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1.
刘守信 《高分子科学》2016,34(8):965-980
A double thermoresponsive ABC-type triblock copolymer(poly(ethyleneglycol)-block-poly(2-(2-methoxyethoxy) ethyl methacrylate)-block-poly(2-(2-methoxy ethoxy) ethyl methacrylate-co-oligo(ethylene glycol) methyl ether methacrylate, PEG-b-PMEO_2MA-b-P(MEO_2MA-co-OEGMA)) was designed and synthesized by reversible additionfragmentation chain transfer polymerization(RAFT). The ABC-type triblock copolymer endowed a thermal-induced twostep phase transition at 29 and 39 °C, corresponding to the thermosensitive properties of PMEO_2 MA and P(MEO_2MA-coOEGMA) segments, respectively. The two-step self-assembly of copolymer solutions was studied by UV transmittance measurement, dynamic light scattering(DLS), transmission electron microscopy(TEM) and so on. The triblock copolymers showed the distinct thermosensitive behavior with respect to transition temperatures, aggregate type and size, which was correlated to the degree of polymerization of thermosensitive blocks and the molar fraction of OEGMA in the P(MEO_2MAco-OEGMA) segments. In addition, micelles could further aggregate to form the hydrogel by the self-associate of PEG chains under the abduction of the concentration and temperature. The transition from sol to gel was investigated by a test tube inverting method and dynamic rheological measurement.  相似文献   

2.
This article reports on the synthesis of a novel amphiphilic polyhedral oligomeric silsesquioxane (POSS) end-capped poly(2-(2-methoxyethoxy)ethyl methacrylate)-co-oligo(ethylene glycol) methacrylate) (POSS-P(MEO2MA-co-OEGMA)). These thermoresponsive organic–inorganic hybrid polymers exhibit critical phase transition temperature in water, which can be finely tuned by changing the feed ratio of OEGMA and MEO2MA. The lower critical solution temperature (LCST) of POSS-P(MEO2MA-co-OEGMA) increases from 31 to 59 °C with the increasing of OEGMA content. Dynamic light scattering (DLS) and transmission electron microscopy (TEM) studies show that these polymers can self-assemble into spherical micelles with the thermosensitive block into the corona and the POSS forming the core, and larger aggregates are formed when the temperature values are above their LCSTs. These thermoresponsive polymers POSS-P(MEO2MA-co-OEGMA) with self-assembly behavior and tunable tempetature-responsive property have the potential applications in material science and biotechnology.  相似文献   

3.
A combination of anionic polymerization, atom transfer radical polymerization (ATRP) and ??click?? chemistry was used to construct trishydrophilic ABC triblock terpolymers composed of a pH-sensitive A block, a water-soluble B block and two different thermo-sensitive C blocks without any block sequence limitation problems. First, an azido end-functionalized poly(2-vinylpyridine)-block-poly(ethylene oxide) (P2VP-b-PEO-N3) diblock copolymer was synthesized by anionic polymerization. In a second step, poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) and poly(oligo(ethylene glycol) methacrylate) (POEGMA) were synthesized via ATRP using an alkyne functionalized initiator. The resulting polymers were attached to the P2VP-b-PEO-N3 diblock copolymer using the 1,3-dipolar Huisgen cycloaddition (??click?? chemistry). For the ??click?? step, P2VP-b-PEO-N3 diblock copolymers with either an azidoacetyl or a 2-azidoisobutyryl group were tested. In the latter case, however, a side reaction involving the cleavage of the formed ??click?? product via nucleophilic substitution occurred, preventing a permanent attachment of PDMAEMA or POEGMA to the P2VP-b-PEO-N3 diblock copolymer. Finally, P2VP-b-PEO-b-POEGMA (with POEGMA=P(MEO2MA-co-MEO8.5MA)) and P2VP-b-PEO-b-PDMAEMA triblock terpolymers were successfully synthesized and used to construct stimuli-responsive hydrogels. A concentrated solution of P2VP56-b-PEO370-b-P[(MEO2MA)89-co-(MEO8.5MA)7] showed a gel?Csol?Cgel transition at pH?7 upon temperature increase, whereas in the case of P2VP56-b-PEO370-b-PDMAEMA70, a gel?Csol or a weak gel?Cstrong gel transition was observed, depending on the applied pH. Finally, the addition of trivalent hexacyanocobaltate(III) ions to the P2VP56-b-PEO370-b-PDMAEMA70 solution induced an upper critical solution temperature for the PDMAEMA block, which led to gel formation. This allows for the construction of light-sensitive hydrogels, utilizing the photo-aquation of hexacyanocobaltate(III) ions.  相似文献   

