Aluminum(III) selective potentiometric sensor based on morin in poly(vinyl chloride) matrix

Al³⁺ selective sensor has been fabricated from poly(vinyl chloride) (PVC) matrix membranes containing neutral carrier morin as ionophore. Best performance was exhibited by the membrane having composition as morin:PVC:sodium tetraphenyl borate:tri-n-butylphosphate in the ratio 5:150:5:150 (w/w, mg). This membrane worked well over a wide activity range of 5.0 × 10⁻⁷ to 1.0 × 10⁻¹ M of Al³⁺ with a Nernstian slope of 19.7 ± 0.1 mV/decade of Al³⁺ activity and a limit of detection 3.2 × 10⁻⁷ M. The response time of the sensor is ∼5 s and membrane could be used over a period of 2 months with good reproducibility. The proposed sensor works well over a pH range (3.5-5.0) and demonstrates good discriminating power over a number of mono-, di- and trivalent cations. The sensor can also be used in partially non-aqueous media having up to 20% (v/v) methanol, ethanol or acetone content with no significant change in the value of slope or working activity range. The sensor has also been used in the potentiometric titration of Al³⁺ with EDTA and for its determination in zinc plating mud and red mud.     

Morphology control of sulfonated poly(ether ketone ketone) poly(ether imide) blends and their use in proton-exchange membranes

Polymer blends based on sulfonated poly(ether ketone ketone) (SPEKK) as the proton-conducting component and poly(ether imide) (PEI) as the second component were considered for proton-exchange membranes (PEMs). The PEI was added to improve the mechanical stability and lower the water swelling in the fuel cell environment. Membranes were cast from solution using N-methyl-2-pyrrolidone (NMP) and dimethylacetamide (DMAc). The ternary, polymer/polymer/solvent, phase diagram was determined to provide guidance on how to control the morphology during solvent casting of blend membranes.

For blends of SPEKK (ion-exchange capacity = 2 mequiv/g) with PEI as the minority component, the morphology consisted of dispersed particles of 0.5–6 μm. Larger particles were achieved by increasing the PEI content and/or lowering the casting temperature. High-temperature annealing after solution casting did not affect the morphology of blend membranes, due to the low mobility and compatibility of the two polymers.

The possible use of SPEKK/PEI blends in PEMs is discussed in terms of existing theories of ion transport in polymers.     

Performance of biodegradable microcapsules of poly(butylene succinate), poly(butylene succinate-co-adipate) and poly(butylene terephthalate-co-adipate) as drug encapsulation systems

Poly(butylene succinate) (PBSu), poly(butylene succinate-co-adipate) (PBSA) and poly(butylene terephthalate-co-adipate) (PBTA) microcapsules were prepared by the double emulsion/solvent evaporation method. The effect of polymer and poly(vinyl alcohol) (PVA) concentration on the microcapsule morphologies, drug encapsulation efficiency (EE) and drug loading (DL) of bovine serum albumin (BSA) and all-trans retinoic acid (atRA) were all investigated. As a result, the sizes of PBSu, PBSA and PBTA microcapsules were increased significantly by varying polymer concentrations from 6 to 9%. atRA was encapsulated into the microcapsules with an high level of approximately 95% EE. The highest EE and DL of BSA were observed at 1% polymer concentration in values of 60 and 37%, respectively. 4% PVA was found as the optimum concentration and resulted in 75% EE and 14% DL of BSA. The BSA release from the capsules of PBSA was the longest, with 10% release in the first day and a steady release of 17% until the end of day 28. The release of atRA from PBSu microcapsules showed a zero-order profile for 2 weeks, keeping a steady release rate during 4 weeks with a 9% cumulative release. Similarly, the PBSA microcapsules showed a prolonged and a steady release of atRA during 6 weeks with 12% release. In the case of PBTA microcapsules, after a burst release of 10% in the first day, showed a parabolic release profile of atRA during 42 days, releasing 36% of atRA.     

