Lignin adsorption on cellulose fibre surfaces: Effect on surface chemistry, surface morphology and paper strength

The adsorption of lignin on cellulose fibres at neutral pH and the effects of calcium ions and a cationic polyelectrolyte (PDADMAC) on the adsorption have been studied. The surface coverage by lignin was determined by electron spectroscopy for chemical analysis (ESCA). The morphology of the lignin layer was studied by atomic force microscopy (AFM). The effect of adsorbed polyelectrolyte and lignin on the strength properties of the paper was also studied. The adsorbed amount of lignin increased monotonically with lignin concentration. Addition of calcium ions resulted in a very high surface coverage by lignin. PDADMAC did not enhance the adsorption of lignin, but without addition of polyelectrolyte the lignin was very weakly attached to the fibre surface. PDADMAC formed complexes with lignin in solution. At high polymer/lignin concentration ratios the charge of the complex was positive and it adsorbed irreversibly as large blobs. At low ratios the complex was easily washed away from the fibre surface. When PDADMAC was pre-adsorbed on the fibre surface the lignin adsorbed as small granules at all lignin concentrations. Neither PDADMAC nor lignin alone increased the strength of pulp sheets significantly. However, together they increased the bonding between fibres.     

Nanostructured micellar films formed via layer-by-layer deposition of photoactive polymer

Photoactive nanostructured micellar films were prepared from the amphiphilic copolymer poly(sodium styrenesulfonate- stat-2-vinylnaphthalene) (PSSS- stat-VN) and cationic polyelectrolyte poly(diallyldimethylammonium chloride) (PDADMAC) or poly(allylamine hydrochloride) (PAH) on quartz and silicon substrates via layer-by-layer (LbL) electrostatic self-assembly. The macromolecules of this amphiphilic copolymer adopt a coiled micellar conformation in aqueous solution that is preserved in the films as evidenced by atomic force microscopy (AFM) and spectroscopic studies. The hydrophobic domains present in the film can serve as host sites for various organic molecules. The probe molecules reside in those isolated nanosize domains. Their aggregation and quenching of their emission is eliminated. The experiments showed a regular growth of multilayer thickness and the content of solubilized compounds in the films. Thus, a defined amount of the hydrophobic compounds of interest may be introduced into these water-processable polymeric films. Some stratification of the films was induced by the presence of stiff nanoparticle-like micelles. That makes these films an important new material for studies of photoinduced energy and electron transfer.     

Microstructures and growth characteristics of polyelectrolytes on silicon using layer-by-layer assembly

Growth processes of nanocomposite layers obtained by polyelectrolytes, poly(sodium 4-styrenesulfonate) (PSS) and poly(diallyldimethylammonium chloride) (PDADMAC), self-assembled on silicon surface using layer-by-layer (LbL) technique were investigated, and theoretical and experimental data are herein reported. Complementary microstructural and compositional analyses techniques (scanning electron microscopy, ellipsometry, X-ray reflectivity, zeta (ξ) potential measurements and attenuated total reflection infrared spectroscopy) were used for deep characterization of the multilayer structure formation. Electrophoretic zeta (ξ) potential measurements indicated that the surface charge was either positive or negative, depending on the polyelectrolyte used (PDADMAC or PSS). ATR-IR spectra confirmed the successfully silanization process and then, the building up of the nanocomposite layer. Morphological investigation and X-ray reflectivity demonstrated the growth process and cross-section size of the bilayers. Ellipsometric measurements were in very good agreement with SEM and XRR, showing once again the successful deposition of polyelectrolyte multilayers.      

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.     

Controlled Stripping of Polyelectrolyte Multilayers by Quaternary Ammonium Surfactants

The quartz crystal microbalance with dissipation technique (QCM‐D) and atomic force microscopy (AFM) have been employed to study the interaction of N‐tetradecyl trimethyl ammonium bromide (TdTmAB) with polyelectrolyte multilayers containing poly(sodium 4‐styrene sulfonate) (PSS) as the polyanion and either poly(allylamine hydrochloride) (PAH) or poly(diallyl dimethyl ammonium chloride) (PDADMAC) as the polycations. The multilayers were exposed to aqueous solutions of TdTmAB. This resulted in a selective removal of PDADMAC PSS layers while layers with PAH as polycation remained stable. It is suggested that PDADMAC/PSS multilayers can be employed as strippable protecting layers.

