Temperature-induced phase transition and intramolecular charge-transfer process based on poly(N-isopropylacrylamide) hydrogel with covalently attached D-π-A type dye

A thermoresponsive poly(NIPAM-co-dye) copolymer with covalently attached D-π-A type dye was prepared by typical radical copolymerization. Software was used to calculate the electron density distribution of the push-pull, intramolecular charge transfer (ICT) operating in donor-π-conjugation-acceptor (D-π-A) configurations of dye monomer 3. It can be constructed an acid/base-induced molecular switch by modulation of intramolecular charge transfer with protonation/deprotonation. The lower critical solution temperature (LCST) behavior was investigated by means of UV-vis spectroscopy that allows the measurement of the phase transition from 25 to 40 °C in aqueous solution. The poly(NIPAM-co-dye) copolymer also exhibited color change when used an acid/base-induced molecular switch via control of intramolecular charge transfer (ICT). The morphology of the internal microstructure of the poly(NIPAM-co-dye) hydrogel was observed by scanning electron microscopy (SEM). The reversible switch could be obtained by thermal and acid/base stimuli.     

Multiple switching behaviors of poly(N-isopropylacrylamide) hydrogel with spironaphthoxazine and D-π-A type dye

A multi-switchable poly(NIPAM-co-SPO-co-D-π-A dye) hydrogel with a photochromic spironaphthoxazine and an electron donor-π-conjugated-electron acceptor (D-π-A) type dye was prepared by typical radical copolymerization. The low critical solution temperature (LCST) behavior was investigated by UV–vis spectroscopy, which allows the measurement of the phase transition from 20 to 40 °C in aqueous solution. The fluorescence intensity of the poly(NIPAM-co-SPO-co-D-π-A dye) was temperature-dependent. Reversible modulation of fluorescence intensity was achieved using alternating irradiation with UV and visible light. Prepared polymer hydrogel also exhibited spectra change when not only used Cu²⁺ cation but also an acid unit.     

Multi-responsive poly(N-isopropylacrylamide) hydrogel with D-π-A type dye

To get a multi-responsive polymer hydrogel, metal sensible and acid/base-switchable D-π-A type dye monomer was synthesized first. The synthesized electron donor-π-conjugated-electron acceptor (D-π-A) type dye monomer 3 was investigated with not only the selective Ni²⁺ and Cu²⁺ metal ion sensing effects, but also an acid/base unit sensing effects in optical properties with UV-vis absorption and fluorescence emission. A thermo-responsive poly(NIPAM-co-dye) copolymer with D-π-A type dye was prepared by typical radical copolymerization. The LCST behavior was investigated by UV-vis spectroscopy, which allows the measurement of the phase transition from 20 to 50 °C in an aqueous solution. The poly(NIPAM-co-dye) copolymer also exhibited color change when not only Ni²⁺ or Cu²⁺ cations were used but also when an acid/base unit was used. The morphology of the internal matrix structure of the poly(NIPAM-co-dye) hydrogel was observed by SEM.     

Synthesis and Properties of Thermosensitive Poly(N-Isopropylacrylamide)/Waterborne Polyurethane Graded Concentration Hybrid Films

Temperature-sensitive hybrid films were synthesized with a concentration gradient by casting and UV curing of N-isopropylacrylamide (NIPAAm) monomers (0%–70%) on the free surface of waterborne polyurethane (WPU) films on a Teflon substrate. The surface hardness and contact angle of the free surface with a water drop increased asymptotically with the addition of NIPAAm, whereas those on the substrate side were virtually unchanged. The diffusion coefficient (D), rates of swelling at 20°C (below the lower critical solution temperature (LCST) of poly(N-isopropylacrylamide) (PNIPAM)) and deswelling at 50°C (above the LCST) increased with increasing NIPAM content, showing favorable thermosensitivity. In addition, the glassy state modulus and glass transition temperature (Tg) of the film increased with increasing NIPAM content, whereas the rubbery modulus decreased due to the increased molecular weight between the crosslinks. In addition, as the NIPAM content increased, the film showed a positive yield with an increased yield and fracture stress and decreased ductility. Above 50% NIPAM, the film became brittle, showing a linear stress–strain relationship.     