4.
郭文莉 《高分子科学》2013,31(2):285-293
To improve the hydrophilicity of poly(styrene-b-isobutylene-b-styrene) (SIBS), this study focuses on the synthesis of novel functional ABA triblock copolymer thermoplastic elastomers (TPEs) with polyisobutylene (PIB) as rubbery segments. The precursor poly{(styrene-co-4-[2-(tert-butyldimethylsiloxy) ethyl]styrene)-b-isobutylene-b-(styrene-co-4-[2-(tert-butyldimethylsiloxy)ethyl]styrene)}(P(St-co-TBDMES)-PIB-P(St-co-TBDMES)) triblock copolymer was first synthesized by living sequential cationic copolymerization of isobutylene (IB) with styrene (St) and 4-[2-(tert-butyldimethylsiloxy) ethyl]styrene (TBDMES) using 1,4-di(2-chloro-2-propyl)benzene (DiCumCl)/titanium tetrachloride (TiCl4)/2,6-di-tert-butylpyridine (DtBP) as the initiating system. Then, P(St-co-TBDMES)-PIB-P(St-co-TBDMES) was hydrolyzed in the presence of tetra-butylammonium fluoride to yield poly{[styrene-co-4-(2-hydroxyethyl)styrene]-bisobutylene-b-[styrene-co-4-(2-hydroxyethyl)styrene]} (P(St-co-HOES)-PIB-P(St-co-HOES)) with pendant hydroxyl groups. P(St-co-HOES)-PIB-P(St-co-HOES) used as the paclitaxel carrier was also investigated in this study. Comparing with SIBS, P(St-co-HOES)-PIB-P(St-co-HOES) has exhibited better compatibility with paclitaxel and higher release rate.  相似文献   

5.
Thermoresponsive double hydrophilic diblock copolymers poly(2‐(2′‐methoxyethoxy)ethyl methacrylate‐co‐oligo(ethylene glycol) methacrylate)‐b‐poly(6‐O‐methacryloyl‐D ‐galactopyranose) (P(MEO2MA‐co‐OEGMA)‐b‐PMAGP) with various compositions and molecular weights were obtained by deprotection of amphiphilic diblock copolymers P(MEO2MA‐co‐OEGMA)‐b‐poly(6‐O‐methacryloyl‐1,2:3,4‐di‐O‐isopropylidene‐D ‐galactopyranose) (P(MEO2MA‐co‐OEGMA)‐b‐PMAlpGP), which were prepared via reversible addition‐fragmentation chain transfer (RAFT) polymerization using P(MEO2MA‐co‐OEGMA) as macro‐RAFT agent. Dynamic light scattering and UV–vis studies showed that the micelles self‐assembled from P(MEO2MA‐co‐OEGMA)‐b‐PMAlpGP were thermoresponsive. A hydrophobic dye Nile Red could be encapsulated by block copolymers P(MEO2MA‐co‐OEGMA)‐b‐PMAGP upon micellization and released upon dissociation of the formed micelles under different temperatures. The galactose functional groups in the PMAGP block have specific interaction with HepG2 cells, and P(MEO2MA‐co‐OEGMA)‐b‐PMAGP has potential applications in hepatoma‐targeting drug delivery and biodetection. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

