Water absorption and desorption from the dipole ordered polymer poly(methylvinylidene cyanide)

From thermal desorption studies, we find evidence that absorbed water in the bulk of poly(methylvinylidene cyanide) is more weakly bound than is the case for copolymer films of poly(vinylidenefluoride-trifluoroethylene). Ultraviolet laser enhanced thermal desorption of absorbed water exhibits little light polarization dependence for poly(methylvinylidene cyanide) in contrast to absorbed water in copolymer films of poly(vinylidenefluoride-trifluoroethylene). The implications of these differences are discussed.     

Loss of water and hydrogen cyanide from aquopentamminecobalt(III) hexacyanoferrate(III)

Previous studies on the non-isothermal decomposition of [Co(NH₃)₅H₂O] [Fe(CN)₆] showed that H₂O and three molecules of HCN are lost simultaneously but the results of the isothermal studies reported here show that these processes can be partially separated. It was found that the first reaction involves the loss of H₂O and two molecules of HCN and the second reaction results in the loss of an additional molecule of HCN. Kinetic studies have been performed and kinetic parameters are reported here and possible mechanisms are discussed.     

Diffusive desorption of small solute molecules from amorphous polymers: poly(methyl methacrylate), poly (vinyl acetate) and poly(n-alkyl 2-cyanoacrylates)

Diffusion coefficients of some aromatic substances in poly(vinyl acetate) and poly(methyl methacrylate) have been measured from desorption rates into aqueous buffers from solid solutions of diffusant in cast polymer films. With ordinary spectrophotometric instrumentation, extension of the measurable range of the diffusion coefficient at infinite dilution to below 10^?21 m² sec^?1 is sometimes possible. Measures values below 10^?12 m² sec^?1 are generally much more quickly obtained, and are apparently at least as reproducible as those obtained by time-lag methods, permitting differential effects of diffusant molecular weight and shape to be studied, with solutes of higher molecular weight than those to which previous published studies were confined. Diffusion coefficients of the same solutes in a number of poly(n-alkyl 2-cyanoacrylates) were measured by desorption from polymer particles and films. The rank order and general dependence of diffusivity upon molecular weight and shape is similar in all three polymers. There is a tendency for the ionic and basic solutes to become bound, probably by covalent linkage, to poly(n-alkyl 2-cyanoacrylate) molecular chain ends.     

Fragmentation of poly(amidoamine) dendrimers in matrix-assisted laser desorption

Fragmentation of different generations of poly(amidoamine) dendrimers was explored in five common MALDI matrices: 2,5-dihydroxybenzoic acid (DHB), 4-hydroxy-3-methoxycinnamic acid (FER), α-cyano-4-hydroxycinnamic acid (ACH), 2,4,6-trihydroxyacetophenone (THAP), and 3-hydroxypicolinic acid (HPA). Of these, DHB was the softest matrix and ACH produced significant fragment intensity already at MALDI threshold, FER and THAP being in between. HPA was not a convenient matrix for dendrimers and produced a specific fragmentation pattern. Fragmentation analysis was mainly concentrated on generation G1, which contains already all essential structural elements. Dendrimers showed complicated fragmentation behavior with multiple fragmentation channels in our MALDI experiments. The relative intensities of these channels depended selectively on choice of the matrix and showed dissimilar dependence on the laser pulse energy. This was attributed to different fragmentation mechanisms, due to different protonation pathways, occurring in the same MALDI plume. The fragmentation pathways were proposed for all observed fragmentation channels. All fragmentation sites of protonated ions were found to be directly attached to the protonation sites and the fragmentation was surplus charge driven in this sense. No charge remote fragmentation channels were detected. Cationized dendrimers showed higher stability than the protonated ions.     

Water sorption/desorption kinetics in poly(ethylene naphthalene-2,6-dicarboxylate) and poly(ethylene terephthalate)

Water sorption/desorption experiments were carried out on films (～ 220 μm thick) of amorphous poly(ethylene naphthalene-2,6-dicarboxylate) (PEN) stored in ambient conditions for different periods of time (0.5-4 years) and of poly(ethylene terephthalate) (PET) with different degrees of crystalinity levels (0-29%) by means of FTIR spectroscopy. Water sorption/desorption kinetics follows Fick's law for all samples investigated. Water sorption isotherms, obtained from gravimetric methods, indicate a larger sorption capacity in the case of PEN materials. The apparent diffusion coefficients (D) are larger in the case of PET samples. The observed D values decrease with storage time (physical aging) of PEN samples and with the crystallinity of PET samples. © 1995 John Wiley & Sons, Inc.     