     

Sorption–Desorption of Copper and Strontium Ions by the Soil. The Influence of Microorganisms on the State of Metals

Sorption of heavy metal (copper and strontium) ions by the meadow chernozem and grey forest soils differing in the content of organic substance was described using the Langmuir equation. The analysis of characteristic sorption coefficients demonstrated that copper possesses the enhanced affinity for the studied soil samples compared to strontium. Maximal values of the sorption of copper (0.085 mmol/g) and strontium (0.045 mmol/g) obtained for the colloidal fraction of meadow chernozem soil (particle diameter d < 1 m) are approximately 1.5 times larger than for the same fraction of grey forest soil; this ratio remains almost the same even when using the coarser fraction (d < 50 m). It was established that up to 90% of metal ions could be present in the soil in an immobile form. An increase in the concentration of heavy metal ions in the soil causes their redistribution between the components of absorbing soil complex and an increase in the fraction of metal in mobile forms (water-soluble, exchange, soluble in weakly acidic medium). Upon the microbiological treatment (bioleaching in the suspension variant) of the soils containing copper or strontium ions, the total content of metal, including its mobile forms, decreases by an order of magnitude.     

Preparation and properties of nanosized fluorescent solid films based on a polyelectrolyte-surfactant complex with organic dyes

A procedure for preparing an organosoluble stoichiometric complex based on a cationic polyelectrolyte and an anionic surfactant is described. A method is proposed for forming monolayers at the water-air interface, along with conditions for preparing fluorescent nanosized solid films based on polyelectrolyte complex and organic dyes using the Langmuir-Blodgett (LB) method. The spectral and luminescent properties of the obtained films are investigated. It is established from the absorption and fluorescence spectra of LB films that electrostatic interaction between the molecules of polyelectrolyte complex and oxazine dyes results in dimer formation.     

Potentiometric back titration as a robust and simple method for specific surface area estimation of lignocellulosic fibers

The specific surface area (SSA) of cellulosic or lignocellulosic fibers is seldom reported in the recent literature on papermaking, despite its close relation with the degree of refining and other key pulp properties. Amidst outdated assays (Pulmac permeability test) and methods that, while accurate, are of doubtful usefulness for papermaking purposes (N₂ adsorption–desorption), we suggest a methodology based on the cationic demand. A commonly used cationic polyelectrolyte, poly(diallyldimethylammonium chloride) (PDADMAC), became adsorbed onto thermomechanical pulp samples. Then, a potentiometric back titration with an anionic polyelectrolyte measured the cationic demand, expressed as microequivalents of PDADMAC per gram of pulp. Multiplying this value by the surface area of a microequivalent of polymer, considering rod-like conformation in the case of minimum ionic strength, yielded the SSA of the lignocellulosic pulp. Our system assumes that the quaternary ammonium groups were anchored through electrostatic and ion–dipole interactions. Measuring the carboxyl content allowed for discriminating between both kinds of forces. Finally, the model could be validated by plotting the estimated SSA values against the Schopper-Riegler degree, attaining high correlation coefficients (R²?~?0.98). Owing to the high molecular weight of the polyelectrolyte of choice (107 kDa), and more particularly in the case of fine-free pulps, SSA values estimated from the cationic demand were consistently lower than those from dye (Congo red) sorption. Instead of being a drawback, the limited diffusion of PDADMAC through fibers can enable papermakers to attain a more helpful quantification of the available surfaces in operations with low residence times.

     

全硫取代三苯甲基自由基酯基衍生物与牛血清白蛋白的相互作用

采用荧光光谱、电子顺磁共振（EPR）波谱、紫外-可见吸收光谱和分子对接等技术研究了全硫取代三苯甲基（TAM）自由基酯基衍生物ET-03与牛血清白蛋白（BSA）的相互作用,发现ET--03与BSA能自发发生结合作用;主要以疏水作用力结合在BSA亚结构域ⅡA（位点Ⅰ）和亚结构域ⅢA（位点Ⅱ）上;ET-03对BSA的荧光猝灭效应为动态、静态混合猝灭机制,且可能存在非辐射能量转移.研究结果表明,酯基衍生化TAM自由基与白蛋白能自发结合,有望用于蛋白构效关系研究;同时也提示将TAM自由基酯基衍生物用于活体成像或自旋标记物时应考虑其与蛋白相互作用的影响.     

