Synthesis and characterisation of poly(2-hydroxyethyl methacrylate) polyelectrolyte complexes

Copolymerisation of charged and neutral monomers is a well-known methodology to introduce charged moieties in a polymeric chain to obtain polyelectrolytes. New polyelectrolyte complexes have been synthesised by radical copolymerisation of neutral methacrylic monomer 2-hydroxyethyl methacrylate (HEMA) with cationic 2-methacryloyloxyethyltrimethyl ammonium chloride and anionic 2-acrylamido-2-methylpropane-sulphonic acid monomers in 10:1:1 and 10:1:2 stechiometric ratio. Chemical structure of the synthesised terpolymers was confirmed by FT-IR spectroscopy, moreover, X-ray photoelectron spectroscopy showed the presence of a cationic charge excess on the 10:1:2 terpolymer surface with respect to 10:1:1 terpolymer. Swelling studies for 10:1:2 terpolymers showed a high water content in the swollen state and a "smart behaviour" upon changes in external stimuli such as pH, while, 10:1:1 terpolymer presented the behaviour of a neutral polymer. Mechanical and differential scanning calorimetry analysis confirmed that terpolymer networks were stabilised by ionic co-operative interactions. Infact, the inclusion of oppositely ionic charges in the polymeric network of p(HEMA) represent a way to achieve higher elastic modulus as they stabilise the terpolymer networks. Cytotoxicity and cytocompatibility studies demonstrated that all materials were not toxic, moreover, the presence of a cationic charge excess on 10:1:2 terpolymer surface was able to promote fibroblast adhesion.     

Synthesis and property study on Eu(III) complexes of modified poly(N-isopropylacrylamide)

Poly(N-isopropylacrylamide) with aromatic end groups (Ar-PNIPAM) were synthesized by atom transfer radical polymerization of N-isopropylacrylamide in isopropanol using phenyl 2-chloropropionate, (4′-phenyl)phenyl 2-chloropropionate, and (2′,6′-diphenyl)phenyl 2-chloropropionate as initiators and CuCl/tris(2-dimethylaminoethyl)amine (Me₆TREN) as a catalytic system. The resulting polymers had narrow polydispersity index of 1.10–1.14 and molecular weights of 3700–4600 g mol⁻¹. Then, novel functional complexes of Ar-PNIPAM, Europium(III) (Eu(III)), and α-Thenoyltrifluoroacetone (TTA) (Ar-PNIPAM/Eu(III)/TTA) with thermosensitive and fluorescent properties were synthesized and characterized by Fourier transform infrared spectra and fluorescence spectroscopy. Metal Eu(III) was not only bonded to oxygen and nitrogen atoms of polymer chain in PNIPAM, but also bonded to TTA. The maximum emission intensity of the complexes at 613 nm was enhanced about 22, 27, 33 times compared with that of the corresponding Eu(III). The lower critical solution temperatures (LCSTs) of Ar-PNIPAM/Eu(III)/TTA were slightly greater compared with that of PNIPAM. Eu(III) complexes had excellent fluorescence performance, the fluorescence spectrum presented characteristic emission of Eu(III) at 613 nm.     

Synthesis and characterization of a novel poly(N-vinyl)-3-[p-nitrophenylazo]carbazolyl-CdS nanocomposites through chemical hybridization

A novel bi-functional photorefractive (PR) poly(N-vinyl)-3-[p-nitrophenylazo]carbazolyl with carbazolyl fragments and chromophoric azophenyl was synthesized by a post azo coupling reaction and characterized by ¹H NMR, elemental analysis, UV–Vis absorption and FTIR spectroscopy. Then chemical hybridized poly(N-vinyl)-3-[p-nitrophenylazo]carbazolyl-CdS nanocomposites with different molar ratio of CdS to poly(N-vinyl)-3-[p-nitrophenylazo]carbazolyl were prepared. It was confirmed that the CdS particles had a nanoscale size and quantum confinement effect adopting transmission electron microscopy and UV–Vis absorption spectroscopy. The generation of photocurrent on illumination and photoconductive properties of the nanocomposites were studied. Significant enhancement in photoconductivity induced by the chemical doping of CdS in poly(N-vinyl)-3-[p-nitrophenylazo]carbazolyl has also been demonstrated.     

