A New Molecularly Imprinted Polymer for Solid-phase Extraction of Cotinine from Human Urine

A molecularly imprinted polymer （MIP）, prepared around a cotinine template, has been synthesized. The feasibility of using the polymer for solid-phase extraction （SPE） of cotinine from biological samples has been investigated. The results show that cotinine can be quantitatively retained and eluted from the polymer. Experiments with human urine samples indicate that clean target analyte is obtained for HPLC with UV detection using the protocol.     

Structure and properties of polystyrene-polyethylene interpenetrating polymer network (ipn)-like systems

A series of samples of polystyrene (PS) –polyethylene (PE) interpenetrating polymer network (IPN)–like system was prepared by synthesis in situ. The measurement of uniaxial compression modulus of the IPN samples was used for the determination of mean molar mass of the polymer chain between two junction points of the polymer network – M̌_C. The electron microscopic records gave an evidence about two phase structure of the IPN samples. Generally, the crystalline part of PE network in all IPN investigated samples is relatively low. The influence of the concentration of crosslinking agent on mechanical behaviour of the IPN samples was studied.     

混合溶剂作淋洗剂的体积排除色谱(SEC)中溶剂化高分子峰和溶剂峰的关系

以混合溶剂作淋洗剂的体积排除色谱(SEC)中高分子样品一般会出现2个峰, 分别是溶剂化高分子峰和自由溶剂峰. 理论分析结果表明, 溶剂化高分子峰面积( A3eff )是“裸高分子”峰面积(A3)和被束缚溶剂峰面积(A1*)的加和, 被束缚溶剂峰面积(A1*)和自由溶剂峰面积(A2*)大小相等符号相反. 以聚苯乙烯(3)-氯仿(1)-甲醇(2)体系为研究对象, 分别对A3eff, A3及A2*进行了实验测定, 证实了理论推断的正确性, 表明由高分子峰和由溶剂峰来求算优先吸附系数是等价的.     

Nuclear magnetic resonance investigation of dynamics in poly(ethylene oxide)-based lithium polyether-ester-sulfonate ionomers

Nuclear magnetic resonance spectroscopy has been utilized to investigate the dynamics of poly(ethylene oxide)-based lithium sulfonate ionomer samples that have low glass transition temperatures. (1)H and (7)Li spin-lattice relaxation times (T(1)) of the bulk polymer and lithium ions, respectively, were measured and analyzed in samples with a range of ion contents. The temperature dependence of T(1) values along with the presence of minima in T(1) as a function of temperature enabled correlation times and activation energies to be obtained for both the segmental motion of the polymer backbone and the hopping motion of lithium cations. Similar activation energies for motion of both the polymer and lithium ions in the samples with lower ion content indicate that the polymer segmental motion and lithium ion hopping motion are correlated in these samples, even though lithium hopping is about ten times slower than the segmental motion. A divergent trend is observed for correlation times and activation energies of the highest ion content sample with 100% lithium sulfonation due to the presence of ionic aggregation. Details of the polymer and cation dynamics on the nanosecond timescale are discussed and complement the findings of X-ray scattering and quasi-elastic neutron scattering experiments.     

Polymer Photochromic Composites and Their Spectral and Kinetic Properties

A method for the synthesis of polymer photochromic composites containing photochromic nitro-substituted spiropyran via mechanical mixing in melt is developed, and dependences of the spectral and kinetic properties of the samples on the nature of chosen thermoplastic polymer matrices (polyolefins, polycarbonate) and their processing temperatures are studied.     

Evaluation of rheological properties and swelling behaviour of sonicated scleroglucan samples

Scleroglucan is a natural polysaccharide that has been proposed for various applications. However there is no investigation on its property variations when the molecular weight of this polymer is reduced. Scleroglucan was sonicated at two different polymer concentrations for different periods of time and the effect of sonication was investigated with respect to molecular weight variations and rheological properties. Molar mass, estimated by viscometric measurements, was drastically reduced already after a sonication for a few min. Sonicated samples were used for the preparation of gels in the presence of borate ions. The effect of borax on the new samples was investigated by recording the mechanical spectra and the flow curves. A comparison with the system prepared with the dialysed polymer was also carried out. The anisotropic elongation, observed with tablets of scleroglucan and borax, was remarkably reduced when the sonicated samples were used for the preparation of the gels.     