Kinetics and Isotherms of Cationic Polyelectrolyte Adsorption on Quartz

The kinetics of the formation of quartz surface charge in the solutions of a cationic polyelectrolyte, poly(styrene-co-dimethyl aminopropylmaleimide) with the molecular mass M = 20000 is studied in the concentration range from 10^–5 to 0.5 g/l in 10^–4 M KCl background solution at pH 6.5. Quartz capillaries with the radius from 5 to 10 m and molecularly smooth surface are used as model systems. Characteristic times of the formation of the surface charge at equilibrium with the solution are calculated from the data on the kinetics of adsorption; these times are equal to 40–50 min for the region of electrostatic adsorption (before the surface charge reversal) and 20–25 min, for the region of hydrophobic adsorption upon the formation of the second adlayer. Based on the steady values of the surface charge, the isotherms and potentials of adsorption of cationic polyelectrolyte are calculated. Electrostatic adsorption isotherm is described by the Langmuir equation with the energy of molecular adsorption of 25.4kT. It is shown that, at polymer concentration above 10^–2 g/l, the conformation of adsorbed molecules ceases to be planar. However, even in this case, we succeed in calculating the surface charge using the Helmholtz and Gouy equations and applying the pressure drops at the capillary ends higher than 10 atm, when under the loading of increasing shear stress in the surface layer the conformation of adsorbed molecules approaches the planar shape. Based on the two-layer model of the formation of surface charge developed earlier, it is shown that the energy of hydrophobic adsorption is smaller than that of electrostatic adsorption and is equal to 17.7kT. Possible physical mechanisms of electrostatic and hydrophobic adsorption of cationic polyelectrolyte molecules on quartz are discussed.     

Breaking of Symmetry of Solitons in the Ion-Radicals of α,ω-Disubstituted Polyenes

Quantum-chemical calculations in the AM1 approximation were made for the optimized geometry and also the electron and spin density distributions in the ion-radicals of ,-substituted polyenes [R—(CH=CH) _n —R]^±·. It was found that a soliton (of hole or electron type) with half-integral spin forms waves for the and components of the electron density, in contrast to the wave for the charges in the ions of polymethine dyes with a closed electron shell, containing a zero-spin soliton. The introduction of terminal groups of medium electron-donating power [—NH₂,—C(CN)₂] leads to the breaking of symmetry of the soliton at n2, whereas in unsubstituted polyenes the symmetrical geometry and symmetrical distribution of the electron and spin density are retained irrespective of the length of the conjugation chain.     

Electrical monitoring of polyelectrolyte multilayer formation by means of capacitive field-effect devices

The semiconductor field-effect platform represents a powerful tool for detecting the adsorption and binding of charged macromolecules with direct electrical readout. In this work, a capacitive electrolyte–insulator–semiconductor (EIS) field-effect sensor consisting of an Al-p-Si-SiO₂ structure has been applied for real-time in situ electrical monitoring of the layer-by-layer formation of polyelectrolyte (PE) multilayers (PEM). The PEMs were deposited directly onto the SiO₂ surface without any precursor layer or drying procedures. Anionic poly(sodium 4-styrene sulfonate) and cationic weak polyelectrolyte poly(allylamine hydrochloride) have been chosen as a model system. The effect of the ionic strength of the solution, polyelectrolyte concentration, number and polarity of the PE layers on the characteristics of the PEM-modified EIS sensors have been studied by means of capacitance–voltage and constant-capacitance methods. In addition, the thickness, surface morphology, roughness and wettabilityof the PE mono- and multilayers have been characterised by ellipsometry, atomic force microscopy and water contact-angle methods, respectively. To explain potential oscillations on the gate surface and signal behaviour of the capacitive field-effect EIS sensor modified with a PEM, a simplified electrostatic model that takes into account the reduced electrostatic screening of PE charges by mobile ions within the PEM has been proposed and discussed.

