Adsorption–desorption phenomena of water vapor on a superabsorbent polymer partially crosslinked with potassium

The objective of this article is to study an amorphous superabsorbent polymer, which is able to absorb up to 300 times its weight of water. Adsorption–desorption phenomena of water vapor on the polymer as a function of temperature showed a reversibility of the adsorption–desorption phenomena. The thermal stability of the polymer at atmospheric pressure was also studied. The kinetic study of the desorption phenomena of water vapor on the polymer according to certain physicochemical parameters was discussed. The results showed that the kinetic regime governing the desorption phenomena of water vapor on the polymer is a process limited by a mono-dimensional diffusion for low masses and by a three-dimensional diffusion for high masses.     

Analysis of hair components by nanoparticle-assisted laser desorption/ionization mass spectrometry imaging

Using a vertical hair-slice section, we compared the components of normal and damaged hair regions using two ionization methods, matrix-assisted laser desorption/ionization and nanoparticle-assisted laser desorption/ionization (Nano-PALDI) mass spectrometry. Nano-PALDI is useful for small-molecule and high spatial resolution (5 μm) analyses due to the lack of noise. Thus, clear images were obtained from thin hair samples. In Nano-PALDI mass spectrometry imaging, cystine and 18-methyleicosanoic acid as endogenous hair components localized in the cuticle and cortex and cuticle of normal hair, respectively. In contrast, both components were absent in damaged hair.     

Water vapor sorption and desorption behavior of some keratins

Summary Sorption and desorption isotherms of water vapor in a number of keratin substrates including excised human stratum corneum, guinea pig and neonatal rat corneum and human hair have been obtained and the data compared to the information available on wool. An attempt was made to analyze the data according to the BET and D'Arcy-Watt equations, Flory-Huggins polymer solution theory and Zimm's clustering function. The results suggest strong binding between the sorbate and keratins in the low relative vapor pressure range, reflecting a sorption process on primary reactive sites (Langmuir) which proceeds up to 0.2-0.3 relative vapor pressure. More confirmation is obtained from isosteric heat of sorption measurements. Extensive clustering and multilayer formation occur in the higher relative vapor pressure range.With 10 figures     

The effect of internal lipids on the water sorption kinetics of keratinised tissues

Water has a large influence on the properties of keratinised tissues. The water diffusion properties of keratinised tissues are known to be governed by the cell membrane complex, which is mainly composed of internal lipids. The main aim of this work was to characterise the differences in the water sorption and desorption behaviour of human hair and stratum corneum (SC) both with and without internal lipids. Absorption and desorption curves were obtained using a thermogravimetric balance equipped with a controlled humidity chamber. The results demonstrate that the role of the intercellular lipids in the SC is more marked than in hair, which is likely due to the greater amount of lipids present in its structure. Therefore, lipid structures in the SC are essential both to prevent changes in the water-holding capacity of the skin and to maintain the water permeability of the SC.     

Thermal desorption characterisation of molecularly imprinted polymers. Part I: a novel study using direct-probe GC-MS analysis

A novel thermal desorption technique using a direct-probe device (Chromatoprobe) attached to a gas chromatograph–mass spectrometer is presented for the thermal pretreatment, characterisation and analysis of molecularly imprinted polymers. The technique is demonstrated as effective for the removal of volatile materials, including template and unreacted monomers, from methacrylic acid–ethylene glycol dimethacrylate copolymers imprinted with 2-aminopyridine. Mass spectrometry is a powerful technique for polymer bleed characterisation. Thermal desorption studies on reloaded template and related compounds are reported as a means of assessing polymer morphology, specific binding by imprinted polymers compared with reference non-imprinted polymers and selective binding by an imprinted polymer for its template. Calibration studies on the thermal desorption technique using an internal standard are presented with R ² > 0.999. The technique provides a novel method for assessment of polymer thermal stability, composition and morphology.     

