Non-Arrhenius kinetics and slowed-diffusion mechanism of molecular aggregation of a rhodamine dye on colloidal particles.

The non-covalent association is important for many fields of science, including processes in living systems. This work elucidates the mechanism of rhodamine 123 molecular aggregation in dispersions of a layered silicate and explains the mystery of the slow kinetics of this process. Chemometric analysis of thousands of spectra recorded by stopped-flow visible spectroscopy identified two parallel diffusion processes described by a two-phase exponential function. The slow and fast processes followed the super-Arrhenius kinetics and were assigned to lateral (surface) diffusion and inter-particle diffusion of dye cations, respectively. This work, supported by a large amount of data and their in-depth analysis, provides the first evidence of how these processes coexist together and provides quantitative analysis of their dependence on the reaction conditions. The implications of this work can be crucial for understanding the mechanism of the non-covalent association of adsorbed molecules in nature.

Foliar dust and heavy metal deposit on leaves of urban trees in Budapest (Hungary).

This work considers dust deposition and the heavy metal (HM) content on leaves of urban trees (Acer platanoides L. 'Globosum,' Fraxinus excelsior L. 'Westhof's Glorie' and Tilia tomentosa Moench.) in order to estimate the trees' capacity to remove dust and HM from the air. Leaves were collected from the Buda Arboretum and from different streets of heavy traffic in Budapest, Hungary, during 2015 and 2016. At each site, five trees were sampled by collecting 6 leaves from each tree from the height of 2-3 m. Dust deposits on the leaves were removed by soaking the fresh foliage in distilled water for 20 h and then washed with ultrasound shaking. Afterward, the leaves were dried to constant weight and then they were digested in nitric acid-hydrogen peroxide treatment, and their Pb, Fe, Ni, Zn and Cu contents were measured using an inductively coupled plasma (ICP AS) spectrometer. The removed dust deposit was dried, and after a similar digestion treatment the Pb, Fe, Ni, Zn and Cu contents were measured using an AURORA AI 1200 AAS appliance. The HM deposit was calculated in mg m-2 leaf surface area. In 2015, the amount of foliar dust deposit from spring to autumn increased from 86.3 to 270.2 mg m-2. The most efficient tree species in trapping dust on their leaves was the silver linden (98.5-123.5 mg m-2), followed by the Norway maple (74.2-84.8 mg m-2) and the common ash (62.8-74.6 mg m-2). The deposit of HM elements showed seasonal differences: the quantity of Fe and Pb deposit on autumnal leaves increased five- to tenfold, while other heavy metals did not show accumulation. Silver linden with its pubescent (hairy) leaf surface proved to be most efficient in entrapping and retaining dust and heavy metals. The 60-100% higher Pb and Fe content of autumnal leaves indicate that over the season leaves may absorb Fe and Pb from the foliar dust. Our results confirmed that the foliar dust is a potential indicator for monitoring the HM content in the air. We also show that foliar dust deposits should be considered when estimating the capacity of urban trees to clean the air.

Effect of Added Surfactant on Poly(Ethylenimine)-Assisted Gold Nanoparticle Formation.

In a variety of applications, functionalization of gold nanoparticles is needed to ensure adequate surface charge and hydrophobicity for their biodistribution, interparticle interactions, or self-organization. In the present paper, we provide an economic way for the synthesis of hydrophobized poly(ethylenimine) (PEI) capped gold nanoparticles at room temperature using sodium dodecyl sulfate (SDS). The approach is based on the controlled competition between the nucleation of gold nanophases within the PEI molecules and the SDS binding onto their amine groups. This can be achieved via utilizing the strongly irreversible nature of the association between the oppositely charged polymer and that of the surfactant molecules. Specifically, by varying the order and timing of SDS addition during the process of gold nanoassembly formation, the size distribution, the morphology, and the local hydrophobic environment of the produced Au-PEI/SDS nanohybrids can be tuned even at one composition of the system. The results may be further exploited for the preparation of noble metal nanoassemblies with controlled hydrophobicity and charge.

Effect of Dilution on the Nonequilibrium Polyelectrolyte/Surfactant Association.