Ultrasonic degradation of poly (styrene-co-alkyl methacrylate) copolymers

The ultrasonic degradation of poly (styrene-co-methyl methacrylate) (SMMA), poly (styrene-co-ethyl methacrylate) (SEMA) and poly (styrene-co-butyl methacrylate) (SBMA) copolymers of different compositions was studied. The copolymers were synthesized and NMR spectroscopy was used to determine the composition, and the glass transition temperatures were determined by DSC. The reactivity ratios were determined by the Kelen–Tudos method and it indicated that the copolymers were random. The effect of solvent, temperature and copolymer composition on the ultrasonic degradation rate of these copolymers was investigated. A model based on continuous distribution kinetics was employed to study the degradation kinetics. The degradation rate coefficients of the copolymers decreased with an increase in the styrene content in the copolymer. At any particular copolymer composition the rate of degradation follows the order: SBMA > SEMA > SMMA. Thermogravimetric analysis (TGA) of the copolymers was carried in order to assess their thermal stability. The same order of degradation was observed for the thermal degradation of the copolymers as that observed for ultrasonic degradation.     

Thermo-responsive copolymer coatings for flow regulation on demand in glass microcapillaries

This study presents thermo-responsive on-demand regulation of water flow rate in glass microcapillaries with a recently developed water-stable, stimuli-responsive poly(methyl methacrylate/N-isopropyl acrylamide) [P(MMA/NIPAM)] copolymer grafted at the inner walls. It is shown that the grafted coatings are stable and can withstand significant tractions under temperature variation. Such microcapillaries allow flow regulation on demand by changing temperature across the lower critical solution temperature (LCST) of the copolymer layer, which makes it swell or shrink, thus changing the bore available for pressure-driven flow. The grafted copolymer layers were subjected to different pressure drops applied to the capillary open ends, as well as to periodic temperature variation across the copolymer LCST to determine the best grafting conditions for microfluidic operation. Then, by varying the temperature, the flow rate in the capillaries was changed periodically on demand due to the swelling/shrinkage of the grafted copolymer layer. It was also shown that the entrapped air bubbles are present in the coating which can result in an apparent slip.     

Towards the higher solubility and thermal stability of poly(aniline-<Emphasis Type="Italic">co</Emphasis>-<Emphasis Type="Italic">m</Emphasis>-bromoaniline)

In the current study, we have described the synthesis and the physical properties of poly(aniline-co-m-bromoaniline) conducting copolymers. The copolymers of different composition are essentially obtained by varying the molar feed ratio of the two monomers. The higher solubility of the copolymers could be procured as compared to polyaniline (PA) in different solvents. The electrical conductivity has been studied by two-probe method; at room temperature, the conductivity of the copolymer decreases upon increasing the molar ratio of m-bromoaniline monomer. The introduction of bromine (–Br) group reduces the degree of conjugation in the polymer chain. Thus, conduction of electrons is prohibited along the conjugated system. In the thermogravimetric analysis (TGA), a three-stage decomposition of the copolymer has been observed. The copolymers of poly(aniline-co-m-bromoaniline) are thermally stable at high temperature. The composition of the copolymer has been confirmed from the binding energies of C–C, C–N, and C–Br in the XPS study.     

Fluorescence Investigations of “Smart” Microgel Systems

Fluorescence techniques, including lifetime, quenching, and time-resolved anisotropy measurements (TRAMS), were used to study microgel systems based upon N-isopropylacrylamide (NI-PAM) using pyrene as a fluorescent probe. These experiments have revealed that poly(N-isopropylacrylamide) (PNIPAM) nanoparticles undergo a phase transition at a lower critical solution temperature (LCST), of ca. 34°C, which involves collapse of the particles into compacted, hydrophobic spheres. A degree of control over the LCST has been achieved by copolymerization of NIPAM with varying amounts of dimethylacrylamide (DMAC). Incorporation of DMAC into the gel has the effect of changing the hydrophobic to hydrophilic balance and shifts the LCST to a higher temperature. Fluorescence methods indicate that the NIPAM/DMAC gels are of a more open, water-swollen nature above the LCST than that of their PNIPAM counterparts.     