The effect of pH on charge, swelling and desorption of the dispersant poly(methacrylic acid) from poly(methyl methacrylate) microcapsules

Poly(methyl methacrylate) microcapsules have been prepared using the solvent evaporation technique with poly(methacrylic acid) (PMAA) as dispersant. The charge, swelling and desorption of PMAA from the microcapsules after treating the suspension with base have been followed using microelectrophoresis, X-ray photoelectron spectroscopy and quartz crystal microbalance with dissipation monitoring on model PMMA surfaces. Basic treatment of the microcapsule suspension leads to temporary colloidal stability through the introduction of charges on the PMAA chain. However, the increase in charge causes a continuous desorption of PMAA from the microcapsule surface, eventually leading to aggregation. If instead poly(diallyldimethylammonium chloride) is added to the base treated microcapsule suspension, good colloidal stability is obtained.     

Polymer drying, 1. Time-studies of desorption from liquid saturated poly(styrene-co-divinylbenzene) microparticles

Time studies of evaporation from liquid-saturated poly[(Sty)₉₈-co-(DVB)₂] particles enmeshed in poly(tetrafluoroethylene) microfibers show that it is possible to distinguish kinetically between volatile sorbed molecules not absorbed to the polymer chain and those that are adsorbed to it. Elimination of the nonadsorbed molecules occurs first, and it follows zero-order kinetics. The subsequent elimination of the residual volatiles, namely the adsorbed molecules, follows first-order kinetics, with a rate constant that remains constant only until the enmeshed microparticles undergo transition from the gel to the glass state. Thereafter, is observed a sequence of up to six independent rate constants in a series of intervals, the durations of which increase exponentially. This is interpreted to mean that after evaporation to the glass transition composition, the total weight of residual adsorbed molecules is given by a linear combination of exponential decay functions for up to six populations of adsorption sites, the rate constants for which reflect the force of association between the sites and the retained molecules.     

Kinetics and mechanism of pH responsive cationic desorption from poly(vinyl alcohol)-borate hydrogel

Desorption of potassium chloride and calcium chloride from poly(vinyl alcohol)-borate hydrogel was studied at different pH from 3 to 10 using phthalate, phosphate and borate buffers. The rate of desorption from hydrogel was evaluated using conductance method for analysis. It was observed that rate of desorption process decreases on increasing pH of solution from acidic medium to basic medium. The mechanism responsible for the desorption of interacted K⁺ and Ca²⁺ ions in hydrogel moiety in acidic, neutral and basic medium were analyzed. The pseudo first order rate constants for desorption process at different pH were summarized and the rate of desorption of monovalent and divalent cations at various pH compared on the basis of standard deviation and linear regression constant values.     

Matrix-assisted laser desorption/ionization-collision induced dissociation of poly(styrene)

Matrix-assisted laser desorption/ionization-collision induced dissociation (MALDI-CID) has been employed for the analysis of poly(styrene) in a tandem hybrid sector-time of flight instrument. Spectra are shown for adducts of poly(styrene) with copper and silver ions. The distributions of fragment ion peaks were found to be consistent from precursor ions containing both metal ions. It is shown how the masses of the end groups of the polymer may be inferred from the mass-to-charge ratios of two of the series of ion peaks that are seen in the MALDI-CID spectra. Mechanisms are proposed for the formation of some of the other series of ion peaks that are observed in the spectra.     