Anionic grafting polymerization of propylene sulfide onto human hair in water

Natural human hair was modified by the graft polymerization of propylene sulfide in an aqueous medium. The amount of the polymer grafted onto the reduced hair was 0.15–0.19 g on 1.0 g of hair. The grafted polymer was isolated by the hydrolysis of the hair in the polymer‐grafted hair under basic conditions and was confirmed to be poly(propylene sulfide) by ¹H NMR, ¹³C NMR, and Fourier transform infrared spectra. The number‐average molecular weights of the isolated polymers from the grafted products were 10,000–12,000. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3778–3786, 2006     

Activated water desorption from poly(methylvinylidene cyanide)

We have investigated water desorption from the polymer poly(methylvinylidene cyanide). The angle resolved thermal desorption spectra show large deviations from the cosn theta distribution for water desorption from poly(methylvinylidene cyanide) indicative of an activated desorption process. The Arrhenius plots obtained from Polanyi-Wigner analysis of the thermal desorption data suggest that a two-state model of desorption applies, while theory suggests that lattice strain in the polymer plays a key role in the thermal desorption of water.     

Polydispersity effects and the interpretation of polymer adsorption isotherms

In many cases, polymer adsorption is studied by measuring adsorption isotherms. Quite often it is found that the results are at variance with theoretical predictions. However, usually these adsorption isotherms are interpreted in terms of a single polymeric solute. Most polymers used in experimental studies are polydisperse and should be treated as mixtures. It is well established that the larger molecules in such mixtures adsorb preferentially over the smaller ones. In this paper we show that many discrepancies between polymer adsorption theory and experiment (e.g., the rounded shape of isotherms, the dependence of the adsorbance on adsorbent concentration, and the lack of desorption upon dilution) can be attributed to polydispersity. A quantitative analysis enables us to calculate isotherms for a polymer of arbitrary molecular weight distribution, provided the dependency of the plateau adsorbance on molecular weight is known. Experiments supporting the theory are reported. The fact that polymers do not desorb upon dilution with solvent is often regarded as a proof that polymer adsorption is irreversible. We show that, if a polydisperse sample is in equilibrium with an adsorbing surface, no detectable desorption may take place upon dilution. Therefore, the adsorption of polymers might well be reversible, even if desorption experiments would indicate apparent irreversibility.     

PARTICLE SIZE DISTRIBUTION IN CONTINUOUS EMULSION POLYMERIZATION WITH FREE RADICAL DESORPTION

A mathematical model of particle size distribution in continuous emulsion polymerization which accounts for the free radical desorption from polymer particles is presented. The desorption rate is based on the diffusion theories which suggest the rate coefficient should be inversely proportional to the surface area of the polymer particles. The number density and total particle number are estimated by our model.

The average number of radicals per particle approaches Smith-Ewart case II In the range of large particle sizes. A means for predicting the nature of average desorption rate is proposed, and it seems to be influenced by concentrations of emulsifier and initiator, and residence times as well     

The properties of water in swollen cross-linked polystyrene sulfo acids

The properties of water in polystyrene sulfo acid gels with various cross-linking degrees were studied by optical volumetry and dynamic desorption porosimetry. The isotherms of water desorption obtained by dynamic desorption porosimetry coincided with isopiestic isotherms, which allowed this method to be recommended for the determination of the amount of water in polymer gels. Joint optical volumetry and dynamic desorption porosimetry studies showed that the interphase boundary in the cross-liked hydrophilic polymer-water system did not coincide with the visible gel boundary, because gels were two-phase systems, which contained water of two types, “free” and “bound.” The influence of the degree of polymer cross-linking on the amounts and properties of water of the two types was studied. It was shown that constants of water distribution in the polymer could be calculated from the dynamic desorption porosimetry data.     

The role of melanin as protector against free radicals in skin and its role as free radical indicator in hair

Throughout the body, melanin is a homogenous biological polymer containing a population of intrinsic, semiquinone-like radicals. Additional extrinsic free radicals are reversibly photo-generated by UV and visible light. Melanin photochemistry, particularly the formation and decay of extrinsic radicals, has been the subject of numerous electron spin resonance (ESR) spectroscopy studies. Several melanin monomers exist, and the predominant monomer in a melanin polymer depends on its location within an organism. In skin and hair, melanin differs in content of eumelanin or pheomelanin. Its bioradical character and its susceptibility to UV irradiation makes melanin an excellent indicator for UV-related processes in both skin and hair. The existence of melanin in skin is strongly correlated with the prevention against free radicals/ROS generated by UV radiation. Especially in the skin melanin (mainly eumelanin) ensures the only natural UV protection by eliminating the generated free radicals/ROS. Melanin in hair can be used as a free radical detector for evaluating the efficacy of hair care products. The aim of this study was to investigate the suitability of melanin as protector of skin against UV generated free radicals and as free radical indicator in hair.     