Polyelectrolyte (PE)/surfactant (S) mixtures play a distinguished role in the efficacy of shampoos and toiletries primarily due to the deposition of PE/S precipitates on the hair surface upon dilution of the formulations. The classical interpretation of this phenomenon is a simple composition change during which the system enters the two-phase region. Recent studies, however, indicated that the phase properties of PE/S mixtures could be strongly affected by the applied solution preparation protocols. In the present work, we aimed at studying the impact of dilution on the nonequilibrium aggregate formation in the sodium poly(styrenesulfonate) (NaPSS)/dodecyltrimethylammonium bromide (DTAB)/NaCl system. Mixtures prepared with hundredfold dilution of concentrated NaPSS/DTAB/NaCl solutions in water were compared with those ones made by rapid mixing of dilute NaPSS/NaCl and DTAB/NaCl solutions. The study revealed that the phase-separation concentration range as well as the composition, morphology, and visual appearance of the precipitates were remarkably different in the two cases. These observations clearly demonstrate that the dilution/deposition process is also related to the nonequilibrium phase properties of PE/S systems, which can be used to modulate the efficiency of various commercial applications.

Impact of Polyelectrolyte Chemistry on the Thermodynamic Stability of Oppositely Charged Macromolecule/Surfactant Mixtures.

The complexation between hexadecyl- and dodecyltrimethylammonium bromides (CTAB and DTAB) with sodium poly[(vinyl alcohol)-co-(vinyl sulfate)] (PVAS) copolymer of low charge density has been investigated using pyrene fluorescence spectroscopy, electrophoretic mobility, turbidity, and dynamic light scattering measurements. The results indicate that the binding of the cationic surfactant occurs in three steps. At low surfactant concentrations, the cationic amphiphile binds to the vinyl sulfate groups. Above charge neutralization, surfactant binding may occur on the surface of the hydrophobic vinyl sulfate/CnTAB nanoassemblies. At even higher concentrations, the surfactant binds on the nonionic vinyl alcohol units of the polyion which reswells the PVAS/CnTAB complexes and makes them highly soluble in water. In earlier studies on oppositely charged ionic surfactants and homopolyelectrolytes the impact of mixing protocols was found remarkable, especially at surfactant excess, where these systems can be trapped in the charge stabilized colloidal dispersion state. In contrast, in the case of PVAS/CnTAB mixtures the effect of mixing is less pronounced and diminishes with increasing ionic strength or decreasing alkyl chain length of the surfactant. These findings are rationalized by taking into account the different binding mechanism of surfactants on oppositely charged homopolyelectrolytes and double hydrophilic copolymers.

Anisometric Polyelectrolyte/Mixed Surfactant Nanoassemblies Formed by the Association of Poly(diallyldimethylammonium chloride) with Sodium Dodecyl Sulfate and Dodecyl Maltoside.

The soluble complexes of oppositely charged macromolecules and amphiphiles, formed in the one-phase concentration range, are usually described on the basis of the beads on a string model assuming spherelike bound surfactant micelles. However, around and above the charge neutralization ionic surfactant to polyion ratio, a variety of ordered structures of the precipitates and large polyion/surfactant aggregates have been reported for the different systems which are difficult to connect to globular-like surfactant self-assembly units. In this article we have demonstrated through SAXS measurements that the structure of precipitates and those of the soluble polyion/mixed surfactant complexes of poly(diallyldimethylammonium chloride) (PDADMAC), sodium dodecyl sulfate (SDS), and dodecyl-maltoside (DDM) are strongly correlated. Specifically, SDS binds to the PDADMAC molecules in the form of small cylindrical surfactant micelles even at very low SDS-to-PDADMAC ratios. In this way, these anisometric surfactant self-assemblies formed in excess polyelectrolyte mimic the basic building units of the hexagonal structure of the PDADMAC/SDS precipitate and/or suspensions formed at charge equivalence or at higher SDS-to-PDADMAC ratios. The presence of DDM reduces the cmc and cac for the system but does not alter significantly the structure of the complexes in either the one-phase or two-phase region. The only exception is for samples at SDS-to-PDADMAC ratios close to charge neutralization and a high concentration of DDM where the precipitate forms a multiphasic or distorted hexagonal structure.

Fine-tuning the nonequilibrium behavior of oppositely charged macromolecule/surfactant mixtures via the addition of nonionic amphiphiles.