Sulphonated poly(ether ether ketone): Synthesis and characterisation

The sulphonation of commercially available PEEK in powder form (Gatone, Gharda Chemicals Limited, India) was carried out using conc. H²SO⁴ under different reaction conditions. The duration of reaction was varied from 3–5 h, polymer concentration 4–10% (w/v) and temperature 35–50C. Structural characterisation of sulphonated polymers was done by elemental analysis, FT-IR and ¹H-NMR spectroscopy. The degree of sulphonation as calculated from ¹H-NMR and elemental analysis (S-content) was found to be in the range of 50–80%. Multistep mass loss was observed in thermogravimetric traces (recorded in N² atmosphere). The first step (50–225 ± 25C) was due to loss of moisture (1–10%) and second step (250–425 ± 25C) has been attributed to volatilization of SO³ from the sulphonic group. The backbone degradation takes place above 450C. The mechanical properties and proton conductivities of various sulphonated samples was also evaluated.     

Photopolymerisation and characterisation of negative temperature sensitive hydrogels based on N,N-diethylacrylamide

Despite the many advantages of photopolymerisation in the fabrication of hydrogels, studies on the synthesis of poly(N,N-diethylacrylamide) (PDEAAm) using this technique have received limited attention in the literature. A series of temperature sensitive hydrogels were prepared by free-radical crosslinking copolymerisation of N,N-diethylacrylamide (DEAAm) with 1-vinyl-2-pyrrolidinone (NVP) and N,N-dimethylacrylamide (DMAAm), respectively. Two ultraviolet (UV) light sensitive initiators were trialled in the synthesis, namely 1-hydroxycyclohexylphenylketone and 2-hydroxy-1-[4-(hydroxy-ethoxy)phenyl]-2-methyl-1-propanone, with poly(ethylene glycol)dimethacrylate being used as the crosslinking agent. The lower critical solution temperatures (LCSTs) of the hydrogels synthesised were shown to be close to body temperature using cloud point measurement and modulated differential scanning calorimetry, which is favourable particularly for ‘smart’ drug delivery applications. The swelling behaviour of the samples was investigated upon stepwise temperature change revealing that the hydrogels underwent reproducible pulsatile swelling behaviour. Oscillatory rheological studies showed that increasing the ratio of crosslinking agent could be used as a means of improving the mechanical properties of the photopolymerised temperature sensitive hydrogels.     

Synthesis of poly(meta-diethynyl benzene) with initiated chemical vapour deposition

In this work, polymerization of meta-diethynyl benzene (MDEB) using iCVD is reported, which opens possibilities for use of polymers as a dielectric insulator in electronic applications that cannot be combined with solvent-based materials. iCVD is a solvent free production method, allowing the deposition of PMDEB layers at a rate of 12 nm/min. The polymers produced have a high molecular weight with a broad distribution (1000 to more than 25,000 g/mole) and a clearly defined Fourier transform infrared spectrum. The presence of a small peak at 2105 cm⁻¹ and a monomer peak in the gel permeation chromatogram (GPC) suggest that that some monomer is incorporated in the layers.     

Synthesis,characterisation and non-isothermal degradation kinetics of novel poly(mono ethylene glycol dimethacrylate-co-4-aminobenzoate)

Synthesis of a novel co-polymer made by the addition polymerisation between MEGDMA and 4-AB by aza-Michael addition (AMA) polymerisation method is a fascinating field of research. The present investigation yielded a hazardous metal catalyst-free and toxic solvent-free methodology. The AMA polymerisation was carried out at five different [ M ₁/M ₂] values under N₂ atmosphere at 100^°C for 2 h. Thus, obtained co-polymer was characterized by Fourier transform infrared spectroscopy, UV–visible reflectance spectroscopy, X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis and scanning electron microscopy (SEM). The SEM image confirmed the formation of polymer nanoparticles. The non-isothermal degradation kinetics was followed with four different models, such as Flynn-Wall-Ozawa, Auggis-Bennet, Kissinger and Friedman method. Among the models used, the Kissinger method yielded the lowest degradation kinetics. The degradation kinetics of the co-polymer was followed with the help of model-free methods. Moreover, it was critically compared with the literature.     