6.
The first example of organostibine mediated controlled/living random copolymerization of styrene (St) and methyl methacrylate (MMA) was achieved by heating a solution of St/MMA/organostibine mediator at 100 °C or St/MMA/organostibine mediator/AIBN with various monomer feed ratios at 60 °C. The addition of AIBN significantly decreased the reaction temperature and enhanced the rate of copolymerization. The structure of poly(St-co-MMA) was verified by 1H NMR. The reactivity ratios at 60 °C were determined by the extended Kelen-Tüd?s method to be γSt = 0.40 and γMMA = 0.44. The ln([M]0/[M]) increased linearly with increasing reaction time. The number-average molecular weights of poly(St-co-MMA) increased linearly with conversion. Poly(St-co-MMA) with expected number-average molecular weight and low polydispersity index was formed. The living characteristic was further confirmed by chain-extension of poly(St-co-MMA) to form poly(St-co-MMA)-b-PMMA.  相似文献   

7.
2‐(2‐Hydroxy‐phenyl)‐4(3H)‐quinazolinone (HPQ), an organic fluorescent material that exhibits fluorescence by the excited‐state intramolecular proton‐transfer (ESIPT) mechanism, forms two different polymorphs in tetrahydrofuran. The conformational twist between the phenyl and quinazolinone rings of HPQ leads to different molecular packing in the solid state, giving structures that show solid‐state fluorescence at 497 and 511 nm. HPQ also shows intense fluorescence in dimethyl formamide (DMF) solution and selectively detects Zn2+ and Cd2+ ions at micromolar concentrations in DMF. Importantly, HPQ not only detects Zn2+ and Cd2+ ions selectively, but it also distinguishes between the metal ions with a fluorescence λmax that is blue‐shifted from 497 to 420 and 426 nm for Zn2+ and Cd2+ ions, respectively. Hence, tunable solid‐state fluorescence and selective metal‐ion‐sensor properties were demonstrated in a single organic material.  相似文献   

8.
A new ratiometric fluorescent chemosensor based on a polyimine macrocycle ligand 1 has been synthesized. The chemosensor can exhibit a pronounced fluorescence response and high selectivity to Zn2+ ion over other 15 metal ions, including Cd2+. Sensor 1 appears an emission peak at 370 nm. Upon the addition of Zn2+ ion, the typical emission peak for 1 at 370 nm is obviously quenched, but a new emission peak at around 470 nm appears and shows a large enhancement due to the formation of a 1:1 Zn2+-1 complex. In addition, there is a good linear relationship between the fluorescence ratio I470nm/I370nm and the concentration of Zn2+, which makes a ratiometric assay of Zn2+ ion possible.  相似文献   

9.
A fluorescent Zn2+ sensor based on the 2-(2-nitrostyryl)-8-methoxyquinoline (2-nitroSQ) has been designed, synthesized, and characterized by various spectral techniques. The designed fluorophore displays high selectivity, sensitive fluorescence enhancement (13-fold), and strong binding affinity toward Zn2+ among the various biologically significant metal ions examined in ACN-H2O (9:1, v/v).  相似文献   

10.
An efficient quinoline-based fluorescent chemosensor (QLNPY) was successfully developed for the detection of zinc ions (Zn2+). This novel chemosensor displayed higher sensitivity and selectivity toward Zn2+ over other competitive metal ions accompanying with obvious fluorescence enhancement. The QLNPY-Zn2+ complex can be further used as a new fluorescent “turn-off” sensor for pyrophosphate (PPi) and sulfur ion (S2?) via a Zn2+ displacement approach. The limits of detection were calculated to be 3.8 × 10?8 M for Zn2+, 3.7 × 10?7 M for PPi and 4.9 × 10?7 M for S2?. The binding mechanism of QLNPY and Zn2+ was investigated through NMR, HR-MS analysis and further studied by crystallographic analysis. Additionally, further application of QLNPY for sequential bioimaging of Zn2+ and PPi was studied in HepG2 cells, suggesting that the quinoline-based chemosensor possesses great potential applications for the detection of intracellular Zn2+ and PPi in vivo.  相似文献   

11.
Herein, we report the highly selective binding of Zn2+ ion by the salicylaldimine based Schiff base chromogenic receptor 1 [(N,N′-bis (salicylidine)-o-phenylenediamine]. Receptor 1 senses Zn2+ ion in aqueous medium by colorimetric and fluorescent response in the presence of other metal ions like Pb2+, Hg2+, Sn2+, Cd2+. Receptor 1 on binding with Zn2+ ion exhibits fluorescence enhancement which is due to the inhibition of the (ESIPT) mechanism.  相似文献   

