Electrosorption of sodium cellulose sulfates with different substitution patterns

Various types of sodium cellulose sulfate (SCS), dissolved in a 1M LiCl solution, were investigated by alternating current (AC)polarography. The SCS samples differed in the degree of substitution (DS), thedistribution of substituents within the anhydroglucose unit (AGU), and alongthechain, due to the method of synthesis. The goal was to study theelectrosorptionbehavior, characterized by the shape of the desorption wave in the polarogram,as a function of the chemical structure of the SCS samples. The shape of thedesorption wave reflects domains of different substitution. A superimpositionofparameters like DS and pattern of substitution on the electrosorption behaviorwas observed. The AC polarography method described can be used as a tool todistinguish between an even or uneven distribution of substituents along thecellulose chain.     

Simple, expedient methods for the determination of water and electrolyte contents of cellulose solvent systems

The concentrations of water, W, and electrolytes present in solutions of LiCl in N,N-dimethylacetamide, LiCl/DMAc, and of tetrabutylammonium fluoride. x-hydrate in DMSO, TBAF.xW/DMSO can be accurately and expediently determined by three independent methods, UV–vis, FTIR and EMF measurement. The first relies on the use of solvatochromic probes whose spectra are sensitive to solution composition. It is applicable to W/LiCl/DMAc solutions but not to TBAF.xW/DMSO, because the charge-transfer complex bands of the probes are suppressed by strong interactions with the latter electrolyte. Integration of ν_OH band of water may be employed in order to determine [W], hence [electrolyte] by weight difference. EMF measurement uses ion-selective electrodes in order to determine [electrolyte], hence [W] by weight difference. Results of the latter method were in excellent agreement with those of FTIR. The reason for the failure of Karl Fischer titration is addressed, and the relevance of the results obtained to functionalization of cellulose under homogenous solution conditions is briefly commented on.     

Grafting amount and structural characteristics of microcrystalline cellulose functionalized with different aminosilane contents

Cellulose - Microcrystalline cellulose (MCC) has unique properties and its use as reinforcement for polymer composites has been increasing. However, the intrinsic incompatibility with most polymers...     

Synthesis,properties, and fungal degradation of castor-oil-based polyurethane composites with different cellulose contents

Different contents of bonded cellulose were dispersed in a matrix of castor-oil-based polyurethane to produce composites with high susceptibility to fungal attack. We chose to bond the cellulose filler with free diisocyanate, to increase the crosslinking density. Measurements indicated physical and chemical interactions between the polyurethane matrix and cellulose filler. The cellulose network significantly enhanced the interfacial adhesion and thus improved the thermal stability and Young’s modulus of the composites. The influences of the amount of cellulose on the surface chemical structure, surface morphology, and mechanical properties after fungal attack were also investigated. The tensile strength and elongation at break of these composites substantially decreased after exposure to fungus. These composites with high content of renewable raw materials present an optimal balance of physical properties and biodegradability, with potential applications as ecofriendly biomaterials.     

EB-radiolysis of carbamazepine: in pure-water with different ions and in surface water

A method for the rapid and simultaneous monitoring of particulate and dissolved ¹³⁷Cs concentration in water was developed. This method uses pleated polypropylene nonwoven fabric filter to collect particulate radiocesium, and nonwoven fabric impregnated with Prussian blue (PB) to absorb dissolved radiocesium. The fabric was placed into cylindrical plastic cartridges (SS-cartridge and PB-cartridge). Traditional monitoring methods, such as evaporative concentration, often require time for pre-processing. However, this method described requires much less pre-processing time before the detection. Experiments conducted with simulated river water demonstrated that almost all of the suspended solids weight was collected in the SS-cartridge, and that more than 92 % of dissolved ¹³⁷Cs was absorbed onto the two PB-cartridges by 2.5 L/min flow rate when the range of the pH was 6–8. This device was applied to monitor Abukuma River water at two locations and the results were compared with those obtained using the filtrating and evaporative concentration method. The suspended solids concentration in river water, calculated by weight gain of the SS-cartridge and by sediment weight after filtration with a 0.45-μm membrane filter, agreed well. The radioactivity of the particulate and dissolved ¹³⁷Cs also agreed well in one of the two replications of this method. In addition, the required time for pre-processing was reduced by 60 times that by filtrating and evaporative concentration method. This method can separately collect and concentrate particulate and dissolved radiocesium rapidly and simultaneously in the field.     

Enthalpies of interaction of water with microcrystalline cellulose having different degrees of dispersion

Changes in enthalpy during the interaction of different kinds of microcrystalline cellulose and water were determined. The integral and differential enthalpies of polysaccharide interactions with water were calculated. The amount of water retained by the cellulose was determined. The effect of mechanical processing on these characteristics was demonstrated.     