Synthesis of polystyrene,poly(styrene/4-vinylpyridine), poly(p-nitrostyrene) and poly(p-aminostyrene)-coated silica and their extraction capabilities for amphetamine

Several novel organic–inorganic hybrid materials, including polystyrene-coated silica (SG-PS), poly(styrene/4-vinylpyridine)-coated silica (SG-PVP), poly(p-nitrostyrene)-coated silica (SG-PS-NO₂) and poly(p-aminostyrene)-coated silica (SG-PS-NH₂), were synthesized in order to improve the extraction methods of harmful stimulants via solid phase extraction. The materials were characterized using infrared spectra (IR), scanning electron microscope (SEM), Brunauer–Emmett–Teller (BET) surface area measurement and thermogravimetric analysis (TG). The application of the new materials in solid phase extraction columns to extract methamphetamine revealed that the extraction capability of poly(styrene/4-vinylpyridine)-coated silica is the best among the four materials, which provides novel supporter materials for extracting amphetamine-derived drugs.     

A versatile approach for the fabrication of Au hollow nanoparticles based on poly(styrene-co-2-aminoethyl methacrylate) template

The hollow Au nanospheres were successfully prepared by the template method. The poly(styrene-co-2-aminoethyl methacrylate hydrochloride) (P(St-co-AEMH)) nanoparticles synthesized by the emulsion polymerization were used as the templates. After coating by Au colloidal nanoparticles and the formation of Au shells, the interior templates were etched out by sulfuric acid, leading to the formation of Au hollow nanospheres. The structure and morphology of the nanoparticles and hollow nanospheres were carefully investigated by the fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray analysis (EDX), wide-angle X-ray diffractometer (WAXD), and thermal gravimetric analysis (TGA) techniques.     

Synthesis, characterization, and application of fluorescence sensing lipobeads for intracellular pH measurements

This paper describes the synthesis and characterization of micrometric phospholipid-coated polystyrene particles, named lipobeads, with pH-sensing capability and their application for intracellular pH measurements in murine macrophages. The phospholipids used to coat the particles are labeled with fluorescein (a pH-sensitive dye) and tetramethylrhodamine (a pH-insensitive dye), which serves as a referencing fluorophore for increased accuracy of the pH measurements. The synthesis of the pH-sensing lipobeads is realized by the covalent attachment of the fluorescent phospholipids to the surface of carboxylated polystyrene particles. The pH dynamic range of the sensing particles is between 5.5 and 7.0 with a sensitivity of 0.1 pH unit. The excitation light intensity is reduced to minimize photobleaching of the fluorescein-phospholipid conjugates. The fluorescent lipobeads are used to measure the pH in single macrophages. The lipobeads are ingested by the macrophages and directed to lysosomes, which are the cellular organelles involved in the phagocytosis process. Despite the high lysosomal levels of digestive enzymes and acidity, the absorbed particles remain stable for over 6 h in the cells when they are stored in a phosphate-buffered saline solution at pH 7.4.     

Synthesis of PbS/poly (vinyl-pyrrolidone) nanocomposite

A simple solution growth method for synthesis of nanocomposite of PbS nanoparticles in poly(vinyl-pyrrolidone) (PVP) polymer is described. The nanocomposite is prepared from methanolic solution of lead acetate (PbAc), thiourea (TU) and PVP at room temperature (∼27 °C). Optical absorption spectrum of PbS/PVP nanocomposite solution shows strong absorption from 300 to 650 nm with significant bands at 400 and 590 nm which is characteristic of nanoscale PbS. Spin-coated nanocomposite films on glass have an absorption edge at ∼650 nm with band gap of 2.55 eV. Fourier transform infrared (FTIR) spectroscopy of PbS/PVP nanocomposite and PVP shows strong chemical bond between PbS nanoparticles and host PVP polymer. The transmission electron microscope (TEM) images reveal that 5-10 nm PbS particles are evenly embedded in PVP polymer. The formation of PbS is confirmed by selective area electron diffraction (SAED) of a typical nanoparticle.     

