Jean‐Franois Nierengarten 《化学:亚洲杂志》2006,1(4):564-574
Oligophenylenevinylene (OPV)‐terminated phenylenevinylene dendrons G1 – G4 with one, two, four, and eight “side‐arms”, respectively, were prepared and attached to C60 by a 1,3‐dipolar cycloaddition of azomethine ylides generated in situ from dendritic aldehydes and N‐methylglycine. The relative electronic absorption of the OPV moiety increases progressively along the fullerodendrimer family C60G1 – C60G4 , reaching a 99:1 ratio for C60G4 (antenna effect). UV/Vis and near‐IR luminescence and transient absorption spectroscopy was used to elucidate photoinduced energy and electron transfer in C60G1 – C60G4 as a function of OPV moiety size and solvent polarity (toluene, dichloromethane, benzonitrile), taking into account the fact that the free‐energy change for electron transfer is the same along the series owing to the invariability of the donor–acceptor couple. Regardless of solvent, all the fullerodendrimers exhibit ultrafast OPV→C60 singlet energy transfer. In CH2Cl2, the OPV→C60 electron transfer from the lowest fullerene singlet level (1C60*) is slightly exergonic (ΔGCS≈0.07 eV), but is observed, to an increasing extent, only in the largest systems C60G2 – C60G4 with lower activation barriers for electron transfer. This effect has been related to a decrease of the reorganization energy upon enlargement of the molecular architecture. Structural factors are also at the origin of an unprecedented OPV→C60 electron transfer observed for C60G3 and C60G4 in apolar toluene, whereas in benzonitrile, electron transfer occurs in all cases. Monitoring of the lowest fullerene triplet state by sensitized singlet oxygen luminescence and transient absorption spectroscopy shows that this level is populated through intersystem crossing and is not involved in photoinduced electron transfer. 相似文献
975.
Novel polynuclear Cu(II) complexes containing derivatives of 1,2,4-trizaole and pivalate ligands, [Cu(3)(mu(3)-OH)(mu-adetrz)(2)(piv)(5)(H(2)O)].6.5H(2)O (1) (adetrz = 4-amino-3,5-diethyl-1,2,4-triazole, piv = pivalate), [Cu(4)(mu(3)-OH)(2)(mu-atrz)(2)(mu-piv)(4)(piv)(2)].2MeOH.H(2)O (2) (atrz = 4-amino-1,2,4-triazole), [Cu(4)(mu(3)-OH)(2)(mu-tbtrz)(2)(mu-piv)(2)(piv)(4)].4H(2)O (3) (tbtrz = 4-tert-butyl-1,2,4-trizaole), and [Cu(4)(mu(3)-O)(2)(mu-admtrz)(4)(admtrz)(2)(mu-piv)(2)(piv)(2)].2[Cu(2)(mu-H(2)O)(mu-admtrz)(piv)(4)].13H(2)O [4 = 4a.2(4b).13H(2)O; admtrz = 4-amino-3,5-dimethyl-1,2,4-triazole], have been prepared and structurally characterized. 1 is an asymmetrical triangular complex containing a [Cu(3)(mu(3)-OH)] core with two Cu---Cu edges spanned by bridging adetrz ligands. 2, 3, and 4a are novel tetranuclear compounds containing a [Cu(4)(mu(3)-O)(2)] or [Cu(4)(mu(3)-OH)(2)] core with Cu---Cu edges spanned by bridging 1,2,4-triazole or pivalate ligands. 4b is a dinuclear compound with one admtrz and one water bridge, and it is the first dinuclear Cu(II) triazole complex with one bridging water molecule. 1 is one of few reported triangular Cu(II) complexes with derivatives of 1,2,4-triazole, while 2, 3, and 4a are the first group of the nonlinear tetranuclear Cu(II) compounds with derivatives of 1,2,4-triazole. Variable-temperature magnetic susceptibility studies on the powder samples of 1-3 reveal the overall antiferromagnetic coupling between Cu(II) ions with J values of -55.6 to -12.8 cm(-1) (1), -216.4 to 0 cm(-1) (2), and -259.8 to 4.8 cm(-1) (3). 相似文献
976.
We report a nanoscale lipid membrane-based sensor of conjugated polydiacetylene (PDA) vesicles for fluorescence detection of organic amines. The vesicle sensor was constructed by incorporation of a BODIPY fluorescent dye into the PDA vesicles. The fluorescent properties of the resulting vesicles can be manipulated by adjusting lipid components, and are controlled by environmental and solution conditions. The fluorescence of the BODIPY dye was significantly quenched in the polymerization of diacetylene lipid vesicles by a UV irradiation process. However, it was sufficiently recovered by external stimuli such as a hike of solution pH. The fluorescence recovery process was reversible, and a decrease in solution pH resulted in repeated quenching. The reported system transforms an external stimulus into a large fluorescence intensity change, demonstrating great potential in developing new signal reporting method for biosensor design. The quench-recovery phenomenon of the BODIPY-PDA is believed to be related to the energy transfer between the dye and the PDA conjugate backbone. The vesicle sensor was applied for detecting an organic amine, triethylamine (TEA) and a large linear relationship was obtained between the increase in fluorescence intensity and the concentrations of TEA. The detection limit of TEA by vesicle sensors using fluorescence recovery was found to be 10 μM. 相似文献
977.