Anisotropy of non-mesogenic polymer networks dispersed in a liquid crystal matrix

We report here original results characterizing in situ the interactions between a smectic liquid crystal phase and a polymer network dispersed in it. These results have been obtained by neutron scattering on smectic liquid crystal (8CB) samples containing a physical network of 1.5wt% polymer. The samples were polymerized in the isotropic, or in the smectic A phases. For the first time it is experimentally proved that the polymerization of non-mesogenic monomers in an aligned smectic A matrix induces anisotropy in the resulting network. The network becomes elongated along the liquid crystal director. When the polymerization is carried out in the isotropic phase the polymer network has an isotropic distribution even if a magnetic field, which orients the liquid crystal director, is later applied. On the other hand, studies show that after several thermal cycles, the liquid crystal orientational order still remained. Without other external constraints, the polymer network freezes the alignment of the liquid crystal. It is probably imposed by pendant reticulates on the diffuse liquid crystal-polymer interfaces.     

An indirect GPC calibration method for the low-molecular-weight region

A new gel permeation chromatography indirect calibration method is proposed for a polymer for which samples of known molecular weight and narrow molecular weight distribution are not available. This method is based on conversion of an experimentally obtained calibration curve for another polymer (polymer standard) through the universal calibration concept but using a new intrinsic viscosity-molecular weight relation. This indirect calibration curve is proposed especially for the low-molecular-weight region, where the method based on the Mark-Houwink-Sakurada equation gives erroneous results.     

Universal calibration in GPC: A new approach for the calculation of molecular weights

A method has been developed for determining simultaneously the molecular weight of a broad-distribution polymer and the Mark-Houwink coefficients for that polymer type by using only GPC and intrinsic viscosity data. Standardized samples of poly(vinyl chloride), polystyrene, polybutadiene, and an experimental cycloolefin polymer were analyzed by this method. Shear-corrected intrinsic viscosities were used in all cases because of the high molecular weights involved. Molecular weight data for all samples were found to be in good agreement with molecular weight data obtained by membrane osmometry and from other GPC techniques. The proposed technique provides a means for calculating the molecular weight of a single polymer sample through universal calibration of GPC without knowledge of the Mark-Houwink coefficients for that polymer type.     

The influence of poly(3-hexylthiophene) regioregularity on fullerene-composite solar cell performance

A comparison of three samples of poly(3-hexylthiophene) having regioregularities of 86, 90, and 96% is used to elucidate the effect of regioregularity on polymer-fullerene-composite solar cell performance. It is observed that polymer samples with lower regioregularity are capable of generating fullerene composites that exhibit superior thermal stability. The enhanced thermal stability of the composites is attributed to a lower driving force for polymer crystallization in the less regioregular polymer samples, which is supported with two-dimensional grazing incidence X-ray scattering and differential scanning calorimetry measurements. Furthermore, it is demonstrated that all three polymer samples are capable of generating solar cells with equivalent peak efficiencies of approximately 4% in blends with [6,6]-phenyl-C61-butyric acid methyl ester. While it may be non-intuitive that polymers with lower regioregularity can exhibit higher efficiencies, it is observed that the charge-carrier mobility of the three polymers is on the same order of magnitude (10(-4) cm2 V(-1) s(-1)) when measured from the space-charge-limited current, suggesting that highly regioregular and crystalline polythiophenes are not required in order to effectively transport charges in polymer solar cells. Overall, these results suggest a design principle for semicrystalline conjugated polymers in fullerene-composite solar cells in which crystallization-driven phase separation can be dramatically suppressed via the introduction of a controlled amount of disorder into the polymer backbone.     

