Reagentless d-sorbitol biosensor based on d-sorbitol dehydrogenase immobilized in a sol–gel carbon nanotubes–poly(methylene green) composite

A reagentless d-sorbitol biosensor based on NAD-dependent d-sorbitol dehydrogenase (DSDH) immobilized in a sol–gel carbon nanotubes–poly(methylene green) composite has been developed. It was prepared by durably immobilizing the NAD⁺ cofactor with DSDH in a sol–gel thin film on the surface of carbon nanotubes functionalized with poly(methylene green). This device enables selective determination of d-sorbitol at 0.2 V with a sensitivity of 8.7?μA?mmol^?1?L?cm^?2 and a detection limit of 0.11 mmol?L^?1. Moreover, this biosensor has excellent operational stability upon continuous use in hydrodynamic conditions.

Hydrophilic films based on poly(acrylic acid)–poly(vinyl methyl ether) blends cross-linked by gamma-radiation

Hydrophilic polymeric films based on blends of poly(acrylic acid) and poly(vinyl methyl ether) (PVME) were prepared by casting technique and were cross-linked by gamma-radiation. The films are soft and elastic in a dry state and form hydrogels upon immersion in water. Effect of absorbed dose on the gel fraction as well as on the swelling of the films in aqueous solutions of different pH is studied. It was found that addition of lower molecular weight PVME decreases the gelation dose, which is likely related to a decrease in glass transition temperature of the blends. In acidic media the films have low swelling degree because of suppression of carboxylic groups ionisation and formation of additional physical cross-links via interpolymer hydrogen bonding.     

Electrogeneration and characterization of a poly(pyrrole–nickel (II) chlorin) electrode

We describe herein, the electrochemical properties of an hydroporphyrin of Ni(II) substituted by two pyrrole groups in organic media (THF and CH₂Cl₂). In the anodic region it has been shown that the electrochemical behaviour of this complex investigated by cyclic voltammetry and coulometry coupled with UV–visible spectroscopy is strongly dependent on the nature of the solvent.Furthermore, the electrochemical oxidation of the pyrrrole groups has led to the first example of an electrogenerated polypyrrole–metallochlorin film. The resulting modified electrodes exhibit the same electrochemical properties as the monomer free in solution. Preliminary experiments have also demonstrated the possibility to study electrochemically this polymeric film in CH₃CN contrary to the Ni(II) chlorin, which is insoluble in this medium.     

Solid polymer nanocomposite electrolytes based on poly(ε-caprolactone)-based waterborne polyurethane–polyethylene oxide and fluorine-doped carbon quantum dot-MXene

The need for higher energy storage capability has encouraged researchers to move toward lithium-metal batteries (LMBs). Due to the safety issue associated with liquid electrolytes, solid polymer electrolytes (SPEs) the main focus on polyethylene oxide (PEO) were at the center of the research. However, high crystallization, fast decomposition, and low thermomechanical stability has limited its application. Low lithium-ion transference number ( $$) is another issue leading to polarization of the SPEs and consequently, triggering dendrite nucleation and growth. Here, we developed a series of SPEs based on PEO-waterborne polyurethane (WPU) and nanoparticles of fluorine-doped carbon quantum dot (fCQD) and MXene. The host polymer matrix was a blend of poly(ε-caprolactone) (PCL)-based WPU and PEO. The use of WPU and the nanoparticles increased the thermomechanical stability and suppressed PEO crystallinity through disrupting the spherulites growth and reducing the thermal stability of the crystallites. Using the WPU led to significant increase in $$ ( $$) compared with previous reports. The prepared SPEs showed high-electrochemical stability and ionic conductivity at $$ and based on the results of cycling performance, a discharge capacity of 120.58 mAh/g and coulombic efficiency of 99.1% was achieved after 200 cycles.     