The various commercial applications of oppositely charged polyelectrolytes (P) and ionic surfactants (S) with added nonionic amphiphiles initiated intensive research on the polyion/mixed surfactant interaction. A large group of earlier studies revealed that one of the major effects of the nonionic cosurfactants is the suppression of the associative phase separation of P/S systems. In contrast, recent studies indicated that in the dilute surfactant concentration range the added uncharged amphiphile enhances the precipitation concentration range. In order to rationalize these observations, the mixtures of poly(diallyldimethylammonium chloride) (PDADMAC), sodium dodecyl sulfate (SDS), and dodecyl maltoside (C12G2) are investigated using a variety of experimental methods. It is shown that the nonionic cosurfactant has two distinct and competing impacts on the mixed surfactant binding onto the polyions. The composition dependent variation of the chemical potentials of the amphiphiles determines which of these effects is the dominant one, explaining the seemingly diverse earlier observations and their interpretations. We also demonstrate that the nonionic amphiphile affects considerably the nonequilibrium features of polyion/ionic surfactant complexation. Namely, the presence of the uncharged surfactant can destabilize the colloidal dispersion of P/S nanoparticles formed in the two-phase composition range. However, at the same concentration range highly stable dispersions of polyion/mixed surfactant nanoparticles can be produced through the application of a new two-step solution preparation technique. This method is based on the order of addition effect of the two surfactants which can be utilized in future scientific and industrial applications.

The impact of nonionic surfactant additives on the nonequilibrium association between oppositely charged polyelectrolytes and ionic surfactants.

The effect of uncharged surfactant additives on the oppositely charged polyion/ionic surfactant complexation is usually described as a direct equilibrium association between the polyelectrolyte molecules and free mixed micelles analogous to the polyion/colloidal particle interactions. This approach predicts that the binding of the ionic surfactant to the polyelectrolyte molecules can be completely suppressed by increasing the nonionic-to-ionic surfactant ratio. In the present work, it is shown that the addition of nonionic surfactants to poly(diallyldimethylammonium chloride)/sodium dodecyl sulfate mixtures considerably enhances the binding of the anionic surfactant to the polycation in the dilute surfactant concentration regime. The dynamic light scattering, turbidity, electrophoretic mobility and fluorescence spectroscopic measurements are consistent with the synergic binding of the ionic and nonionic surfactants to the polyelectrolyte molecules. The enhanced surfactant binding could be utilized for the preparation of stable colloidal dispersions of novel polyion/mixed surfactant nanoparticles over a wide composition range provided that adequate mixing protocols are used. These results clearly indicate that the nonionic surfactant additives can be successfully used to tune the nonequilibrium association of oppositely charged macromolecules and amphiphiles.

Effect of linear nonionic polymer additives on the kinetic stability of dispersions of poly(diallyldimethylammonium chloride)/sodium dodecylsulfate nanoparticles.

In this article, the impact of different neutral polymers on the kinetic stability of charge-stabilized poly(diallyldimethylammonium chloride) (PDADMAC)/sodium dodecylsulfate (SDS) colloidal dispersions is analyzed using dynamic light scattering, electrophoretic mobility, turbidity, and coagulation kinetics measurements. Poly(ethyleneoxide) (PEO), poly(vinylpyrrolidone) (PVP), and dextran of comparable molecular masses as well as a higher-molecular-weight dextran sample were tested as nonionic additives. The light scattering and mobility data indicate that the PEO and PVP molecules may adsorb on the surface of the PDADMAC/SDS nanoparticles formed in the presence of excess surfactant. The primary effect of these additives is manifested in enhanced coagulation of the PDADMAC/SDS nanoparticles due to bridging at lower polymer concentrations and depletion flocculation at higher polymer concentrations. These findings are in sharp contrast to the earlier published effect of the same nonionic polymers on the poly(ethyleneimine) (PEI)/SDS colloidal dispersions, which can be sterically stabilized at appropriate PEO or PVP concentrations. However, the adsorption of the investigated dextran samples is negligible on the PDADMAC/SDS nanoparticles. Therefore, dextran molecules may cause only depletion flocculation in the PDADMAC/SDS system in the vicinity of the critical overlap concentration.