Rapid radiochemical sample preparation for alpha spectrometry using polymer ligand films

Rapid radioanalytical methods are adversely affected by many different sample-matrix interferences, which make analyzing samples a difficult and time consuming process. A new method for preparing radioactive samples for analysis by alpha spectrometry has been demonstrated. In this technique, a selective extractive ligand is immobilized in a polymer film coated on a metal surface. This polymer ligand film is then used to extract plutonium and other radioactive analytes from solution over a short period of time. The prepared substrate is then counted directly by alpha spectroscopy in a small single detector alpha spectrometer. The method has been demonstrated for the analysis of americium and plutonium in liquid samples such as water and urine.     

Correction of the mark–houwink–sakurada equation in the low-molecular-weight range

A relation is proposed which gives the error in determination of molecular weights of polymer samples using the extrapolation of the Mark–Houwink–Sakurada equation into the low-molecular-weight region. The error is directly related to the exponent α of the Mark–Houwink–Sakurada equation and the relation is the same for a number of polymer + solvent systems.     

Novel molecularly imprinted polymer prepared by nanoattapulgite as matrix for selective solid-phase extraction of diethylstilbestrol

Using nanoattapulgite as matrix, both diethylstilbestrol surface molecularly imprinted polymer and non-imprinted polymer were synthesized in this work. Compared with each other, the diethylstilbestrol surface molecularly imprinted polymer is superior to non-imprinted polymer in adsorption capacity, selectivity and mass transfer property. The maximum static adsorption capacities of diethylstilbestrol surface molecularly imprinted polymer, non-imprinted polymer and nanoattapulgite for diethylstilbestrol was 105.14, 78.54 and 28.50 mg g⁻¹, respectively. As the packing material of solid-phase extraction, the diethylstilbestrol surface molecularly imprinted polymer has been applied to concentrating diethylstilbestrol in pond water and fish samples. A corresponding analytical method to determine diethylstilbestrol has been developed. The limit of detection for diethylstilbestrol in pond water sample and fish samples were 3 μg L⁻¹ and 15 μg kg⁻¹.     

Synthesis,characterization and polymer reactions of poly[5,5′-methylene-bis(8-hydroxyquinoline)-7,7′-diylethylene]

Poly[5,5′-methylene-bis(8-hydroxyquinoline)-7,7′-diylethylene] (MQE) has been prepared by Friedel-Craft polycondensation of 5,5′-methylene-bis(8-hydroxyquinoline) (MBQ) with 1,2-dichloroethane and ethylene glycol in the presence of an acid catalyst under various experimental conditions. Polymer reactions such as hydroxyethylation, carboxymethylation and methylation of one polymer sample were carried out with a view to investigating the effect of these reactions on the properties of the polymer. The polymer samples and the products of methylation (M-MQE) and carboxymethylation (C-MQE) are insoluble in all solvents, except formic acid. A polymer similar in structure to C-MQE was prepared by Friedel-Craft condensation of a carboxymethylated derivative of MBQ with ethyleneglycol. The hydroxyethylated product of polymer sample (MQE-2) is soluble even in DMF and is highly soluble in pyridine. The polymer samples were characterized by i.r. and u.v., estimation of molecular mass, by non-aqueous conductometric titration and solution viscometric study in formic acid and in aqueous sulphuric acid. Various empirical relations were applied to correlate appropriate viscosity parameters with concentration of solution.     

Visualization of structural rearrangements during annealing of solvent-crazed poly(ethylene terephthalate)

A direct microscopic procedure is used for studying structural rearrangements during the annealing of PET samples after solvent crazing. Even at room temperature, solvent-crazed PET samples experience shrinkage which is provided by processes taking place in crazes. This shrinkage is observed at temperatures up to the glass transition temperature of PET and proceeds via drawing together of crack walls. Once the glass transition temperature is attained during annealing, the spontaneous self-elongation of the polymer sample occurs. The mechanism of this phenomenon is proposed. The low-temperature shrinkage of the polymer sample is related to the entropy contraction of highly dispersed material in crazes that has a lower glass transition temperature than that of the bulk polymer. This shrinkage cannot be complete, owing to crystallization of the oriented polymer in the volume of the crazes. As a result of crystallization, the oriented and crystallized polymer in the crazes coexists with the regions of the unoriented initial PET. As the annealing temperature approaches the glass transition temperature of the bulk PET, its strain-induced crystallization takes place. As a result, the regions of the unoriented polymer between crazes are elongated along the direction of tensile drawing and the sample experiences contraction in the normal direction.     