Modification of properties of ion exchange membranes. VII. Relative transport number between various cations of cation exchange membrane having cationic polyelectrolyte layer and mechanism of selective permeation of particular cations

Electrodialytic behavior of cation exchange membrane having cationic polyelectrolyte layer on its surface (relative transport number between two cations, P, current efficiency, and electric resistance of the membrane during the electrodialysis) was measured using various cations, and the mechanism of selective permeation of lower-valent cations than the higher and of larger hydrated cations than the smaller was investigated. The following conclusions were obtained: (1) the cationic polyelectrolyte layer narrowed the pathway for ions; (2) when the pathway was made narrower by other methods, the remarkable change of the permselectivity of the membrane did not occur; (3) the effectiveness of the cationic polyelectrolyte layer was depressed by the treatment with anionic polyelectrolytes to neutralize the cationic charge on the membrane surface; and (4) the cation with larger hydrated diameter (potassium ions) more easily permeated through the membrane having the polyelectrolyte layer than that with the smaller hydrated diameter (sodium ions). It is concluded that the change of P by the cationic charge layer on the membrane surface is based on the difference in the strength of the electrostatic repulsion between two cations against the cationic charge layer.     

Colossal Stability of Gas‐Phase Trianions: Super‐Pnictogens

Multiply charged negative ions are ubiquitous in nature. They are stable as crystals because of charge compensating cations; while in solutions, solvent molecules protect them. However, they are rarely stable in the gas phase because of strong electrostatic repulsion between the extra electrons. Therefore, understanding their stability without the influence of the environment has been of great interest to scientists for decades. While much of the past work has focused on dianions, work on triply charged negative ions is sparse and the search for the smallest trianion that is stable against spontaneous electron emission or fragmentation continues. Stability of BeB₁₁(X)₁₂³⁻ (X=CN, SCN, BO) trianions is demonstrated in the gas phase, with BeB₁₁(CN)₁₂³⁻ exhibiting colossal stability against electron emission by 2.65 eV and against its neutral adduct by 15.85 eV. The unusual stability of these trianions opens the door to a new class of super‐pnictogens with potential applications in aluminum‐ion batteries.     

Pluronic/Polyethylenimine Shell Crosslinked Nanocapsules with Embedded Magnetite Nanocrystals for Magnetically Triggered Delivery of siRNA

Pluronic/polyethylenimine shell crosslinked nanocapsules with embedded magnetite nanocrystals (PPMCs) were developed for magnetically triggered delivery of siRNA. The positively charged PPMCs formed stable nanosized polyelectrolyte complexes via electrostatic interactions with negatively charged siRNA‐polyethylene glycol conjugate (siRNA‐s‐s‐PEG) that was linked via a cleavable disulfide linkage. PPMC/siRNA‐s‐s‐PEG polyelectrolyte complexes were efficiently taken up by cancer cells upon exposure to a magnet, thereby enhancing intracellular uptake and silencing effect of siRNA. The present study suggests that these novel nanomaterials could be potentially utilized for magnetically triggered delivery of various nucleic acid‐based therapeutic agents.

     

Gas Phase Ion Chemistry of Transition Metal Clusters: Production, Reactivity, and Catalysis

This review focuses on the use of mass spectrometry to examine the gas phase ion chemistry of metal clusters. Ways of forming gas phase clusters are briefly overviewed and then the gas phase chemistry of silver clusters is discussed to illustrate the concepts of magic numbers and how reactivity can be size dependent. The chemistry of other bare and ligated metal clusters is examined, including mixed metal dimer ions as models for microalloys. Metal clusters that catalyze gas phase chemical reactions such as the oxidation of CO and organic substrates are reviewed. Finally the interface between nanotechnology and mass spectrometry is also considered.     

Evaluation of the Donnan model for polyelectrolytes using the composite Poisson-Boltzmann equations

The validity of the macroscopic Donnan model for polyelectrolytes in an electrolyte solution is examined by taking into account the effects of the varying potential distribution across the boundary between a polyelectrolyte and the surrounding solution, using the composite Poisson-Boltzmann equations for the polyelectrolyte interior and the surrounding solution. Calculations are made for a planar polyelectrolyte of thickness 2d and a planar polyelectrolyte layer of thicknessd covering a rigid surface, both showing the identical potential distribution. A simple expression for a correction factor for these effects is derived which enables to evaluate various corrected quantities in the polyelectrolyte interior such as the average potential, the average ionic concentration, the average degree of dissociation and the apparent dissociation constant of ionizable groups in the polyelectrolyte. It is found that when d1 (where indicates the Debye-Hückel parameter) the macroscopic Donnan model can safely be applied, while as d decreases the effects of the varying potential distribution become appreciable.     