Biodegradable water absorbent synthesized from bacterial poly(amino acid)s

Biodegradable hydrogels prepared by gamma-irradiation from microbial poly(amino acid)s have been studied. pH-Sensitive hydrogels were prepared by the gamma-irradiation of poly(gamma-glutamic acid) (PGA) produced by Bacillus subtilis and poly(epsilon-lysine) (PL) produced by Streptomyces albulus in aqueous solutions. When the gamma-irradiation dose was 19 kGy or more, and the concentration of PGA in water was 2 wt.-% or more, transparent hydrogels could be produced. For the 19 kGy dose, the produced hydrogel was very weak, however, the specific water content (wt. of absorbed water/wt. of dry hydrogel) of this PGA hydrogel was approximately 3,500. The specific water content decreased to 200, increasing when the gamma-irradiation dose was over 100 kGy. Under acid conditions or upon the addition of electrolytes, the PGA hydrogels shrunk. The PGA hydrogel was pH-sensitive and the change in the volume of the hydrogel depended on the pH value outside the hydrogel in the swelling medium. This PGA hydrogel was hydrodegradable and biodegradable. A new novel purifier reagent (coagulant), made from the PGA hydrogels, for contaminated turbid water has been found and developed by Japanese companies. A very small amount of this coagulant (only 2 ppm in turbid water) with poly(aluminum chloride) can be used for the purification of turbid water. A PL aqueous solution also can change into a hydrogel by gamma-irradiation. The specific water content of the PL hydrogel ranged from 20 to 160 depending on the preparation conditions. Under acid conditions, the PL hydrogel swelled because of the ionic repulsion of the protonated amino groups in the PL molecules. The rate of enzymatic degradation of the respective PL hydrogels by a neutral protease was much faster than the rate of simple hydrolytic degradation.     

Isothermal desorption of water from anatase

The variation in the water content of anatase was studied as a function of the equilibrium water vapour pressure in the range from 2660 Pa to 0.0013 Pa at 295 K. It was found that anatase contains at most 2.68 mole of physically adsorbed H₂O per mole of TiO₂, with an additional 0.34 mole of H₂O per mole of TiO₂ which does not desorb even at 0.0013 Pa.

---

Zusammenfassung Bei einer Temperatur von 295 K wurde die Veränderlichkeit des Wassergehaltes von Anatas mit einem Ausgleichsdruck zwischen 2660 Pa und 0.0013 Pa untersucht. Es wurde festgestellt, daß Wasser in Anatas teilweise durch unterschiedlich starke physikalisch Adsorption gebunden ist.

     

Determination of chloride by displacement of hydrogen cyanide from mercury(II) cyanide

A method, based on the passivity of mercury(II) cyanide in dilute sulphuric acid and its reaction with hydrochloric acid to produce hydrogen cyanide, has been developed for the determination of small amounts of chloride. Hydrogen cyanide, distilled from a mercury(II) cyanide-halide-dilute sulphuric acid system is found by iodometric measurement to be directly proportional to the amount of chloride or bromide and of hydrogen ion in acids such as sulphuric acid. A linear correlation also holds for iodide but the stoichiometry is different, the titration values being about three times larger than expected. By conversion of the cyanide into a dye by means of the pyridine-pyrazolone reagent, 0.014-0.43 mug ml chloride concentrations have been determined. The method is also applicable to bromide and sulphuric acid in small amounts but not to fluoride and iodide. Results are reproducible to within +/-2%.     

Photon stimulated ion desorption studies from poly(sulphone) using synchrotron radiation in a single-bunch mode

Photon stimulated ion desorption (PSID) studies from poly(sulphone) (PS) have been carried out by using high-resolution time-of-flight mass spectrometry. Synchrotron radiation at the Brazilian Synchrotron Light Source (LNLS) operating in a single-bunch mode was used as excitation source. PS was excited at the sulphur 1s-edge and the desorption of small and large fragments has been observed. The results are discussed in terms of the X-ray induced electron stimulated desorption mechanism. The present results contrast with previous ones reported for poly(3-methylthiophene) (PMeT), in which the observation of S⁺ and S²⁺ was interpreted solely in terms of an Auger-stimulated ion desorption mechanism.     