Binding properties of aminopolycarboxylato ligands bound to cellulose

The uptake of metal ions by EDTA bound to cellulose niters has been examined and compared with the corresponding uptake by iminodiacetic acid and N-methyliminodiacetic acid bound to cellulose. The results are interpreted in terms of steric hindrance, geometric factors, electrostatic interactions and thermodynamics.     

Molecular dynamic study of thermodynamic properties of water clusters containing sodium or chlorine ions

The molecular dynamic method with design is used to calculate the thermodynamic properties of isolated water clusters containing Na⁺ or Cl^-. The number of water molecules in the clusters is from 2 to 14. The size dependence of the microscopic analogs of pressure, isothermal compressibility, and surface tension of the clusters is determined. The effect of positive and negative ions on heteromolecular nucleation in vapor is discussed. Translated fromZhurnal Strukturnoi Khimii, Vol. 38, No. 6, pp. 1092–1102, November–December, 1997.     

Dilute solution properties of sodium cellulose disulphate

Sodium cellulose sulphate (NaCaS), with degree of substitution (DS) of 1.90, was synthesized by reacting samples of cellulose, covering a wide range of average molecular weight, with S03/dimethyl formamide complex. A solution of NaCS in 0.5 M aq. NaCl was studied by solution viscometry, light scattering and membrane osmometry. The solution was dialysed against solvent. The following MarkHouwink-Sakurada equation and relation between the z-average radius of gyration and weightaverage molecular weight, Mw, were established for $\text{7.2 × 10}{}^4\text{?}\text{M}{}_{\mathrm{w}}\text{? 1.5 × 10}{}^6\text{at 25°}$.The NaCS with salt system was analysed according to the theory of linear non-ionic polymers. Flory's viscosity parameter φ is significantly molecular weight dependent. The partially free draining effect and the excluded volume effect were estimated and the former predominated. The unperturbed chain can be regarded as Gaussian and its dimension A was found to be 1.21 × 10^?8 cmand the conformation parameter a was 2.9.     

Template-assisted self assembly of two lipophilic polyion aggregates derived from sodium tetraphenyl imidodiphosphinate-complexes containing sodium ions in four different coordination environments

The molecular structures of two lipophilic polyion aggregates derived from tetraphenyl imidodiphosphinate are described: [Na(crown ether)][MNa(2)[Ph(2)P(O)NP(O)Ph(2)](4)] with crown ether = 15-crown-5 for 1and benzo-15-crown-5 for (M = Na(+) for 1 and Na(H(2)O)(+) for 2).     

Effect of different sodium halides on the self-association of tertiary butanol in water

The molecular self-association of hydrophobic substances is an important process for many biological systems. Here, the authors study the effect of salt on the molecular self-association of t-butanol in water solution, using NMR techniques. They compare the effects of different sodium halides (NaCl, NaBr, and NaI) as a function of their concentration.     

FT Raman investigation of sodium cellulose sulfate

FT Raman investigation of sodium cellulose sulfates (NaCS) was reported. Different NaCS were prepared by two diverse sulfation methods and their total degrees of substitution (DS) of sulfate groups were determined through either ¹³C-NMR spectroscopy or elemental analysis. Subsequently, these NaCS were characterized with FT Raman spectroscopy. The caused bands through the introduction of the sulfate groups in cellulose chain were explained and assigned. Additionally, a strong linear correlation between the areas under the bands ascribed to the stretching vibrations of C–O–S groups and the total DS of NaCS was presented. A rapid method of quantifying the total DS of NaCS was established. Finally, sodium sulfate (Na₂SO₄), a salt that is very often produced during the sulfation of cellulose, was found to be analyzable even with a weight content of 0.12% in NaCS. The method of quantifying the content of this salt in NaCS was investigated with Raman spectroscopy.     

Molecular parameters of sodium cellulose xanthate in dilute solution

Molecular parameters of sodium cellulose xanthate in NaOH solution have been determined by means of light scattering and viscometry. The effect of the degree of substitution on the molecular configuration of sodium cellulose xanthate has been studied for three series of samples of varying degree of substitution. The expansion factor has been determined from the expression due to Orofino and Flory. The effective bond length b and the ratio of the unperturbed dimension to the dimension assuming free rotation of the chain units (R?_o²/R?_f²)^1/2, have also been determined. It is concluded that sodium cellulose xanthate in dilute solution is a loosely coiled molecule, comparable to other cellulose derivatives in chain stiffness.     

Preconcentration of heavy metals ions from aqueous solutions by means of cellulose phosphate: an application in water analysis

Cellulose phosphate (CELLPHOS) was studied as a collector for analytical preconcentration of traces of Cd(II), Cr(III), Cu(II) and Ni(II) from aqueous sample solution. It has been proved that using chromatographic columns packed with CELLPHOS for preconcentration and 1.0 mol 1(-1) HCl for elution the adsorbed analytes are quantitatively enriched. An enrichment factor of 20 (100 ml sample, 5 ml concentrate) was achieved by this separation procedure, which was applied to a series of water analyses (river, sea, bog water).     