Liquid chromatography of polymer mixtures by a combination of exclusion and full adsorption mechanisms. Three- and four-component polymer blends

Summary Coupling of full adsorption-desorption and size-exclusion chromatography (FAD-SEC) has been applied to the separation and molecular characterization of three- and four-component polymer blends. The method is based on the full adsorption of alln orn−1 components of the polymer blend in a specially designed FAD minicolumn. By appropriate eluent switching the adsorbed polymers are desorbed stepwise from the FAD minicolumn into an on-line SEC column for molecular characterization. It is shown that the desorption isotherms of particular blend components give valuable information about the appropriate displacer composition. The exact position of the desorption isotherms depends, however, both on the amount of polymer adsorbed and in the presence of other, chemically different, polymers within FAD column. The nature and composition of the displacer must, therfore, be adjusted if the intervals between the desorption of particular blend components are to be large enough to prevent displacement overlap. Presented at: Balaton Symposium on High-Performance Separation Methods, Siófok, Hungary, September 3–5, 1997.     

Water adsorption on and desorption from crystalline copolymers of vinylidene fluoride with trifluoroethylene

Water adsorption and absorption on crystalline polyvinylidene fluoride with 30% trifluoroethylene, P(VDF-TrFE, 70:30), was examined by thermal desorption spectroscopy. Two distinctly different water adsorption sites are identified: one adsorbed species that resembles ice and another species that interacts more strongly with the polymer thin film. The existence of the latter species is consistent with X-ray diffraction studies of water absorbed into the bulk of copolymers of polyvinylidene fluoride with trifluoroethylene crystalline thin films. There are strong steric effects observed in the angle-resolved thermal desorption that may be a result of the large polymer thin film surface dipoles.     

Peculiarities of Polyacrylic Acid Adsorption on Copper Oxide Powder

The adsorption of polyacrylic acid on copper(II) oxide powder from aqueous solutions was studied. The amount of the adsorbed polymer was shown to increase with time reaching its maximum over 6–7 min. The desorption kinetics of copper polyacrylates was studied by measuring variations in copper ion concentration in the solution. The rate of desorption was found to be independent of the initial concentration of polyacrylic acid. A decrease in the dispersed phase concentration did not actually affect the initial rate of the polymer desorption. However, it caused a drastic fall in the rate of desorption after 1–1.5 min. A mathematical model was proposed for describing the experimental data.     

Sorption and Diffusion of Water and Ethanol in Polyethersulfone Hollow Fiber Membranes

Study on solubility and transport phenomena of penetrant in polymer membrane is of significance for appraising separation ability, selecting membrane materials, designing or exploring membrane separation technology. There are many ways, in which the sorption/desorption method is a more acceptable one for its relatively simple procedures and affable conditions, to study the transport properties of penetrant in polymer. As our best knowledge, many experiments and measured data are reported for flat sheet, while no for hollow fiber membrane using sorption/desorption method. In this paper, we hope to appraise the separation ability of hollow fibers through sorption experiments of water and ethanol vapors in fibers by a proposed separation factor in infinite dilution.     

Matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry combined with multidimensional scaling,binary hierarchical cluster tree and selected diagnostic masses improves species identification of Neolithic keratin sequences from furs of the Tyrolean Iceman Oetzi

The identification of fur origins from the 5300‐year‐old Tyrolean Iceman's accoutrement is not yet complete, although definite identification is essential for the socio‐cultural context of his epoch. Neither have all potential samples been identified so far, nor there has a consensus been reached on the species identified using the classical methods. Archaeological hair often lacks analyzable hair scale patterns in microscopic analyses and polymer chain reaction (PCR)‐based techniques are often inapplicable due to the lack of amplifiable ancient DNA. To overcome these drawbacks, a matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOF MS) method was used exclusively based on hair keratins. Thirteen fur specimens from his accoutrement were analyzed after tryptic digest of native hair. Peptide mass fingerprints (pmfs) from ancient samples and from reference species mostly occurring in the Alpine surroundings at his lifetime were compared to each other using multidimensional scaling and binary hierarchical cluster tree analysis. Both statistical methods highly reflect spectral similarities among pmfs as close zoological relationships. While multidimensional scaling was useful to discriminate specimens on the zoological order level, binary hierarchical cluster tree reached the family or subfamily level. Additionally, the presence and/or absence of order, family and/or species‐specific diagnostic masses in their pmfs allowed the identification of mammals mostly down to single species level. Red deer was found in his shoe vamp, goat in the leggings, cattle in his shoe sole and at his quiver's closing flap as well as sheep and chamois in his coat. Canid species, like grey wolf, domestic dog or European red fox, were discovered in his leggings for the first time, but could not be differentiated to species level. This is widening the spectrum of processed fur‐bearing species to at least one member of the Canidae family. His fur cap was allocated to a carnivore species, but differentiation between brown bear and a canid species could not be made with certainty. Copyright © 2012 John Wiley & Sons, Ltd.     