12.
Prabhpreet Singh 《Tetrahedron》2006,62(26):6379-6387
The dipod 1,2-bis(8-hydroxyquinolinoxymethyl)benzene (3) and tetrapod 1,2,4,5-tetrakis(8-hydroxyquinolinoxymethyl)benzene (5) have been synthesized through nucleophilic substitution of respective 1,2-bis(bromomethyl)benzene (2) and 1,2,4,5-tetra(bromomethyl)benzene (4) with 8-hydroxyquinoline (1). For comparison, 1,3,5-tris(8-hydroxyquinolinoxymethyl)benzene derivatives (7a and 7b) have been obtained. The complexation behavior of these podands towards Ag+, Co2+, Ni2+, Cu2+, Zn2+, and Cd2+ metal ions has been investigated in acetonitrile by fluorescence spectroscopy. The sterically crowded 1,2,4,5-tetrapod 5 displays unique fluorescence ‘ON-OFF-ON’ switching through fluorescence quenching (λmax 395 nm, switch OFF) with <1.0 equiv of Ag+ and fluorescence enhancement (λmax 495 nm, switch ON) with >3 equiv Ag+ and can be used for estimation of two different concentrations of Ag+ at two different wavelengths. The addition of Cu2+, Ni2+, and Co2+ metal ions to tetrapod 5 causes fluorescence quenching, i.e., ‘ON-OFF’ phenomena at λmax 395 nm for <10 μM (1 equiv) of these ions but addition of Zn2+ and Cd2+ to tetrapod 5 results in fluorescence enhancement with a gradual shift of λem from 395 to 432 and 418 nm, respectively. Similarly, dipod 3 behaves as an ‘ON-OFF-ON’ switch with Ag+, an ‘ON-OFF’ switch with Cu2+, and an ‘OFF-ON’ switch with Zn2+. The placement of quinolinoxymethyl groups at the 1,3,5-positions of benzene ring in tripod 7a-b leads to simultaneous fluorescence quenching at λmax 380 nm and enhancement at λmax 490 nm with both Ag+ and Cu2+. This behavior is in parallel with 8-methoxyquinoline 8. The rationalization of these results in terms of metal ion coordination and protonation of podands shows that 1,2 placement of quinoline units in tetrapod 5 and dipod 3 causes three different fluorescent responses, i.e., ‘ON-OFF-ON’, ‘ON-OFF’, and ‘OFF-ON’ due to metal ion coordination of different transition metal ions and 1, 3, and 5 placement of three quinolines in tripod 7, the protonation of quinolines is preferred over metal ion coordination. In general, the greater number of quinoline units coordinated per metal ion in 5 compared with the other podands points to organization of the four quinoline moieties around metal ions in the case of 5.  相似文献   

13.
In this study, simple on–off fluorescent/UV–visible (UV–Vis) probes were easily prepared using 2-(2-hydroxyphenyl)thiazolidine-4-carboxylic acid ( Sen-1 ) and/or 2-(2-hydroxy-5-nitrophenyl)thiazolidine-4-carboxylic acid ( Sen-2 ) for fast detection of Zn2+ ions. Their sensing properties towards common metal ions were investigated using UV–Vis and fluorescence spectroscopies. Sen-1 and Sen-2 displayed a significant change with the addition of Zn2+ ions in the UV–Vis spectra. The addition of Zn2+ ions induced a 104 nm bathochromic shift for Sen-1 . The binding ratio towards Zn2+ metal ions was determined to be 1:1 by using Job plot analysis and fluorescence spectroscopy. The association constant and free energy (ΔG) of Sen-1 and Sen-2 towards Zn2+ ions were calculated by the Benesi–Hildebrand equation. The limit of detection of Sen-1 towards Zn2+ ions is 3.73 × 10−8 M, which is about 1/100 of the value recommended by the World Health Organization for drinking water. Sen-1 was successfully applied to detect Zn2+ ions in water samples and the fluorescence test strip was prepared for visual detection of Zn2+ ions. Finally, the quantum chemical parameters of Sen-1 and Sen-2 , such as highest occupied molecular orbital, lowest unoccupied molecular orbital, and chemical hardness, were investigated by the Becke, three-parameter, Lee–Yang–Parr, Hartree–Fock, and M062x methods.  相似文献   