Adsorption of Dye Molecules and Its Potential for the Development of Photoactive Hybrid Materials Based on Layered Silicates.

The present paper gives a brief account of the latest advances in understanding of the mechanism and implications of dye adsorption with a special focus on layered silicate surfaces. It has been clearly demonstrated that the controlled adsorption of novel or already well-known dyes has equally great yet unexplored potential. In principle, the well-engineered surface confinement of the molecules may lead to their aggregation, adsorption, or intercalation-induced fluorescence emission even with conventional dyes, which are not considered as luminophores in solutions or in the solid state. We envision the utilization of silicate-based heterogeneous systems to produce novel polymer blended films or structured liquids, as well as to develop a plethora of other photophysical and biomedical applications.

Structuring liquids through solvent-assisted interfacial association of oppositely charged polyelectrolytes and amphiphiles.

HYPOTHESIS: Sculpting liquids into different shapes is usually based on the interfacial interactions of functionalized nanoparticles or polymers with specific ligands, leading to exciting material properties due to the combination of the mobility of liquid components with the solid-like characteristic of the arrested liquid/liquid interface. There is an intense interest in novel structured liquids produced from simple compounds with versatile application potentials. Complexes of oppositely charged commercial polyelectrolytes and traditional aliphatic surfactants are good candidates for this goal since they reveal rich structural features and could adsorb at various interfaces. However, they have not been applied yet for structuring liquids. EXPERIMENTS: The interfacial interactions and film formation between aqueous sodium poly(styrene) sulfonate solutions (NaPSS) and hexadecylamine (HDA) solutions in various alkanols were investigated by surface tension measurements and ATR-IR spectroscopy. 3D printing experiments also assessed the robustness of the formed films. FINDINGS: Arrested fatty alcohol/water interfaces were formed due to the interfacial association of NaPSS, HDA, and alkanol molecules, which also act as cosurfactants in the surface region. These solid films enable the synthesis of temperature-sensitive all-in-liquid constructs and offer alternatives to bulk polyion/mixed surfactant assemblies prepared earlier through numerous synthesis steps.

Broadband UV-to-green photoconversion in V-doped lithium zinc silicate glasses and glass ceramics.

We report on photoluminescence of vanadium-doped lithium zinc silicate glasses and corresponding nanocrystalline Li2ZnSiO4 glass ceramics as broadband UV-to-VIS photoconverters. Depending on dopant concentration and synthesis conditions, VIS photoemission from [VO4]3 is centered at 550-590 nm and occurs over a bandwidth (FWHM) of ~250 nm. The corresponding excitation band covers the complete UV-B to UV-A spectral region. In as-melted glasses, the emission lifetime is about 34 µs up to a nominal dopant concentration of 0.5 mol%. In the glass ceramic, it increases to about 45 µs. For higher dopant concentration, a sharp drop in emission lifetime was observed, what is interpreted as a result of concentration quenching. Self-quenching is further promoted by energy transfer to V4+ centers (2<Гt4→2Гt3). Partitioning of vanadium into V5+ and V4+ was examined by electron paramagnetic resonance and X-ray photoelectron spectroscopy. Suppression of V5+-reduction requires careful adjustment of the optical basicity of the host glass and/or synthesis conditions.

Preparation of stable electroneutral nanoparticles of sodium dodecyl sulfate and branched poly(ethylenimine) in the presence of pluronic F108 copolymer.

Mixing of polyelectrolyte solutions with solutions of oppositely charged surfactants usually leads to phase separation in a certain concentration range. However, since the charge-neutralized polyelectrolyte/surfactant nanoparticles might be utilized as versatile nanocarriers of different substances, it would be desirable to prevent their aggregation for some applications. As it was revealed in earlier investigations, the complete suppression of precipitation may be achieved only in mixtures of ionic surfactants and appropriate copolymer polyelectrolytes with nonionic and ionic blocks. In this work, we present a method that could prevent phase separation in mixtures of homopolyelectrolytes and oppositely charged surfactants. Specifically, it is shown that nonaggregating electroneutral nanocomplexes of branched poly(ethylenimine) (PEI) and sodium dodecyl sulfate (SDS) can be prepared in the presence of the amphiphilic triblock copolymer Pluronic F108, provided that an adequate mixing protocol is used for preparation of the PEI/SDS/F108 mixtures.