Studies on Diels–Alder thermoresponsive networks based on ether–urethane bismaleimide functionalized poly(vinyl alcohol)

Thermoreversible networks obtained by the Diels–Alder cycloaddition reaction of poly(vinyl furfural) with urethane bismaleimides containing polyether chain were synthesized. The formation of the networks was confirmed by attenuated total reflectance in conjunction with Fourier transform infrared spectroscopy (ATR–FTIR). The materials thermal properties were investigated using differential scanning calorimetry (DSC) and a coupling of dynamic thermogravimetry with Fourier transform infrared spectroscopy and mass spectrometry (TG–FTIR–MS) for pyrolysis behaviour under nitrogen atmosphere. A thermal decomposition mechanism of the networks and poly(vinyl furfural) was discussed via evolved gas analysis. The thermoreversibility of the networks was demonstrated by the presence of the endothermic peak characteristic to the retrodienic process on the DSC heating curves and also the appearance of the exothermic peak, due to the dienic process, on the DSC cooling curve. The dynamic contact angle and free surface energy values of the networks were determined. Measures of the heterogeneity and roughness of the surfaces suggested that the surfaces of the networks’ films are more homogenous than the initial poly(vinyl furfural) surface. Dynamic water vapour sorption studies were conducted.     

Preparation and characterization of microspheres based on blend of poly(lactic acid) and poly(ɛ-caprolactone) with poly(vinyl alcohol) as emulsifier

In this paper, microspheres were prepared by oil-in-water (o/w) emulsion solvent evaporation method. Biodegradable polymer such as blend of poly (lactic acid) (PLA) and poly(?-caprolactone) (PCL) with certain compositions and characteristics was used to prepare the microspheres with poly(vinyl alcohol) (PVA) as an emulsifier. This study observed the microspheres particle’s size distribution at various concentrations of PVA (1%, 1.5%, 2%, and 2.5% PVA). The PVA volume variations effects during the process (50, 100, 150, 200, and 250 mL) were also observed. The blend of PLA and PCL is formed only by physical interaction between them. This can be seen from the FTIR spectrum which shows both PLA and PCL component. The microspheres physical size and appearance were observed by optical microscope (MO). The overall results of this study showed that the formula which used 50–150 mL of 2.5% polyvinyl alcohol produced the microspheres with the most uniform size distribution.     

Studies on core–shell structural nano-micelles based on star block copolymer of poly(lactide) and poly(2-(dimethylamino)ethyl methacrylate)

Inorganic/polymer hybrid star-shaped block copolymer nano-micelles were synthesized. In the synthetic route, multi-hydroxyl polyhedral oligomeric silsequioxane(POSS-(OH)₃₂) was employed as the starting molecule to initiate ring-opening polymerization of d,l-lactide. 2-(Dimethylamino)ethyl methacrylate was found to polymerize at the end of polylactic acid chains, following mechanism of atom transfer radical polymerization. The well-defined star block copolymer core–shell nano-micelles were finally obtained. The structures of the copolymer and the micelles were characterized extensively. The micelles exhibited a regular spherical shape with an average diameter of 170 nm which was confirmed by transmission electron microscopy and dynamic laser scattering. The sizes of both the core and the shell were controlled by adjusting the feed ratios during the syntheses. The micelles demonstrated pH- and temperature-sensitive behaviors.     

Electropolymerized biotinylated poly (pyrrole–viologen) film as platform for the development of reagentless impedimetric immunosensors

We describe herein the synthesis and electrochemical polymerization of a viologen monomer functionalized by a biotin group and the use of its redox properties for the impedimetric sensing of protein binding. The electrochemical oxidation of the pyrrole group at 0.85 V in CH₃CN led to a biotinylated polypyrrole film allowing the successive anchoring of an avidin layer and a biotinylated cholera toxin layer. EIS performed at ?0.45 V/SCE without redox probe in solution showed the specific immobilization of the anti-cholera toxin antibody.     

Formation of polymer–colloid complexes of aluminoxane particles with poly(acrylic acid) and its copolymers with acrylamide

Formation of polymer–colloid complexes formed by positively charged aluminoxane particles with a size of ~4.6 nm, which constitute the main part of the dispersed phase in aluminum polyhydroxychloride sols with poly(acrylic acid) and acrylic acid copolymers with acrylamide, is studied. Conditions of preparing water-soluble polymer–colloid complexes are determined. It is shown that water-soluble polycomplexes are obtained through the interaction of aluminoxane particles with acrylic acid–acrylamide copolymers containing no more than 0.8 mol% acrylic acid units. In the polymer–colloid complex, aluminoxane particles are uniformly distributed over polyelectrolyte macromolecules and the optimum composition is attained at the molar ratio of components Z equal to 1:1. In semidilute solutions, the addition of aluminoxane particles to the copolymer brings about formation of the gel featuring viscoelastic properties. For all copolymers, the maximally elastic properties of the gels are attained at Z ≈ 1.     