Copolyacrylates with phenylalanine and anthracene entities prepared by ATRP and microwave irradiation

In this study, two amino acid copolymers containing anthracene incorporated either on the one end, poly(N-acryloyl-l-phenylalanine-co-methyl methacrylate)-1 or as pendant groups, poly-(N-acryloyl-l-phenylalanine-co-methyl methacrylate)-2 were prepared directly from N-acryloyl-l-phenylalanine (APhe) and methyl methacrylate (MMA) through atom transfer radical polymerization (ATRP) and microwave-assisted synthesis. In the first case, 9-(chloromethyl)anthracene was used as an ATRP-initiator to obtain a copolymer that contains amino acid sequences and anthracene end-capped units (0.03 molar fraction). Rapid synthesis of copolymer under microwave irradiation (250 W) in the presence of 1,1′-azobis(cyclohexanecarbonitrile) used as an initiator was followed of a functionalization of the formed copolymer with an anthracene derivative yielding copolyacrylate with pendant anthracene (0.02 molar fraction). The structure of the copolymers was verified by ¹H NMR, UV-Vis and FTIR spectroscopy, gel permeation chromatography (GPC), and fluorescence spectroscopy. The fluorescence quenching process of anthracene which exists in copolymers by FeCl₃, cobalt acetate, nitrobenzene, maleic anhydride, diethylaniline and nitromethane in DMF solutions shows that this involves an electron transfer between the excited state anthracene and the present transitional metal cations, more efficiently being FeCl₃ for poly-(APhe-co-MMA)-1 and cobalt acetate for the latter copolymer.     

Synthesis of novel magnetic phosphazene-containing polymer microspheres with active hydroxyl groups

Monodisperse magnetic phosphazene-containing polymer microspheres with active hydroxyl groups were prepared at room temperature by ultrasonic irradiation. The morphology and structure of the magnetic poly(cyclotriphosphazene-co-4,4′-sulfonyldiphenol) (PZS) microspheres were characterized and the coordination behavior between magnetic nanoparticles and PZS microspheres was investigated. The magnetic measurements reveal that the magnetic microspheres are superparamagnetic with saturation magnetization of 34.9 emu/g. The paper presents a simple, economic and environmentally friendly route to preparing monodisperse magnetic hybrid inorganic-organic microspheres with functional groups.     

Preferential surface segregation of homopolymer and copolymer blend films

Surface film properties of the homopolymers polystyrene (PS), poly(methyl methacrylate) (PMMA), poly(butyl methacrylate) (PBMA) and the copolymer poly(methyl methacrylate)-co-poly(butyl methacrylate) (PMMA-co-PBMA) and their blends with PS have been examined by atomic force microscopy (AFM) and contact angle measurements. The total and the Lifshitz-van der Waals, acid and base components of the surface free energy together with the work of adhesion and its components, the cohesive energy density and the solubility parameters of the homopolymer, copolymer and blend films were determined. Films of about 3 μm were considered. The results are discussed in terms of surface migration mechanisms based on surface free energy and solubilities of the polymers in the solvent, toluene in this paper. AFM imaging and contact angles revealed surface enrichment at the air polymer interface of PBMA for both the PS/PBMA blend and the copolymer PMMA-co-PBMA, whereas the PS/PMMA and PS/PMMA-co-PBMA blend film surfaces show island-like phase-separated structure of typical size 27.4-86.5 nm in diameter and 6.9-15.6 nm in height for PS/PMMA, while for PS/ PMMA-co-PBMA film surface the typical size is 49.6-153.3 nm in diameter and 1.6-14.2 nm in height.     

P(NIPAM-co-AA)/Clay nanocomposite hydrogels exhibiting high swelling ratio accompanied by excellent mechanical strength

In this paper, a series of P(NIPAM-co-AA)/Clay composite hydrogels (abbreviated as NAC gels) with high swelling ratio and excellent mechanical strength were synthesized and characterized by DMA, SEM, and IR. In NAC gels composed of a unique organic P(NIPAM-co-AA)/inorganic (clay) network, the inorganic clay acts as a multifunctional cross-linker in place of an organic cross-linker as used in the conventional chemically cross-linked hydrogels (abbreviated as OR gels). The NAC gels exhibit excellent swelling ratio, and there was no detectable change in properties on altering the concentration of clay, while the swelling ratio tends to decrease slightly when C _clay increases up to 25 wt%, which was revealed in swelling measurements. IR spectra show that clay has been intercalated by copolymers. Furthermore, results of DMA reveal that the composite hydrogel has an excellent mechanical strength by using a wide range of clay concentration, while the moduli improve with increasing C _clay.     