Electrochemical deposition of poly(trans-[RuCl2(4-vinylpyridine)4]) and its reductive desorption: cyclic voltammetry and electrochemical quartz crystal microbalance studies

The electropolymerization of trans-[RuCl(2)(vpy)(4)](vpy = 4-vinylpyridine) on Au or Pt electrodes was studied by cyclic voltammetry and the electrochemical quartz crystal microbalance (EQCM) technique. Cyclic voltammetry of the monomer in DMSO on Au shows reductions at -2.0 and -2.2 V. Potential cycling over the first wave leads to polymer formation; however, scanning over the second wave leads to desorption of the polymer. These observations were confirmed by EQCM measurements which also revealed a high polymerization efficiency. Electrolysis, EQCM and XPS measurements showed that desorption was associated with substitution of chloride ligands by DMSO when the polymer was in a highly reduced state. The film also showed reversible mass changes due to the oxidation and accompanying ingress of charge-balancing anions and solvent into the film. Measurements on the dried films revealed that large quantities of solvent are trapped in the film during the electropolymerization process.     

Mechanism of hydrostimulated displacement of aromatic compounds from cellulose triacetate films

The effect of temperature on the rate of desorption into water of naphthalene, diphenyl, benzophenone, para-terphenyl, α-naphthol, stilbene, anthracene, and dibutyl phthalate introduced into cellulose triacetate films was studied. It was shown that in water, the removal rate of these compounds from the films increases sharply as compared to desorption into air. The relation between the activation energies and pre-exponential factors characterizing the desorption rate was found in the form of a compensatory effect. The nature of the compensatory effect is explained by osmotic phenomena due to hydrophobic hydration of the polymer. We conclude that mobile polymeric chains of non-crystalline polymer are structured around water and Ar-compound molecules as sponge-like structures forming fringed nanoporous capsules. The simultaneous presence of molecules of different compounds in the polymer was found to cause osmotic competition for a place in the sponge; water absorbed by the chain sponge enhances the volume pulsations of nanocapsules. It was revealed that diffusion occurs because of thermal fluctuations inducing the reorganization of nanoporous capsules and their movement together with Ar-molecules in the matrix by the principle of peristalsis.     

Preparation of Porous Polymer Networks of <Emphasis Type="Italic">N</Emphasis>-Vinylpyrrolidone with Triethylene Glycol Dimethacrylate and Determination of Their Specific Surface Area Using Rose Bengal Dye

Porous polymer networks of N-vinylpyrrolidone with triethylene glycol dimethacrylate were prepared by three-dimensional radical copolymerization using template approach based on incorporation of macromolecular nanoobjects with porogen function. The adsorption of Rose Bengal dye from aqueous solutions onto the copolymers prepared and its desorption were studied by electronic absorption spectroscopy. The specific surface area of the porous polymer networks was estimated from the Rose Bengal adsorption data. The porous polymer networks adsorb riboflavin from aqueous solution. The riboflavin desorption is characterized by complex pattern due to washout from pores of different size.     

Dielectric sorption analysis of pigmented epoxy coatings UV degraded at elevated pressures

Pigmented epoxy coatings were UV degraded for various periods at elevated pressures (1-100 bar) and investigated with dielectric sorption analysis (DSA). Differences in dynamics of absorption behaviour for degraded polymer occurred due to increased hydrophilicity, crosslinking and porosity. Degradation at all pressures showed desorption, caused by swelling of the coating and shrinking of pore size. The amount of water sorption and desorption rose linearly from 1 bar to 50 bar and from 50 bar on no further increase in degradation was found. Longer degradation times at 100 bar also resulted in a linear trend. At lower frequencies double peaks were found as a result of water desorption, polymer relaxation, water-hydrophilic cluster interactions and polymer swelling, indicating a frequency dependence. The double peak could be fitted by two independent curves, whereas a single exponential term sufficed to fit the desorption of water for all frequencies. Pressure is clearly an accelerating degradation parameter in combination with an UV source.