Studies on synthesis and properties of poly(ferrocenyldimethylsilanes) and poly(ferrocenylmethylphenylsilanes)

Poly(ferrocenyldimethylsilane) and poly(ferrocenylmethylphenylsilane) have been prepared via the thermal ring-opening polymerization of the corresponding strained, silicon-bridged ferrocenophanes. It was found that the molecular weights of resultant polymers depend on the polymerization time. Their electrochemical behavior in aqueous electrolytes was investigated by cyclic voltammetry.     

Elaboration of poly(ethyleneimine) coated poly( , -lactic acid) particles. Effect of ionic strength on the surface properties and DNA binding capabilities

Poly( , -lactic acid) (PLA)-based particles, obtained by the emulsification–diffusion process, were surface-modified by electrostatic adsorption of poly(ethylenimine) (PEI). The amount of immobilized PEI and the conformation of the polycation at the interface were dependent on the ionic strength of the media. In the absence of salt, or at low ionic strength, the adsorbed amounts of PEI, the surface charge and the critical concentration for coagulation (CCC) of the modified particles were lower than when the adsorption was achieved at elevated ionic strength. Moreover, at low salt concentration, isotherms were of Langmuir type, suggesting the formation of monolayers. The differences in PEI surface conformation had consequences on the DNA binding capacity of the particles, on the plasmid DNA conformation at the interface and on the DNA release in various media. When PEI was adsorbed in a 50 mM phosphate buffer, the amount of bound plasmid and the strength of binding were higher than when PEI was adsorbed in water. From these differences in physico-chemical properties, one can expect differences in transfection or immunization performances of the vectors.     

Rapid assessment of DNA damage induced by polystyrene nanosphere suspension using a photoelectrochemical DNA sensor

Nanomaterials have been used increasingly in a wide variety of applications, and some of them have shown toxic effects on experimental animals and cells. In this study, a previously established photoelectrochemical DNA sensor was employed to rapidly detect DNA damage induced by polystyrene nanosphere (PSNS) suspensions. In the sensor, a double-stranded DNA film was assembled on a semiconductor electrode, and a DNA intercalator, Ru(bpy)2(dppz)2+ (bpy = 2,2'-bipyridine, dppz = dipyrido[3,2-a:2',3'-c]phenazine...     

New architectures of poly(ethylene glycol) and poly(methylthiirane) in block copolymers

Two synthetic ways were experimented to prepare new architectures of block copolymers made of poly(ethylene glycol) (PEG) and poly(methylthiirane). The coupling of both blocks conveniently end-capped as well as anionic polymerization of methylthiirane initiated by PEG-thiols gave readily the copolymers. Their characterization by ¹H NMR, SEC and IR confirmed the expected structures.     

A novel quartz crystal microbalance gas sensor based on porous film coatings. A high sensitivity porous poly(methylmethacrylate) water vapor sensor

We describe a novel and generally applicable approach for creating voids in films deposited on the surface of solid substrates. Such films are advantageous when a quartz crystal microbalance (QCM) is the basis of a sensor. We show that films with large void volumes produce more sensitive sensors than with the original film. Poly(methylmethacrylate) (PMMA) was used as the polymer layer deposited on a quartz crystal microbalance (QCM) to demonstrate our technique for the model system of water vapor analysis in flowing nitrogen gas. A film of pure PMMA on a QCM is a sensor for water vapor in a gas phase. A more sensitive sensor was created by dip coating QCM crystals into solutions containing mixtures of PMMA and poly(d,l-lactide) (PDLL) and then evaporating the solution films on the QCM crystals to form mixed polymer films of varying PDLL content. The PDLL was then removed from the mixed polymer films by exposure to a NaOH solution to form pure PMMA films having various void volumes. A leached PMMA film that originally contained 50% by weight PDLL had a 3.7 times larger QCM sensitivity for water vapor than a pure PMMA film.     