14.
By appending a pair of carboxamidoquinoline pendants onto 1,2-diaminocyclohexane scaffold via N-alkylation, multifunctionalized ACAQ was designed and synthesized as a water soluble fluorescent ratiometric chemosensor for Zn2+. In 50% aqueous methanol buffer pH 7.4 solution, upon excitation at 316 nm, ACAQ (5 μM) displayed a selective ratiometric fluorescence changes with a shift from 410 to 490 nm in response to the interaction with Zn2+. After binding with 1 equiv of Zn2+, ACAQ exhibited a 12-fold enhancement in I490/I410 characterized by a clear isoemissive point at 440 nm. The metal sensor binding mode was established by Job’s plot and the combined fluorescence and 1H NMR spectroscopic method. The selectivity of the probe toward biological relevant cations and transition metal ions was proven to be good. In addition, the interference caused by Cu2+ and Cd2+ in the quantitation of Zn2+ can be completely eliminated by the use of diethyldithiocarbamate as the screening agent. Exploitation of ACAQ as the sensing probe, ratiometric determination of Zn2+ with the limit of detection (LOD) at 28.3 nm can be realized. In addition, the unique responsive properties of the probe toward Fe3+ and Zn2+ were used to construct a fluorescent switch. The membrane permeability of ACAQ to living cells and bio-imaging of Zn2+ were demonstrated.  相似文献   

15.
A new diarylethene with ethylimidazo[2,1-b]thiazole-6-hydrazide unit was synthesized, and its photochromic and fluorescent behaviors have been systematically investigated by the stimulation of lights and metal ions in methanol. This new diarylethene exhibited high selectivity and sensitivity toward Al3+ and Zn2+. The addition of Al3+ and Zn2+ displayed excellent colorimetric response behaviour with the concomitant color change from colorless to yellow, which could be easily observed by the naked eye. Upon addition of Al3+, the fluorescence intensity was enhanced by 180–fold and the emission peak of 1O–Al3+ blue-shifted by 15?nm accompanied with a color change from colorless to bright blue. In contrast, when stimulated with Zn2+, its fluorescence intensity was enhanced by 35–fold and the emission peak of 1O–Zn2+ red-shifted by 16?nm with an evident color change from black to bright green. The LOD for Al3+ and Zn2+ were determined to be 2.97?×?10?9?mol?L?1 and 5.98?×?10?9?mol?L?1, respectively. Moreover, a logic circuit was constructed with the fluorescence intensity as the output signal responding to the light and chemical species as the inputs.  相似文献   

16.
Functional star-shaped 4-arm poly(ethylene glycol)-b-poly[(ε-caprolactone-co-γ-amino-ε-caprolactone)] (4-arm PEG-b-P(CL-co-ACL) was synthesized through ring-opening polymerization. The structure of the copolymer was confirmed by 1H NMR, Fourier transform infrared spectroscopy (FTIR), and gel permeation chromatography (GPC). To further understand the copolymers, the difference of the conversion rate between ε-caprolactone (CL) and γ-(carbamic acid benzyl ester)-ε-caprolactone (CABCL) and the detailed deprotection condition were studied. The thermal property of the copolymer was analyzed by WAXR and differential scanning calorimetry (DSC), which demonstrated that the thermal property could be well adjusted. The pH-responsive behavior of the copolymers was studied in detail by dynamic light scattering (DLS), pH titration, and pyrene fluorescence methods, which indicated that it could form micelles and exhibit pH responsibility. Moreover, the copolymer was nontoxic and had good biocompatibility according to the results by 3-(4,5)-dimethylthiahiazo (-z-y1)-3,5-di-phenytetrazoliumromide (MTT) assay.  相似文献   