Preparation of poly(vinylidene fluoride) nanocomposite membranes based on graft polymerization and sol–gel process for polymer electrolyte membrane fuel cells

Proton conducting nanocomposite membranes consisting of poly(vinylidene fluoride-co-chlorotrifluoroethylene)-graft-poly(styrene sulfonic acid), i.e., P(VDF-co-CTFE)-g-PSSA graft copolymer and sulfonated silica and were prepared using a sol–gel reaction and subsequent oxidation of a silica precursor, i.e., (3-mercaptopropyl) trimethoxysilane (MPTMS). The successful formation of amorphous phase nanocomposite membranes was confirmed via FT-IR and wide-angle X-ray scattering. All membranes were semi-transparent and mechanically strong, as characterized by a universal tensile machine. Transmission electron microscopy and small-angle X-ray scattering analysis revealed that silica 5–10 nm in size were homogeneously dispersed in the matrix at up to 5 wt.% of MPTMS. At higher concentrations, the silica grew to more than 50 nm in size, which disrupted the microphase-separated structure of the graft copolymer. As a result, both proton conductivity (0.12 S/cm at 25 °C) and single cell performance (1.0 W/cm² at 75 °C) were maximal at 5 wt.% MPTMS.     

Charge mediation by ruthenium poly(pyridine) complexes in 'second-generation' glucose biosensors based on carboxymethylated β-cyclodextrin polymer membranes

Four different poly(pyridine) complexes of ruthenium, viz. Ru(II)(trpy)(phen)(OH(2))](2+) (1), trans-[Ru(III)(2,2'bpy)(2)(OH(2))(OH)](2+) (2), [(2,2'bpy)(2)(OH)Ru(III)ORu(III)(OH)(2,2'bpy)(2)](4+) (3), and [Ru(II)(4,4'bpy)(NH(3))(5)](2+) (4) (2,2'bpy=2,2'-bipyridine, 4,4'bpy=4,4'-bipyridine, trpy=2,2',2"-terpyridine, phen=1,10-phenanthroline), were tested as non-physiological charge mediators of 'second-generation' glucose biosensors. The membranes for these biosensors were prepared by casting anionic carboxymethylated beta-cyclodextrin polymer films (beta-CDPA) directly onto the Pt or glassy carbon (GC) disk electrodes. Simultaneously, glucose oxidase (GOD) was immobilized in the films by covalent bonding and the Ru complexes were incorporated both by inclusion in the beta-CD molecular cavities and by ion exchange at the fixed carboxymethyl cation-exchange sites. The leakage of the mediator from the polymer has been minimized by adopting a suitable pre-treatment procedure. The biosensors catalytic activities increased in the order 1<2<3<4, as established by linear sweep voltammetry. In case of complexes 2-4, the enzymatic glucose oxidation was mediated by the Ru complexes at their redox potentials. However, this oxidation was mediated by oxygen in case of complex 1 where H(2)O(2) was detected as the reaction product. The effectiveness of the mediators used in the presence of oxygen has been estimated using Pt and GC supports. The redox potential of the mediator does not depend on the support used, while the oxidation of H(2)O(2) proceeds on GC at much higher positive potentials than on Pt. The sensitivity and the linear concentration range of the biosensor studied varied significantly. For complex 4, which forms stable inclusion complex with beta-CD, the biosensor sensitivity was the highest and equal to 7.2 micro A mM(-1) cm(-2), detectability was as low as 1 mM, but the linear concentration range was limited only to 4 mM. In contrast, for complexes 2 and 3 the sensitivity was 0.4 and 3.2 micro A mM(-1) cm(-2), while the linear concentration range extended up to at least 24 and 14 mM glucose, respectively. Even though some common interfering substances, such as ascorbate, paracetamol or urea, are oxidized at potentials close to those of the Ru complex redox couples, their electro-oxidation currents at physiological concentrations are insignificant compared to those due to the biocatalytic oxidation of glucose. The biosensor response to glucose is reversible as demonstrated by the inhibition of GOD activity by Cu(II). That is, the Cu(II) concentration required to inhibit by half the response to glucose of the biosensor containing complex 2 was 1.0 mM. This inhibitory effect was fully reversed by addition of citrate, a ligand forming sufficiently stable complex with Cu(II).     