Polypyrrole/poly(methylmethacrylate) blend as selective sensor for acetone in lacquer

A film of α-naphthalene sulfonate-doped polypyrrole/poly(methylmethacrylate), PPy/α-NS⁻/PMMA, obtained from solution mixing was successfully used as sensing material for acetone vapor in lacquer with a high degree of selectivity based on electrical conductivity over acetic acid and a high degree of stability over the humidity change. Compared with pure PPy/α-NS⁻, the selectivity ratio of acetone/acetic acid response of PPy/α-NS⁻/PMMA blend with a PMMA/PPy weight ratio of 3.0 was ca. 3.9 times higher. The film was found to be insensitive to moisture unless the relative humidity (RH) was lower than 20% RH in which the selectivity ratio of acetone/acetic acid response was enhanced. The time required to reach the equilibrium for acetone exposure was found to increase slightly with increasing humidity.     

Effect of poly(butylene succinate) on the morphology evolution of poly(vinylidene fluoride) in their blends

The effect of PBS on the morphological features of PVDF has been investigated by optical and atomic force microscopies under various conditions.It was found that neat PVDF forms largeγform spherulites with extraordinarily weak birefringence at 170℃.Adding 30%PBS makes PVDF exhibit intrigued flower-like spherulitic morphology.The growth mechanism was explained by the decrease of the supercooling and the materials dissipation.Increasing the PBS content to 70%favors the formation of ring banded spherulites.Temperature dependent experiments verify theα→γphase transition occurs from the junction sites of theαandγcrystals,while starts from the centers ofαspherulites in the blends.Ring banded structures could be observed in neat PVDF,70/30 blend and 30/70 blend when crystallized at 155℃,withoutγcrystals.The band period of PVDFαspherulites increases with crystallization temperature as well as the amount of PBS content.At 140℃,spherulites in neat PVDF lose their ring banded feature,while coarse spherulites consisting of evident lamellar bundles could be found in 30/70 blend.     

Chemical modification of poly(lactic acid) and its use as matrix in poly(lactic acid) poly(butylene adipate-co-terephthalate) blends

Poly(lactic acid), PLA, was chemically modified with maleic anhydride (MA) by reactive extrusion. The effect of this modification on molar mass (MM) and acidity was assessed by means of size-exclusion chromatography (SEC) and titration, respectively. PLA MM decreased in the presence of MA solely and of MA and peroxide. Reduction in MM was monitored by the increase in acidity. PLA blends containing poly(butylene adipate-co-terephthalate) (PBAT) were prepared through different mixing protocols, PLA/PBAT, PLA-g-MA/PBAT and PLA/PBAT/MA/peroxide (PLA/PBAT in situ). SEC results and rheological properties revealed reduction in MM and viscosity of the modified blends. PLA/PBAT presented increase in MM and bimodal MM distribution. The calculated interfacial tension was significantly lower for the modified blends, despite the lower average particle area of PLA/PBAT. Surprisingly, the modified blends presented higher yield strength than that predicted by the rule of mixtures, which might indicate interfacial reactions.     

Synthesis of poly(sulfonium cation) as an alkylating reagent

Methyl 4-phenylthiophenyl sulfoxide is polymerized to poly(methyl-4-phenylthiophenylsulfonium) in poly(phosphoric acid) with a yield higher than 90%. The demethylation of poly(sufonium cation) is examined to control the composition ratio of the thiophenylene unit in the polycation. The polycation is soluble in common solvents due to the alternative structure of phenylene sufide and phenylenesulfonium cation and is easily converted to poly(phenylene sulfide) through the demethylation with a nucleophile. The poly(sulfonium cation) can be applicable as an alkylating agent for phenol, aniline and benzoic acid to the corresponding to anisole, N-methyl aniline, N,N-dimethyl aniline and benzoic methyl ester, respectively, with high conversion through the demethylation. These products can be isolated without a complicated purification because poly(phenylene sulfide) is precipitated in the mixture as the side product due to the poor solvent solubility.     