17.
Zhaochao Xu  Jingnan Cui  Rong Zhang 《Tetrahedron》2006,62(43):10117-10122
The design, synthesis, and photophysical evaluation of a new naphthalimide-based fluorescent chemosensor, N-butyl-4-[di-(2-picolyl)amino]-5-(2-picolyl)amino-1,8-naphthalimide (1), were described for the detection of Zn2+ in aqueous acetonitrile solution at pH 7.0. Probe 1 showed absorption at 451 nm and a strong fluorescence emission at 537 nm (ΦF=0.33). The capture of Zn2+ by the receptor resulted in the deprotonation of the secondary amine conjugated to 1,8-naphthalimide so that the electron-donating ability of the N atom would be greatly enhanced; thus probe 1 showed a 56 nm red-shift in absorption (507 nm) and fluorescence spectra (593 nm, ΦF=0.14), respectively, from which one could sense Zn2+ ratiometrically and colorimetrically. The deprotonated complex, [(1-H)/Zn]+, was calculated at m/z 619.1800 and measured at m/z 618.9890. In contrast to these results, the emission of 1 was thoroughly quenched by Cu2+, Co2+, and Ni2+. The addition of other metal ions such as Li+, Na+, K+, Mg2+, Ca2+, Fe3+, Mn2+, Al3+, Cd2+, Hg2+, Ag+, and Pb2+ produced a nominal change in the optical properties of 1 due to their low affinity to probe 1. This means that probe 1 has a very high fluorescent imaging selectivity to Zn2+ among metal ions.  相似文献   

18.
We have developed naphthalimide-based fluorescent chemosensors that exhibit fluorescence enhancement upon binding Zn2+ ion in 10 mM HEPES buffer (pH 7.4) at 25 °C. The fluorescence enhancement was induced by a PET inhibition process in which electron transfer from the nitrogen lone pair electrons of the Dpa unit to naphthalimide was blocked upon the binding of the sensor to Zn2+. The longer the linker length (n = 1-3) of the sensor, the less the PET efficiency becomes. Among the sensors (1, 2, and 3) examined, 1 shows the highest selectivity and sensitivity for Zn2+ over other transition metal ions and alkali metal ions in water.  相似文献   

19.
Nanocarriers are employed to deliver photosensitizers for photodynamic therapy (PDT) through the enhanced penetration and retention effect, but disadvantages including the premature leakage and non-selective release of photosensitizers still exist. Herein, we report a 1O2-responsive block copolymer (POEGMA-b-P(MAA-co-VSPpaMA) to enhance PDT via the controllable release of photosensitizers. Once nanoparticles formed by the block copolymer have accumulated in a tumor and have been taken up by cancer cells, pyropheophorbide a (Ppa) could be controllably released by singlet oxygen (1O2) generated by light irradiation, enhancing the photosensitization. This was demonstrated by confocal laser scanning microscopy and in vivo fluorescence imaging. The 1O2-responsiveness of POEGMA-b-P(MAA-co-VSPpaMA) block copolymer enabled the realization of self-amplified photodynamic therapy by the regulation of Ppa release using NIR illumination. This may provide a new insight into the design of precise PDT.  相似文献   

20.
Electrospray ionization-tandem mass spectrometry experiments were used to provide evidence regarding the sites of interactions between zinc metal ions and angiotensin peptides. The electrospray ionization mass spectra of histidine-containing human angiotensin II (Asp-Arg-Val-Tyr-Ile-His-Pro-Phe) and angiotensin I (Asp-Arg-Val-Tyr-Ile-His-Pro-Phe-His-Leu) in the presence of zinc show abundant multiply charged ions for the zinc-attached peptide [M + aZn2+ +(c ? 2a)H+]c+, where a = 1, 2 and c is charge. From collisionally activated dissociation experiments, with both low energy (triple quadrupole mass spectrometry) and high energy collisions (linked scan at constant B/E with a double focusing instrument) of the [M + Zn]2+ and [M + Zn + H]3+ ions for angiotensin II, a [b 6 + Zn]2+ species is produced as the most abundant product ion, suggesting that the zinc interaction site is in the vicinity of the His6 residue. Additionally, tandem mass spectra from the zinc-attached ions for angiotensin I show abundant [b 6 + Zn]2+ and [b 9 + Zn]2+ products, providing evidence that both His6 and His9 are involved in zinc coordination.  相似文献   

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