Effect of salt on the equilibrium and nonequilibrium features of polyelectrolyte/surfactant association.

The impact of an electrolyte on aqueous mixtures of oppositely charged macromolecules and surfactants is usually explained by assuming an equilibrium association between the components. In this work, it is shown that the nonequilibrium character of polyelectrolyte/surfactant systems plays a crucial role in the interpretation of the effect of salt. Experimental investigations of mixtures of sodium poly(styrenesulfonate) (PSS) and hexadecyltrimethylammonium bromide (CTAB) reveal two distinct effects of added sodium chloride (NaCl). At small and moderate NaCl concentrations, the major impact of the electrolyte is manifested in the reduction of the kinetically stable composition range in which the PSS/CTAB mixtures are trapped in the nonequilibrium colloidal dispersion state. The application of high salt concentrations, however, primarily affects the equilibrium phase properties through considerably decreasing the amount of surfactant bound to the polyelectrolyte.

Novel self-assemblies of oppositely charged polyelectrolytes and surfactants in the presence of neutral polymer.

In this Letter, the effect of addition of poly(ethylene oxide) (PEO) on the nature of the self-assemblies of sodium dodecyl sulfate (SDS) and branched poly(ethyleneimine) (PEI) is investigated. We demonstrate that the neutral polymer adsorbs onto the surface of the polyelectrolyte/surfactant nanoparticles, which may result in sterically stabilized colloidal dispersions of the nanoparticles with hydrophobic core and hydrophilic corona. The kinetic stability is maintained even at high ionic strengths, where the charge stabilization of the PEI/SDS dispersions is inefficient. These results might be exploited to improve the efficiency of those formulations, which contain oppositely charged macromolecules and amphiphiles.

Nonequilibrium features of the association between poly(vinylamine) and sodium dodecyl sulfate: the validity of the colloid dispersion concept.

The effect of different mixing protocols on the bulk and surface properties of the aqueous mixtures of linear poly(vinylamine) (PVAm) and sodium dodecyl sulfate (SDS) has been investigated using pH, electrophoretic mobility, dynamic light scattering, coagulation kinetics, and surface tension measurements. For the preparation of the solutions, two kinds of mixing protocols were applied. The so-called "stop flow mixing" enables a very rapid mixing whereas in the case of "gentle mixing" the mixing of the components is less efficient. At high surfactant concentrations a kinetically stable colloid dispersion of the PVAm/SDS particles is formed via the application of the stop flow mixing method. The mixing protocols have a significant effect on the bulk properties of the PVAm/SDS system, in particular, at the low pH range and at large PVAm concentrations. The effect of mixing can be qualitatively understood in terms of the enhanced local rate of coagulation of the PVAm/SDS complexes as well as of the appearance of polyelectrolyte/surfactant aggregates via the application of a less efficient mixing. The study also reveals that the applied methods of solution preparation do not have a major impact on the bound amount of the surfactant as well as on the surface tension isotherms of the system. This latter finding is attributed to the hindered adsorption of the large polyelectrolyte/surfactant aggregates at the air/water interface.

Competitive adsorption of neutral comb polymers and sodium dodecyl sulfate at the air/water interface.

The interfacial behavior of aqueous solutions of four different neutral polymers in the presence of sodium dodecyl sulfate (SDS) has been investigated by surface tension measurements and ellipsometry. The polymers comprised linear poly(ethylene oxide) with low and high molecular masses (10(3) and 10(6) Dalton (Da), respectively), and two high molecular mass methacrylate-based comb polymers containing poly(ethylene oxide) side chains. The adsorption isotherms of SDS, determined by Gibbs analysis of surface tension data, are nearly the same in the presence of the high molecular mass linear polymer and the comb polymers. Analysis of the ellipsometric data reveals that while a single surface layer model is appropriate for films of polymer alone, a more sophisticated interfacial layer model is necessary for films of SDS alone. For the polymer/surfactant mixtures, a novel semiempirical approach is proposed to determine the surface excess of polymer, and hence quantify the interfacial composition, through analysis of data from the two techniques. The replacement of the polymer due to surfactant adsorption is much less pronounced for the high molecular mass linear polymer and for the comb polymers than for the low molecular mass linear polymer. This finding is rationalized by the significantly higher adsorption driving force of the larger polymer molecules as well as by their more amphiphilic structure in the case of the comb polymers.