Resistivity mapping: An example of aged conducting polymer

A simple multi-contact measurement method, which can be used to map the electrical resistivity of small disc-shaped samples of conducting polymer during temperature ageing, was examined for its resolution and accuracy. The method is based on electrical impedance tomography (EIT), which is used especially in medicine to visualise boundaries between areas having different electrical resistivities. In order to eliminate experimental errors, a computer simulation was used for testing. The time series of resistivity maps were recorded during ageing of real polymer samples. The contour maps and their time development are presented graphically and discussed.     

PoraPLOT Q: A porous layer open tubular column coated with styrene-divinylbenzene copolymer

A porous polymer is deposited on the inner wall of fused silica capillary columns. The retention characteristics of this porous polymer were evaluated and found to be comparable with Porapak Q. The porous polymer has a high retention volume which enables the separation of permanent gases at ambient temperatures or higher. The hydrophobic character of the porous polymer allows the injection of water containing samples without changing retention due to adsorption of water. The inertness of the porous polymer allows the elution of a range of apolar and polar compounds. The maximum temperature of the porous polymer was estimated to be 250°C. With this new type of capillary column, high resolution separations are obtained in combination with short analysis times.     

Preparation of 17β‐estradiol‐imprinted material by surface‐initiated atom transfer radical polymerization and its application

A novel 17β‐estradiol molecularly imprinted polymer was grafted onto the surface of initiator‐immobilized silica by surface‐initiated atom transfer radical polymerization. The resulting molecularly imprinted polymer was characterized by elemental analysis and thermogravimetric analysis. The binding property of molecularly imprinted polymer for 17β‐estradiol was also studied with both static and dynamic methods. The results showed that the molecularly imprinted polymer possessed excellent recognition capacity for 17β‐estradiol (180.65 mg/g at 298 K), and also exhibited outstanding selectivity for 17β‐estradiol over the other competitive compounds (such as testosterone and progesterone). Then, the determination of trace 17β‐estradiol in beef samples was successfully developed by using molecularly imprinted polymer solid‐phase extraction coupled with high‐performance liquid chromatography. The limit of detection was 0.25 ng/mL, and the amount of 17β‐estradiol in beef samples was detected at 2.83 ng/g. This work proposed a sensitive, rapid, reliable, and convenient approach for the determination of trace 17β‐estradiol in complicated beef samples.     

Paradoxes of thermodynamics of aqua-vapor-polymer interface equilibrium

Schroeder’s paradox is the different equilibrium degree of swelling for a hydrophilic polymer in saturated aqueous vapor and in liquid water; it is experimentally verified by the registration of increasing volume of spherical polymer samples upon the processes of vapor and liquid water sorption. Specimens of three main classes of hydrophilic cross-linked polymers were tested. These had gel, hypercrosslinked, and macroporous structures that differed by the scale of the Schroeder effect. A similar effect is typical also for hydrophobic polymers upon swelling in liquid organic solvents and their saturated vapor. The paradox is explained by the lower activity of a sorbate in a saturated vapor compared to its activity in a liquid phase. The ability of many samples of cross-linked polymers with different degrees of saturation with a sorbate to be at equilibrium with the saturated vapor of a sorbate is explained by the differences in the inner structure of these samples, i.e., by differing in the swelling combinations and the intensity of the interchain interactions in a polymer network.     

Etude électrochimique en milieu aqueux d'une électrode composite: graphite,polymère échangeur d'ions,cations de métaux de transition, électrolyte support—I. Réalisation de l'électrode et détermination du domaine d'étude

A carbon paste electrode (graphite, ion-exchange polymer, transition cations, buffer electrolyte) was achieved and the properties of the compounds were studied. The range of pH over which the metallic cation is most fixed on the polymer was determined. Electronic conductivity measurements of the samples show that their resistance increases greatly when the ratio of polymerised active material exceeds 50%.