Stable superhydrophobic surfaces over a wide pH range

A stable superhydrophobic surface was fabricated by solidifying poly(epoxy-terminated polydimethylsiloxane-co-bisphenol A) [P(ETPDMS-co-BPA)] copolymer on a rough substrate. The low surface energy of the copolymer and the geometric structure at micrometer scale of the surface contribute to the superhydrophobic property. The as-prepared surface shows stable superhydrophobicity over a wide pH range (1-14) and the wettability is excellent stable to heating, water, corrosive solution and organic solvent treatments. The procedure is simple and time-saving as well as utilizing non-fluorine-containing compounds.     

Multifunctional core–shell nanoparticles: superparamagnetic,mesoporous, and thermosensitive

Multifunctional core–shell composite nanoparticles (NPs) have been developed by the combination of three functionalities into one entity, which is composed of a single Fe₃O₄ NP as the magnetic core, mesoporous silica (mSiO₂) with cavities as the sandwiched layer, and thermosensitive poly(N-isopropylacrylamide-co-acrylamide) (P(NIPAAm-co-AAm)) copolymer as the outer shell. The mSiO₂-coated Fe₃O₄ NPs (Fe₃O₄@mSiO₂) are monodisperse and the particle sizes were varied from 25 to 95 nm by precisely controlling the thickness of mSiO₂-coating layer. The P(NIPAAm-co-AAm) were then grown onto surface-initiator-modified Fe₃O₄@mSiO₂ NPs through free radical polymerization. These core–shell composite NPs (designated as Fe₃O₄@mSiO₂@P(NIPAAm-co-AAm)) were found to be superparamagnetic with high r ₂ relaxivity. To manipulate the phase transition behavior of these thermosensitive polymer-coated NPs for future in vivo applications, the characteristic lower critical solution temperature (LCST) was subtly tuned by adjusting the composition of the monomers to be around the human body temperature (i.e. 37 °C), from ca. 34 to ca. 42 °C. The thermal response of the core–shell composite NPs to the external magnetic field was also demonstrated. Owing to their multiple functionality characteristics, these porous superparamagnetic and thermosensitive NPs may prove valuable for simultaneous magnetic resonance imaging (MRI), temperature-controlled drug release, and temperature-programed magnetic targeting and separation applications.     

A novel method for the synthesis of polystyrene-graft-silica particles using random copolymers based on styrene and triethoxyvinylsilane

In the present research, random copolymers based on triethoxyvinylsilane (TEVS) and styrene (St) are synthesized and structurally characterized. According to the reactivity ratios of the monomers determined by infrared analysis; St tends to form blocks whilst TEVS is expected to be incorporated as isolated units. A sample of poly(styrene-co-triethoxyvinylsilane) synthesized at low conversion using a monomer feeding ratio St:TEVS of 2:3 was used as macrosilane in the synthesis of polystyrene-g-silica particles. The grafting reaction was confirmed by infrared spectroscopy, thermogravimetric analysis and by the evaluation of the morphological characteristics of the hybrid particles.     

Sonochemical synthesis of novel thermo-responsive polymer and tungsten dioxide composite for the temperature-controlled reversible “on-off” electrochemical detection of β-Blocker metoprolol

Thermo-responsive polymer nanocomposite based on poly (styrene-co-N-isopropylacrylamide) hybrid tungsten dioxide (WO₂@PS-co-PNIPAM) was synthesized by a facile ultrasonic irradiation (Frequency; 20 kHz, power; 180 W, calorimetrically determined power; 5.73 W in the bath, and Type; probe) method in the presence of water as inisolv. The as-synthesized WO₂@PS-co-PNIPAM modified glassy carbon electrode (WO₂@PS-co-PNIPAM/GCE) was acting as a reversibly switched detection for the electrooxidation of metoprolol (MTP), with the thermal stimuli response of the PNIPAM. In below lower critical solution temperature (LCST), the PS-co-PNIPAM expanded to embed the electroactive sites of WO₂, and the MTP could not proceed via the polymer to attain electronic transfer, indicating the “off” state. Rather, in above LCST, the PS-co-PNIPAM shrank to reveal electroactive sites and expand cyclic voltammetric background peak currents, the MTP was capable to undergo electro-oxidation reaction usually and produce the response current, indicating “on” state. Additionally, the proposed sensor had excellent sensitivity (2.21 µA µM⁻¹ cm⁻²), wide dynamic range (0.05–306 µM), and a low limit of detection of 0.03 µM for MTP. Intriguingly, the fabricated sensor demonstrates the good selectivity towards the detection of MTP among the possible interfering compounds. Eventually, the WO₂@PS-co-PNIPAM/GCE has been utilized in the analysis of MTP in human blood serum samples.     