Novel nanocomplexes of hyperbranched poly(ethyleneimine), and dodecyl maltoside.

The aqueous complexes of poly(ethyleneimine) (PEI), sodium dodecyl sulfate (SDS) and dodecyl maltoside (C12G2) have been studied under dilute conditions using dynamic light scattering, electrophoretic mobility, surface tension and pH measurements. According to the surface tension data the complexation between PEI and C12G2 can be neglected while a strong interaction was detected between PEI and SDS. The charged nature and size of the PEI-SDS-C12G2 complexes vary in a similar manner with SDS concentration as for the PEI-SDS systems. At large excess of SDS a kinetically stable colloid dispersion of the compact PEI-SDS-C12G2 particles forms. The electrophoretic mobility measurements indicate that the charge reversal of the PEI molecules occurs at lower SDS concentrations in the presence than in the absence of dodecyl maltoside. The enhanced charge inversion of PEI affords a significant extension of the concentration range with kinetically stable dispersion of the polyelectrolyte-surfactant nanoparticles compared with the PEI-SDS system. The pH of the PEI-SDS-C12G2 mixtures also reveals a peculiar dependence on the surfactant concentration. These latter findings are explained by the synergistic binding of the ionic and non-ionic surfactants to both the uncharged and charged amine groups of the PEI. It can be concluded that the addition of sugar surfactants is an efficient way to increase the kinetic stability and manipulate the pH of the mixtures of oppositely charged weak polyelectrolytes and surfactants.

Adsorption of alkyl trimethylammonium bromides at the air/water interface.

A number of features of the adsorption of alkyl trimethylammonium bromides with nc=10,12,14, and 16 at the air/water interface were studied. First, the adsorption isotherms were calculated from experimental surface tension vs concentration curves by means of the Gibbs equation. Second, a novel method was used to estimate the adsorption free energy change. From the analysis of these data it was concluded that the hydrophobic driving force for the adsorption first increases with increasing adsorbed amount and then levels off in a plateau, which holds true for all four homologues. This peculiar behavior was interpreted by the formation of a thin liquid-like alkane film at the air/water interface once a certain adsorbed amount is exceeded. The hydrophobic contribution to the standard free energy change of adsorption was compared with those values previously determined for alkyl sulfate homologues. This comparison suggests that the alkyl trimethylammonium type surfactants behave as if their alkyl chain was approximately one methylene group shorter than those of the corresponding alkyl sulfates.

A review of numerical models to predict the atmospheric dispersion of radionuclides.

The field of atmospheric dispersion modeling has evolved together with nuclear risk assessment and emergency response systems. Atmospheric concentration and deposition of radionuclides originating from an unintended release provide the basis of dose estimations and countermeasure strategies. To predict the atmospheric dispersion and deposition of radionuclides several numerical models are available coupled with numerical weather prediction (NWP) systems. This work provides a review of the main concepts and different approaches of atmospheric dispersion modeling. Key processes of the atmospheric transport of radionuclides are emission, advection, turbulent diffusion, dry and wet deposition, radioactive decay and other physical and chemical transformations. A wide range of modeling software are available to simulate these processes with different physical assumptions, numerical approaches and implementation. The most appropriate modeling tool for a specific purpose can be selected based on the spatial scale, the complexity of meteorology, land surface and physical and chemical transformations, also considering the available data and computational resource. For most regulatory and operational applications, offline coupled NWP-dispersion systems are used, either with a local scale Gaussian, or a regional to global scale Eulerian or Lagrangian approach. The dispersion model results show large sensitivity on the accuracy of the coupled NWP model, especially through the description of planetary boundary layer turbulence, deep convection and wet deposition. Improvement of dispersion predictions can be achieved by online coupling of mesoscale meteorology and atmospheric transport models. The 2011 Fukushima event was the first large-scale nuclear accident where real-time prognostic dispersion modeling provided decision support. Dozens of dispersion models with different approaches were used for prognostic and retrospective simulations of the Fukushima release. An unknown release rate proved to be the largest factor of uncertainty, underlining the importance of inverse modeling and data assimilation in future developments.