Synthesis and characterization of conducting poly (1-aminonaphthalene), poly (2-aminonaphthalene) and poly (aniline-co-1-aminonaphthalene)

Poly (1&2)-aminonaphthalene and poly (aniline-co-1-aminonaphthalene) have been synthesized in high yields by chemical oxidative polymerization method. The polymers are soluble in polar solvents such as DMSO, NMP etc. In PNA-2 as head-to-tail coupling cannot occur, the electrical conductivity is lower than PNA-1. The copolymer exhibits distinct morphology, higher viscosity, characteristic exciton peak, appreciable thermal stability and electrical conductivity compared to PNA-1.     

Nickel (II) ions sensing properties of dimethylglyoxime/poly(caprolactone) electrospun fibers

A novel dimethylglyoxime (DMG)/poly(caprolactone) (PCL) blend was electrospun into fibers to serve as an optical sensor for the nickel detection based on the formation of a red Ni(DMG)₂ complex. DMG was mixed with PCL at 10, 20 and 30% (w/w) in a mixture of N, N-dimethylformamide (DMF) and dichloromethane (DCM) (50/50, v/v) prior electrospunning process. The best fibers were prepared under an electric field of 20 kV and a distance between needle and collector of 20 cm. From scanning electron microscopy (SEM), the average diameter of the fibers remained nearly constant with increasing amount of DMG. The optimum mass ratio of DMG and PCL was found to be 20:80 as it produced fibers with the smallest diameter distribution and the best sensing property. The formation of the Ni(DMG)₂ complex was confirmed by Fourier transform infrared spectroscopy (FT-IR). The colorimetric response of the PCL/DMG electrospun fibers were then tested against the nickel ions over a concentration range of 1-10 ppm using reflectance spectroscopy. Good linearity between the reflectance values at 547 nm and the concentrations was obtained (R² = 0.9925). These proposed DMG and PCL fibers could be used as the naked-eye sensor for nickel in waste water.     

Hollow spherical nanocapsules of poly(pyrrole) as a promising support for Pt/Ru nanoparticles based catalyst

Poly(pyrrole) hollow spherical nanocapsules (HSNCs-PPy) were prepared and used as an efficient support matrix to PtRu nanoparticles. γ-Radiation was utilized to load PtRu nanoparticles into Ppy-HSNC matrix. The advantageous characteristics of HSNCs-Ppy/PtRu catalyst as a support matrix for loading PtRu catalysts are presented.     

聚乙二醇改性聚乳酸的合成与性能表征

以外消旋乳酸(D,L-LA)和不同数均分子量(Mn)的聚乙二醇(PEG)为原料,通过熔融缩聚法,合成了系列聚乳酸聚乙二醇(PLEG)。最佳工艺条件为:以(Sn(Oct)2)为催化剂,m(Sn(Oct)2)为0.8%,n(PEG)∶n(D,L-LA)=1∶600,聚合温度170℃,压力0.096 MPa条件下,反应8h。用特性粘度测试、FT-IR、XRD、接触角等对其进行表征,实验结果表明系列PLEG中PLEG-800接触角为63°,表明其亲水性能最好;PEG-800和乳酸共聚合成的PLEG的粘均分子量最大,可达48997,与PDLLA相比,结晶度有较大提高,亲水性得到改善。     

Impedance spectroscopy measurements of charge carrier mobility in 4,4'-N,N'-dicarbazole-biphenyl thin films doped with tris(2-phenylpyridine) iridium

The charge carrier mobility of green phosphorescent emissive layers, tris(2-phenylpyridine) iridium [Ir(ppy)₃]-doped 4,4'-N,N'-dicarbazole-biphenyl (CBP) thin films, has been determined using impedance spectroscopy (IS) measurements. The theoretical basis of mobility measurement by IS rests on a theory for single-injection space-charge limited current. The hole mobilities of the Ir(ppy)₃-doped CBP thin films were measured to be 10^− 10–10^− 8 cm²V^− 1 s^− 1 in the 2–7 wt.% Ir(ppy)₃-doped CBP from the frequency dependence of both conductance and capacitance. These hole mobility values are much lower than those of the undoped CBP thin films (~ 10^− 3 cm²V^− 1 s^− 1) because the Ir(ppy)₃ molecules act as trapping centers in the CBP host matrix. These mobility measurements in the Ir(ppy)₃-doped CBP thin films provide insight into the hole injection process.     