Hoechst-naphthalimide dyad with dual emissions as specific and ratiometric sensor for nucleus DNA damage

A ratiometric fluorescent sensor (Hoe-NI) was developed for high specific nucleus labeling and monitoring of nuclear DNA damage in living cells.     

Crystallization behavior and biodegradation of poly(3-hydroxybutyrate) and poly(ethylene glycol) multiblock copolymers

Block copolymerization by using isocyanates is an effective method for incorporating PHB and PEG because it can prepare copolymers with good properties, such as toughness, strength, and so on. In this study, we adopted soil suspension system to estimate the biodegradability of a series of PHB/PEG multiblock copolymers with different compositions and block lengths. In the degradation process, the changes in weight loss, molecular weight, and tensile strength were periodically measured to determine the biodegradability, and the surface morphology was also observed by SEM. In contrast to pure PHB, the weight loss of the copolymer was relatively lower. On the other hand, the tensile strength and molecular weight experienced apparent decrease, and for BHG1000-3-1, they reached 46.7% and 77.7% of the initial value, respectively. SEM observation showed that the surface was covered with numerous erosion pits. All these indicate that the degradation indeed took place and long-chain molecules have been hydrolyzed into shorter ones. The crystallization behavior was also investigated by DSC and WAXD. The results showed that both the segments, PEG and PHB, can form crystalline phases at lower PHB contents ranging from 29% to 44%, and when PHB component was more than 60%, only PHB phase can crystallize.     

The use of a polymer inclusion membrane in a paper-based sensor for the selective determination of Cu(II)

A disposable paper-based sensor (PBS) is described for the determination of Cu(II) in natural and waste waters at approximately 2 cents per measurement. The device makes use of a polymer inclusion membrane (PIM) to provide the selectivity for Cu(II). The PIM consists of 40 wt% di(2-ethlyhexyl) phosphoric acid (D2EHPA) as the carrier, 10 wt% dioctyl phthalate (DOP) as a plasticizer, 49.5 wt% poly(vinyl chloride) (PVC) as the base polymer and 0.5 wt% (m m⁻¹) 1-(2′-pyridylazo)-2-naphthol (PAN) as the colourimetric reagent. High selectivity under mildly acidic conditions (HCl, pH 2.0) is achieved for Cu(II) in the presence of frequently encountered metal ions in natural and waste waters such as Fe(III), Al(III), Zn(II), Cd(II), Pb(II), Ca(II), Mg(II), and Ni(II).     

pH-effects in the complex formation of polymers I. Interaction of poly(acrylic acid) with poly(acrylamide)

The effects of polymer concentration, molecular weight of poly(acrylic acid) (PAA), addition of sodium, potassium, ammonium and copper (II) chlorides on the complex formation ability of the system PAA-poly(acrylamide) (PAAM) have been studied in aqueous solutions. The critical pH values of the complexation were determined in different conditions. The complex formation ability of PAAM is compared with other non-ionic polymers. It was shown that an increase in polymers concentration, molecular weight of PAA and ionic strength favours the complexation and shifts the critical pH values to the higher pH region. An addition of CuCl₂ to the mixture of two polymers enhances the complexation drastically due to the formation of triple complexes.     

Polycationic graft copolymers of poly(N-vinylpyrrolidone) as non-viral vectors for gene transfection