Homogeneous blend membrane made from poly(ether sulphone) and poly(vinylpyrrolidone) and its application to water electrolysis

A homogeneous blend membrane has been successfully prepared from poly(ether sulphone) (PES) and poly(vinylpyrrolidone) (PVP), which have been usually thought to be immiscible to each other. The PES–PVP membrane possesses combined advantages of the hydrophobic and hydrophilic components; specifically, both good mechanical strength and excellent hydrophilicity have been achieved simultaneously. The success of achieving such special properties can be ascribed to the appropriate choice of solvent for membrane casting, N,N-dimethylformamide (DMF) in this case, and the post-treatment of the membrane in alkaline ethanol solution for obtaining hydrophilicity. Membranes with different blending ratios were characterized with tensile test, scanning electron microscopy (SEM), transmission electron microscopy (TEM), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and electrochemical measurements. The membrane was found to function well as a diaphragm in water electrolysis. In comparison with the traditional asbestos diaphragm, an energy saving of ca. 10% can be reached upon employing PES–PVP membranes in water electrolysis.     

Chiral poly(ureidophthalimide) foldamers in water

Poly(ureidophthalimide)s decorated with hydrophilic side chains, that ensure solubility in aqueous media, have been synthesized and characterized by UV/Vis and circular dichroism (CD) spectroscopy. Temperature and concentration dependent CD measurements in water have revealed an almost temperature and concentration independent Cotton effect, indicative for a strong intramolecular organization. Similar studies in THF demonstrate the dynamic nature of the secondary architecture, a characteristic of foldamers. In addition, the bisignated Cotton effect in water is opposite in sign to that in THF, suggestive for a solvent-dependent preference for one helical handedness. Mixing experiments prove the dominance of water in determining the handedness of the helical architecture. The solvent allows for control over the helical architecture and thus governs the supramolecular synthesis.     

Continuous desorption rate measurement from a shallow-bed of poly(styrene-divinylbenzene) particles with correction for experimental artifacts

A 0.50 mm high bed, containing ca. 3 mg of the nominally non-porous poly(styrene-divinylbenzene) (PS-DVB) sorbent Hamilton PRP-infinity, is located in a valve. After the bed is pre-equilibrated with a (7/3) methanol/water solution of naphthalene (NA), the valve is switched and (7/3) methanol/water solvent flows continuously through the bed at a high linear velocity. This causes NA to desorb into a constantly refreshed solvent, creating a "shallow-bed" contactor with an "infinite bath" kinetic condition. The effluent from the bed passes through a UV-absorbance detector which generates the observed instantaneous desorption rate curve for NA. The same experiment is performed using the solute phloroglucinol (PG), which is not sorbed by PRP-infinity and serves as an "impulse response function marker" (IRF-Marker). The resulting peak-shaped IRF curve is used in two ways (i.e. subtraction and deconvolution) in order to correct the observed instantaneous rate curve of NA for the following experimental artifacts: hold-up volume of the bed and valve, transit-delay time between the bed and the detector and instrument bandbroadening of the NA zone. The cumulative desorption rate curve, which is a plot of moles NA desorbed versus time, is obtained by integration. It is found to be accurately described by the theoretical equation for homogeneous spherical diffusion. The diffusion coefficient of NA inside the PRP-infinity particles (5.0+/-0.6) x 10(-11) cm2/s, agrees with the literature value that was obtained from the sorption rate of NA into the same particles. This constitutes virtually conclusive evidence for diffusion control of intra-particle kinetics of NA in the PS-DVB matrix of PRP-infinity and related polymers. The influence of both sorbent and solute properties on the method is evaluated.     

Preparation of poly(fumaric acid) from poly(di-t-butyl fumarate) and poly(di-trimethylsilyl fumarate)

Polymerization conditions of di-t-butyl fumarate and di-trimethylsilyl fumarate were studied in detail. They cannot be polymerized by either anionic or coordination initiators, but radical and radiation polymerizations are successful. Characterization of poly(di-t-butyl fumarate), obtained thereby, with ¹H-NMR spectrum suggests that the backbone of the chain is stiff. From analysis of thermal properties of poly(di-t-butyl fumarate), it is found to be completely converted to poly(fumaric acid) by pyrolysis around 200°C. Poly(di-trimethylsilyl fumarate), on the other hand, can be quantitatively hydrolyzed with acid to the same polyacid, too. The preliminary measurement of the dissociation behaviors of poly(fumaric acid) was done by potentiometric titration, which shows that the titration curves of poly(fumaric acid) are different from those of poly(acrylic acid) and poly(maleic acid).