Optical and morphological characterisation of a silver nanoparticle/fluorescent poly(phenylenethynylene) composite for optical biosensors

Thiol silver nanoparticles prepared by the phase transfer method have been mixed with a fluorescent poly(phenylenethynylene) sequenced with dithioester-diethylsulfide moieties in order to develop a nanocomposite for its possible application in optical biosensors for the detection and attack of fungi such as Paecilomyces variotii. Films have been prepared by dipping technique and characterized by AFM, XPS, UV-Visible and fluorescence spectroscopy. Optical Absorption properties of the nanocomposite are similar to those of the polymer with an absorption tail in the visible which supports the presence of silver nanoparticles. Despite the lack of fluorescence of the nanoparticles, the composite emits in the yellow green region and the intensity of the fluorescence of the nanocomposite film decreases after the immersion in the culture thus permitting the detection of the fungus by this technique. The fungus can be deposited on films of both the polymer and nanocomposite, nevertheless only in the latter case, an attack on mycelium is observed revealing the fungicidal effect of silver nanoparticles in the nanocomposite.     

2,4,6-Tris (2-pyridyl)-1,3,5-triazine nanobelts as an effective fluorescent sensing platform for DNA detection

In the present study, we report on the use of 2,4,6-tris (2-pyridyl)-1,3,5-triazine nanobelts (TPTNBs) as an effective fluorescent sensing platform for DNA detection for the first time. The general concept used in this approach is based on adsorption of fluorescently labeled single-stranded DNA (ssDNA) probe by TPTNB, due to the strong pi-pi stacking between unpaired DNA bases and TPTNB. As a result, the fluorophor is brought into close proximity of TPTNB, leading to fluorescence quenching. Upon presence of the target ssDNA, specific hybridization with the target takes place to form a double-stranded DNA (dsDNA). The resultant dsDNA cannot be adsorbed by TPTNB due to its rigid conformation and the absence of unpaired DNA bases. Thus, the fluorophor is seperated from TPTNB accompanied by fluorescence recovery. The present system shows a detection limit as low as 3 nM and has a high selectivity down to single-base mismatch.     

Synthesis and characterization of 5,7-dimethyl-8-hydroxyquinoline and 2-(2-pyridyl)benzimidazole complexes of zinc(II) for optoelectronic application

Bis(5,7-dimethyl-8-hydroxyquinolinato)zinc(II) (Me₂q)₂Zn and 5,7-dimethyl-8-hydroxyquinolinato(2-(2-pyridyl)benzimidazole) zinc(II) Me₂q(pbi)Zn have been synthesized and characterized by various techniques. These metal complexes have high thermal stability (>300 °C) and high glass transition temperatures (>150 °C). The vacuum deposited films of these materials show good film forming property and are suitable for opto-electronic applications. Multilayered organic electroluminescent (EL) devices have been fabricated having structure ITO/α-NPD/zinc complex/BCP/Alq₃/LiF/Al, which produce emission with chromaticity having Commission Internationale d’Eclairage (CIE) coordinates x = 0.506 and y = 0.484 for (Me₂q)₂Zn; x = 0.47 and y = 0.52 for (Me₂q)(pbi)Zn complex. The electroluminescence spectra show peak emission centered at 572 and 561 nm respectively for these materials.     

Synthesis, characterization and hydrolytic degradation of degradable poly(butylene terephthalate)/poly(ethylene glycol) (PBT/PEG) copolymers

Hydrolytic degradable PBT/PEG copolymer was synthesized by macromolecular transesterification method from PBT and PEG macromonomers. The resultant copolymers were characterized by ¹H-NMR and GPC. The non-isothermal crystallization behavior of these copolymers was studied by differential scanning calorimetry (DSC). The water absorption and hydrolytic degradation behavior of PBT/PEG copolymers were also studied in detail. This work was partly presented in 6^th ASBM, July 19–22, 2004, Emei City, Chingdu, China. Fan LY is the co-first author for this work.