Interpenetrating polymer networks from castor oil based polyurethanes and poly(methyl acrylate)—IV

Castor oil and toluene-2,4-diisocyanate were reacted to form liquid prepolyurethane under various experimental conditions, varying the NCO/OH ratio. The prepolyurethanes (PPU) thus obtained were interpenetrated with methylacrylate monomer containing ethylene glycol dimethacrylate, using radical polymerization initiated by benzoyl peroxide. The PPU/MA interpenetrating polymer networks were obtained as transparent tough films by transfer moulding. They were characterized by resistance to chemical reagents, thermal behaviour and mechanical properties. The mechanothermal behaviour was studied by dynamic mechanical analysis. The morphology was examined by Scanning Electron Microscopy. Dielectric properties were studied.     

Effect of conductive polypyrrole in poly(acrylonitrile-co-butyl acrylate) water–based binder on the performance of electrochemical double-layer capacitors

Journal of Solid State Electrochemistry - Electrochemical double-layer capacitors (EDLCs) have been widely studied due to their high-power densities, despite their low energy densities compared...     

Nonwoven blend composites based on poly(3-hydroxybutyrate)–chitosan ultrathin fibers prepared via electrospinning

With the use of scanning electron microscopy, differential scanning calorimetry, and electron paramagnetic resonance, the structural–dynamic analysis of ultrathin fibrous matrixes based on poly(3-hydroxybutyrate) and blend composites of this polymer with chitosan is performed. It is shown that the addition of a small amount of chitosan causes change in the morphologies of the matrixes and leads to a marked increase in their melting enthalpies. It is found that the studied fibers contain amorphous regions with various morphologies. The dynamics of the spin probe TEMPO in these regions is investigated, and its change under the influence of increased temperature, an aqueous medium, and ozone is examined. The mechanism controlling the effects of chitosan, temperature, and an oxidative aggressive medium on the structuring of fibers is advanced.     

Double-imprinted polymer based on cross-linked poly(vinylimidazole–trimethylolpropane trimethacrylate) in solid phase extraction for determination of lead from wastewater samples by UV–vis spectrophotometry

The monitoring of the heavy metal pollution in wastewater is increasingly becoming a crucial global issue since they tend to accumulate in food chains and can cause many biological abnormalities. In this work, it was developed a novel lead ion-imprinted polymer (IIP) using sodium dodecyl sulphate (SDS) as a second template to be used as adsorbent in solid phase extraction (SPE) for determination of lead from wastewater samples by UV–vis spectrophotometry. The polymer called IIP–SDS was synthesised by a double-imprinting process with lead (template) and SDS (template). IIP–SDS was characterised by infrared spectroscopy Fourier transform infrared spectroscopy, thermogravimetric analysis and scanning electron microscopy. IIP–SDS showed good recovery for lead (around 82.0%), while the IIP (only lead as template) was 72.2% and non-IIP was 44.9%. Thus, the double-imprinting process for the preconcentration of Pb²⁺ proved to be a more adequate methodology than IIP with a single template. The optimised parameters of sample preparation were washing solvent (2.0 mL of tetrahydrofuran), type and volume of eluent (5 mL of 1 mol L^?1 hydrochloric acid), sample amount (30 mL of water spiked with 10.0 µg mL^?1), amount of IIP–SDS (400 mg) and sample pH (pH = 4.5). Linearity ranged from 10 to 125 µg L^?1 with r > 0.992. The limit of detection and quantification were 6.3 and 10 µg L^?1, respectively. The precision (relative standard deviation, %) and accuracy (relative error, %) were lower than 15%. Finally, IIP–SDS may be an alternative and effective adsorbent for SPE procedures in monitoring of wastewater samples.     

New polymer electrolytes based on polyethylene glycol diacrylate–LiBF4–1-ethyl-3-methylimidazolium tetrafluoroborate with the introduction of alkylene carbonates

Russian Chemical Bulletin - Polymer gel electrolytes based on polyethylene glycol diacrylate (PEG DA), salt LiBF4, and 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF4) were synthesized and...