Binding of sodium dodecyl sulfate with linear and branched polyethyleneimines in aqueous solution at different pH values

Isothermal titration microcalorimetry (ITC), conductivity, and turbidity measurements have been carried out to study the interaction of sodium dodecyl sulfate (SDS) with polyethyleneimines (PEI) including linear PEI and branched PEI at different pH values of 3, 7, and 10. In all cases, the polymers show a remarkable affinity toward SDS. At pH 3, the polymer PEI is a strong polycation, and the binding is dominated by electrostatic 1:1 charge neutralization with the anionic surfactant. At pH 7, the electrostatic attraction between SDS and PEI is weak, and the hydrophobic interaction becomes stronger. At the natural pH of 10, PEI is essentially nonionic and binds SDS in the form of polymer-bound surfactant aggregates. The charge neutralization concentration (C1) of SDS for the PEI-SDS complex can be derived from the curves of variation of the enthalpy, conductivity, and turbidity with SDS concentration. There is good agreement between the results from the three methods and all show a decrease with increasing pH. The total interaction enthalpies (deltaH(total)) of PEI with SDS are obtained from the observed enthalpy curves and the difference enthalpy (deltaH*) between the total enthalpy of branched PEI with SDS, and the total enthalpy of linear PEI with SDS can be derived from the obtained deltaH(total). The difference deltaH* increases dramatically as pH increases, which indicates that the interactions are different for linear PEI and branched PEI at high pH values. A schematic map of the different states of aggregation is presented.     

Hybrid particles of polystyrene and carboxymethyl cellulose as substrates for copper ions

The synthesis of hybrid particles was carried out by emulsion polymerization of styrene in complexes formed by carboxymethyl cellulose (CMC), a polyanion, and a cationic surfactant, cetyltrimethylammonium bromide (CTAB). CMC chains with variable molecular weights and degrees of substitution were tested. The polymerization condition chosen was that corresponding to CMC chains fully saturated with CTAB and to the onset of pure surfactant micelle formation, namely, at the critical aggregation concentration. The hybrid particles were characterized by zeta potential and light scattering measurements. The period of colloidal stability in the ionic strength of 2.0 mol L(-)(1) NaCl was observed visually. Upon increasing the CMC chain length, the particle characteristics remained practically unchanged, but the colloid stability was increased. The increase in the CMC degree of substitution led to particles with more negative zeta potential values. The adsorption of copper ions (Cu(2+)) on the surface of hybrid particles could be described by the Langmuir model, as determined by potentiometric measurements. The increase in the mean zeta potential values and X-ray absorption near-edge spectra evidenced the immobilization of Cu(2+) ions on the hybrid particles.     

Dissipative crystallization of sodium salts of carboxymethyl cellulose

Drying dissipative patterns were observed at room temperature on a cover glass, a watch glass, and a Petri glass dish during the course of dryness of aqueous solution of sodium salts of carboxymethyl cellulose (NaCMC) having different molecular weights in the presence of sodium chloride and in their absence. Without salt, the polymers were slightly hygroscopic and did not dry up completely on the substrates. Single crystals of the NaCMC without salt were short rodlike and quite similar to those of the other polysaccharides studied hitherto, i.e., hydroxypropyl cellulose and sodium dextran sulfate. Morphology of the polymer crystals were short rods, long dendritic rods, and/or hedrite assemblies depending on location in the dried film and in the presence of sodium chloride. Spoke-like orientation of the long dendritic rods appeared on a cover glass and a watch glass especially for NaCMC of low molecular weights.     

Effect of ionic strength and type of ions on the structure of water swollen polyelectrolyte multilayers

This study addresses the effect of ionic strength and type of ions on the structure and water content of polyelectrolyte multilayers. Polyelectrolyte multilayers of poly(sodium-4-styrene sulfonate) (PSS) and poly(diallyl dimethyl ammonium chloride) (PDADMAC) prepared at different NaF, NaCl and NaBr concentrations have been investigated by neutron reflectometry against vacuum, H(2)O and D(2)O. Both thickness and water content of the multilayers increase with increasing ionic strength and increasing ion size. Two types of water were identified, "void water" which fills the voids of the multilayers and does not contribute to swelling but to a change in scattering length density and "swelling water" which directly contributes to swelling of the multilayers. The amount of void water decreases with increasing salt concentration and anion radius while the amount of swelling water increases with salt concentration and anion radius. This is interpreted as a denser structure in the dry state and larger ability to swell in water (sponge) for multilayers prepared from high ionic strengths and/or salt solution of large anions. No exchange of hydration water or replacement of H by D was detected even after eight hours incubation time in water of opposing isotopic composition.