Modification of properties of ion exchange membranes. VI. Electrodialytic transport properties of cation exchange membranes with a electrodeposition layer of cationic polyelectrolytes

When a cation exchange membrane is immersed in a cationic polyelectrolyte solution to form a thin layer on the membrane surface, the membrane properties are changed: permselectivity between cations with different electric charges (a relative transport number of the calcium ions to sodium ions, P), current efficiency, and electric resistance of the membrane. Here the more compact the cationic polyelectrolyte layer, the more outstanding the change in permselectivity. To make a more compact layer, an electrodeposition method was adopted and a change in the permselectivity of the resultant cation exchange membrane was investigated. By using the electrodeposition method a strongly basic polyelectrolyte with a larger molecular weight effectively changed the permselectivity of the cation exchange membrane: the P value dropped to about 0.3 from about 2.5 of the P of the untreated membrane during electrodialysis of the sodium chloride—calcium chloride system, and an increase in the electric resistance of the membrane (i.e., organic fouling) due to a cationic surface-active agent could be prevented. It is noteworthy that by using the strongly basic polyelectrolyte with a larger molecular weight the electrodeposition method was effective, whereas the immersion method was ineffective. Furthermore, even with the electrodeposition method the cationic polyelectrolyte which had a relatively smaller molecular weight resulted in a more remarkable change in the P value than did that with a larger molecular weight. In the electrodeposition method the amount of polyelectrolyte cohered onto the membrane surface in creased with an increase in the concentration of the polyelectrolyte, and weakly basic polyelectrolyte, and weakly basic polyelectroyte (polyethyleneimine) was also available independent of its molecular weight.     

Benzylic and pyridinium head groups controlled surfactant-polymer aggregates of mixed cationic micelles and anionic polyelectrolytes

The oppositely charged electrostatic interactions between cationic single and mixed micelles of benzyldimethylhexadecylammonium chloride (BHDACl), hexadecylpyridinium bromide (HPyBr), hexadecylpyridinium chloride (HPyCl), and their mixtures with anionic polyelectrolytes, namely carboxymethylcellulose sodium salt (CMC) and polystyrene sulfonate sodium salt (PSS) were studied with the help of conductivity (), viscosity (), turbidity (), and NMR studies. showed single aggregation process, which was represented by apparent critical micelle concentration, acmc, of each surfactant in aqueous polyelectrolyte solution. Both and demonstrated strong electrostriction effects in the case of BHDACl-polyelectrolyte systems due to weak electrostatic interactions in view of steric hindrances created by benzylic group of BHDACl. ¹H NMR results showed that the head group proton resonances of BHDACl upon incorporation of HPyBr or HPyCl in the presence of CMC or PSS remained identical to that in pure water, which demonstrated very weak interactions between BHDACl and polyelectrolytes. A less shielding of pyridinium head group protons by BHDACl in the presence of polyelectrolytes in comparison to that in pure water indicated favorable electrostatic interactions between pyridinium head groups and anionic polyelectrolytes. HPyBr in comparison to HPyCl showed stronger interactions with polyelectrolytes.     

Cationic Spherical Polyelectrolyte Brushes as Nanoreactors for the Generation of Gold Particles

Summary: If long polyelectrolyte chains are attached densely to colloidal latex particles, a spherical polyelectrolyte brush results. These spherical polyelectrolytes are dispersed in water and carry a high charge. We demonstrate that these systems can be used to immobilize ions of heavy metals, such as gold, as counter‐ions. Reduction of these ions leads to metallic nanoparticles. In this way the brush layer attached to the surface of the particles becomes a “nanoreactor” that may be used for chemical conversions of the metal ions. We show that the reduction of AuClequation/tex2gif-stack-1.gif ions within these nanoreactors leads to well‐defined and rather monodisperse gold nanoparticles that are attached to the surface of the core. A stable dispersion of polymeric core particles with attached nanoparticles results. All results reported here suggest that chemical reactions of ions immobilized in spherical polyelectrolyte brushes provide a new route to composite particles of inorganic and organic materials.

Transmission electron micrograph of gold particles on a core‐shell system.