Novel graft copolymers of 2-(dimethylamino)ethyl methacrylate (DMAEMA) with N-vinylpyrrolidone (NVP) were designed and synthesized by the free radical copolymerization of DMAEMA with precursor polymers of vinyl-functionalized poly(N-vinylpyrrolidone) (PVP). The ability of the PVP- grafted copolymers to bind and condense DNA was confirmed by ethidium bromide displacement assay, agarose gel electrophoresis and transmission electron microscopy. The presence of PVP in the copolymers had a favorable effect on the biophysical properties of polymer/DNA complexes. Colloidal stable complexes obtained from the copolymer systems, were shown to be separate, uniformly spherical nanoparticles by transmission electron microscopy. The approximate diameter of the complexes was 150–200 nm, as determined by dynamic light scattering studies. These results confirm an important role played by the PVP grafts in producing compact stable DNA complexes. The ζ-potential measurements revealed that the incorporation of the PVP grafts reduced the positive surface charge of polymer/DNA complexes. The cytotoxicity of the copolymers decreased with an increasing fraction of PVP. Furthermore, in vitro transfection experiments with these copolymers showed improved ability of transfection in cell culture, demonstrating an important role for PVP grafts in enhancement of the transfection efficiency.      

Synthesis and degradation of nontoxic biodegradable waterborne polyurethanes elastomer with poly(ε-caprolactone) and poly(ethylene glycol) as soft segment

In this study, in order to obtain waterborne polyurethanes (WBPUs) with biocompatibility, biodegradability as well as good mechanical properties, a series of nontoxic cross-linked waterborne polyurethanes were designed and synthesized with isophorone diisocyanate (IPDI), poly(ε-caprolactone) (PCL), poly(ethylene glycol) (PEG), 1,4-butandiol (BDO) and l-lysine without any other organic agent involved in the whole synthetic process. The bulk structures and properties were characterized by DSC, IR and Instron, mainly focused on the effect of amount of PEG. Their corresponding biodegradability was examined with Lipase AK. The result showed that the prepared waterborne polyurethanes had very good tensile properties, allowing them to be well used as biomaterials. And the change of tensile properties with increasing of amount of PEG in the polymers could be assigned to the change of microphase separation, as indicated by DSC and IR data. A quite good biodegradability was achieved as judged from the change of tensile properties as a function of time. The current work demonstrated a new synthetic approach that can be more promising to prepare both nontoxic and biodegradable polyurethanes for soft tissue engineering applications or drug delivery.     

Y-shaped block copolymers of poly(ethylene glycol) and poly(N-isopropylacrylamide) synthesized by ATRP

Novel Y-shaped block copolymers of poly(ethylene glycol) and poly(N-isopropylacrylamide),PEG-b-(PNIPAM)_2,were successfully synthesized through atom transfer radical polymerization(ATRP).A difunctional macroinitiator was prepared by esterification of 2,2-dichloroacetyl chloride with poly(ethylene glycol) monomethyl ether(PEG).The copolymers were obtained via the ATRP of N-isopropylacrylamide(NIPAM) at 30℃with CuCl/Me_6TREN as a catalyst system and DMF/H_2O(v/v = 3:1) mixture as solvent.The resulting copo...     

The miscibility of poly(vinyl alcohol)/poly(N-vinylpyrrolidone) blends investigated in dilute solutions and solids

Poly(vinyl alcohol) (PVA) (polymer A) and poly(N-vinylpyrrolidone) (PVP) (polymer B) are known to form a thermodynamically miscible pair. In the present study the conclusion on miscibility of PVA/PVP solid blends, confirmed qualitatively (DMTA, FTIR) and quantitatively (DSC, χ_AB = − 0.69 at 503 K) is compared with the miscibility investigations of PVA/PVP solution blends by the technique of dilute solution viscometry. The miscibility of the ternary (polymer A/ polymer B/ solvent) system is estimated on the basis of experimental and ideal values of the viscosity parameters k, b and [η]. It is found that the conclusions on miscibility or nonmiscibility drawn from viscosity measurements in dilute solution blends depend: (i) on the applied extrapolation method used for the determination of the viscosity interaction parameters, (ii) on the assumed definition of the ideal values and (iii) on the thermodynamic quality of the solvent, which in the case of PVA depends on its degree of hydrolysis. Hence, viscometric investigations of dilute PVA/PVP solution blends have revealed that viscometry, widely used in the literature for estimation of polymer-polymer miscibility can not be recommended as a sole method to presume the miscibility of a polymer pair.