丙烯酰胺-甲基丙烯酸共聚物结构的NMR研究

用¹H NMR谱,¹³C NMR谱,DEPT谱,gHMQC,gHMBC二维谱和质子弛豫时间等方法研究了在紫外光辐照条件下丙烯酰胺(AM) -甲基丙烯酸(MAA)共聚合反应,讨论了AM-MAA共聚合反应时间与转化率的关系、共聚单体的连接方式、共聚物序列结构以及不同辐照时间下形成的共聚物链运动. 结果表明在紫外光辐照条件下,AM-MAA共聚物链节中同时存在多种连接方式,当反应时间为45 min时,共聚合转化率可达100%. 从自旋-晶格弛豫时间（T₁）和自旋-自旋弛豫时间（T₂）测定中得出,在辐照1小时范围内,时间越长聚合物长链分子运动速度越快,但主链的链段运动变化不明显.     

Poly(4-vinylpyridine) supported acidic ionic liquid: A novel solid catalyst for the efficient synthesis of 2,3-dihydroquinazolin-4(1H)-ones under ultrasonic irradiation

A novel poly(4-vinylpyridine) supported acidic ionic liquid catalyst was synthesized by the reaction of 4-vinylpyridine with 1,3-propanesultone, followed by the polymerization and the addition of the heteropolyacid. Due to the combination of polymer features and ionic liquid, it acted as a heterogeneous catalyst to effectively catalyze the cyclocondensation reaction of anthranilamide with aldehydes under ultrasonic irradiation and afforded the corresponding 2,3-dihydro-4(1H)-quinazolinones compounds in good to excellent yields. In addition, the catalyst could be easily recovered by the filtration and reused six times without significant loss of catalytic activity. More importantly, the use of ultrasonic irradiation can obviously accelerate the reaction.     

Design, synthesis and characterization of a highly luminescent Eu-complex monomer featuring thenoyltrifluoroacetone and 5-acryloxyethoxymethyl-8-hydroxyquinoline

A multi-functional ligand, 5-acryloxyethoxymethyl-8-hydroxyquinoline (Hamq), was synthesized, which contained a polymerizable C=C double bond for the copolymerization with other vinyl monomers and acted as photon antenna able to transfer energy to Eu³⁺ ions effectively. The triplet state energy of Hamq was determined to be 22,370 cm⁻¹ via the phosphorescence spectra of Hamq and its gadolinium complex. The title complex monomer Eu(tta)₂(amq) was prepared by coordination reaction of Hamq with europium isopropoxide and 2-thenoyltrifluoroacetone (Htta) in dry organic solvents under argon atmosphere and characterized by elemental analysis and IR spectrum. The photophysical properties of the complex were studied in detail with UV-vis, luminescence spectra, luminescence lifetime and quantum yield. The complex exhibited nearly monochromatic red emission at 612 nm, a remarkable luminescence quantum yield at room temperature (30.6%) upon ligand excitation and a long ⁵D₀ lifetime (389 μs), which indicated that the ligand Hamq could sensitize the luminescence of Eu(III) ion efficiently in Eu(tta)₂(amq), resulting in a strong luminescence of its copolymer poly[MMA-co-Eu(TTA)₂(amq)] under UV excitation. The excellent luminescence properties of the complex made it not only a promising light-conversion molecular device but also an excellent luminescent monomer.     

Superparamagnetic nanocomposites based on poly(styrene-b-ethylene/butylene-b-styrene)/cobalt ferrite compositions

Magnetic nanoparticles were created in or around the sulfonated (s) polystyrene domains in a phase separated poly[styrene-b-(ethylene-co-butylene)-b-styrene)] block copolymer (BCP) using an in situ inorganic precipitation procedure. The sBCP was neutralized with a mixed iron/cobalt chloride electrolyte and the doped samples were converted to their oxides by reaction with sodium hydroxide and further washing with water. Transmission electron microscopy indicated the presence of nanoparticles in the 5–25 nm size range. The metal oxide particle structures were studied using select area electron diffraction, which revealed that they are of the cobalt iron oxide composition (CoFe₂O₄). These nanocomposites were shown, using a superconducting quantum interference device magnetometer, to be superparamagnetic at 300 K and ferrimagnetic at 5 K. Nanocomposites consisting of smaller particles have a blocking temperature of 70 K, whereas it was 140 K for larger particles.