Ramadan Ahmed Mekheimer Kamal Usef Sadek Hisham Ahmed Abd El‐Nabi Afaf Abd El‐Hameid Mohamed Ehab Anwer Ebraheem Michael B. Smith 《Journal of heterocyclic chemistry》2005,42(4):567-574
Ethyl 3‐amino‐4‐chlorothieno[3,2‐c]quinoline‐2‐carboxylate ( 4 ) is a versatile synthon, prepared by reacting an equimolar amount of 2,4‐dichloroquinoline‐3‐carbonitrile ( 1 ) with ethyl mercaptoacetate ( 2 ). Ethyl 5‐alkyl‐5H‐1‐thia‐3,5,6‐triazaaceanfhrylene‐2‐carboxylates 9a‐c , novel perianellated tetracyclic heteroaro‐matics, were prepared by refluxing 4 with excess of primary amines 7a‐c to yield the corresponding amino‐thieno[3,2‐c]quinolines 8a‐c . Subsequent reaction with an excess of triethyl orthoformate (TEO) furnished 9a‐c . Reaction of 4 with TEO in Ac2O at reflux, gave the simple acetylated compounds, thieno[3,2‐c]‐quinolines 12 and 13 . Refluxing 4 with benzylamine ( 7d ) gave 10 , and subsequent treatment with TEO gave the tetracyclic compound 11 . Refluxing 13 with an excess of alkylamines 7a‐d gave the fhieno[3,2‐c]quino‐lines 15 . Refluxing the aminothienoquinolines 8b with an excess of triethyl orthoacetate gave thieno[3,2‐c]quinoline 17 , while heating with Ac2O gave 18 and 19 , with small amounts of 16 . Reaction of 8a,b with ethyl chloroformate and phenylisothiocyanate generated the new 1‐thia‐3,5,6‐triazaaceanthrylenes 20a,b and 21a,b , respectively. Diazotization of 8a‐c afforded the novel tetracyclic ethyl 5‐alkyl‐5H‐1‐fhia‐3,4,5,6‐tetraazaaceanthrylene‐2‐carboxylates 22a‐c in good yields. 相似文献
978.
Hui‐Bo Zhou Wen Dong Mao Liang Dai‐Zheng Liao Zong‐Hui Jiang Shi‐Ping Yan Peng Cheng 《无机化学与普通化学杂志》2004,630(4):498-500
A three‐dimensional cyano‐bridged copper(II) complex, [Cu(dien)Ag(CN)2]2[Ag2(CN)3][Ag(CN)2] ( 1 ) (dien = diethylenetriamine), has been prepared and characterized by X‐ray crystallography. Complex 1 crystallized in the monoclinic space group P21/n with a = 6.988(2), b = 17.615(6), c = 12.564(4) Å, β = 90.790(5)°. The crystal consists of cis‐[Cu(dien)]2+ units bridged by [Ag(CN)2]— to form a zig‐zag chain. The Ag atoms of the free and bridging [Ag(CN)2]— link together to form additional infinite zig‐zag chains with short Ag···Ag distances. The presence of Ag···Ag interactions effectively increases the dimensionality from a 1‐D chain to a 3‐D coordination polymer. 相似文献
979.
A fluorescent aminoacid was designed for selective and sensitive detection of Cu(II) in aqueous solution. The designing of this Cu(II) fluorescent chemosensing molecule, N ± (1‐naphthyl). aminoacetic acid (NAA), was based on the binding of Cu(II) to aminoacetic acid and the novel charge transfer photophysics of 1‐aminonaphthalenes. The fluorescence of NAA was found quenched by Cu (II) and several other metal ions of similar electronic structure such as Co(II), Ni(II) and Zn(II). The quenching was shown to occur via electron transfer within the metal‐NAA complex, which required an optimal combination of high binding affinity and favorable redox properties of the components in the metal‐NAA complex and hence afforded selective fluorometric detection of Cu(II). The calibration graph obeyed Stern‐Volmer theory and was shown for Cu(II) over the range of 0–2.75 ± 10–4 mol/L. The quenching constant of Cu(II) was measured as 8.0 ± 103 mol/L that was two orders of magnitude higher than those of Co(II), Ni(II) and Zn(II). The 3SD limit of detection for Cu(II) was 8.00 ± 10?6 mol/L with a coefficient of variation of 1.65%. Linear range for quantitative detection of Cu(II) was 2.67 ± 10?5‐2.75 ± 10?4 mol/L. The method was applied to synthetic sample measurements which gave recoveries of 105%‐112%. 相似文献
980.
The inside cover picture shows the journey of developing PIP amine directing group for C—H activation, from controlling the reactivity and diastereoselectivity to enantioselectivity. In the presence of Pd or base metal catalysts, PIP amine enabled the activation of inert C—H bonds to form diverse C—C and C—heteroatom bonds. Its tuneable structure has triggered the design of chiral auxiliaries for diastereoselective C—H activation. More recently, enantioselective activation of unbiased methylene C—H bonds has been achieved by cooperative effects between PIP amine and axial chiral ligands. More details are discussed in the article by Shi et al. on page 647–656.