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PubMed2000

Organo-clay formulations of the hydrophobic herbicide norflurazon yield reduced leaching.

The study aimed to reduce leaching of the hydrophobic herbicide norflurazon (4-chloro-5-methylamino-2-(alpha,alpha, alpha)-trifluoro-m-tolylpyridazin-3-(2H)-one) by adsorbing it on clays or organo-clays. The surface of the clay mineral montmorillonite was modified from hydrophilic to hydrophobic by preadsorbing it with organic cations, of which thioflavin-T (TFT) at a loading corresponding to (5)/(8) of the cation-exchange capacity of the clay mineral yielded the highest affinity of adsorption of norflurazon. Pillared clay (PC) used without organic cations exhibited enhanced affinity for norflurazon adsorption, much higher than that of montmorillonite or sepiolite. Fourier transform infrared (FTIR) results showed interactions between aromatic moieties of preadsorbed TFT and the herbicide. Stronger interaction of the herbicide with a clay mineral or organo-clay corresponded to its slower release. Formulations prepared on the basis of montmorillonite-TFT and PC were more effective in reducing herbicide leaching in soil columns in comparison to the commercial formulation, whereas the herbicidal efficiencies were comparable.

Aluminum Silicates↗
PubMed2006

Effect of surfactant and solvent properties on the stacking behavior of non-aqueous suspensions of organically modified clays.

Montmorillonite clay was treated with quaternary ammonium surfactants with 1-3 long chains of 10-18 carbons to form organoclays which can be suspended in non-aqueous solvents. The effects of surfactant chain length, number of long chains, and the properties of the solvent on the colloidal behavior of the surfactant coated clay plates were studied using small-angle X-ray scattering. The scattering data were modeled using a one-dimensional aggregation theory to describe the stacking of the clay plates. The plates self-organize into stacks with a reproducible basal spacing in the range of 30-50 A, and for each surfactant, the basal spacing falls into one of two preferred distances. We interpret this by considering that the surfactant layer on the clay has two strata, one being the polar near-clay headgroup region and the other the nonpolar alkane chain region. Polar solvents will swell the polar stratum preferentially while nonpolar solvents will swell the nonpolar stratum of the surfactant. As the nonpolar stratum is larger than the polar one, the nonpolar solvents increase the basal spacing between the clay plates more than the polar solvents. The number of long chains on the surfactant does not have an effect on the basal spacing, as the density of surfactant molecules on the surface is low enough to allow the unimpeded swelling of the chains. The one-dimensional aggregation theory can be used to determine the number of plates in a stack, but the effect of changing clay particle size or concentration is not as great as would be expected from this theory. This may be due to the formation of large-scale structures in the suspensions which prevent a true equilibrium stack size being attained.

Aluminum Silicates↗
PubMed1999

Clay catalysis of oligonucleotide formation: kinetics of the reaction of the 5'-phosphorimidazolides of nucleotides with the non-basic heterocycles uracil and hypoxanthine.

The montmorillonite clay catalyzed condensation of activated monocleotides to oligomers of RNA is a possible first step in the formation of the proposed RNA world. The rate constants for the condensation of the phosphorimidazolide of adenosine were measured previously and these studies have been extended to the phosphorimidazolides of inosine and uridine in the present work to determine of substitution of neutral heterocycles for the basic adenine ring changes the reaction rate or regioselectivity. The oligomerization reactions of the 5'-phosphoromidazolides of uridine (ImpU) and inosine (ImpI) on montmorillonite yield oligo(U)s and oligo(I)s as long as heptamers. The rate constants for oligonucleotide formation were determined by measuring the rates of formation of the oligomers by HPLC. Both the apparent rate constants in the reaction mixture and the rate constants on the clay surface were calculated using the partition coefficients of the oligomers between the aqueous and clay phases. The rate constants for trimer formation are much greater than those dimer synthesis but there was little difference in the rate constants for the formation of trimers and higher oligomers. The overall rates of oligomerization of the phosphorimidazolides of purine and pyrimidine nucleosides in the presence of montmorillonite clay are the same suggesting that RNA formed on the primitive Earth could have contained a variety of heterocyclic bases. The rate constants for oligomerization of pyrimidine nucleotides on the clay surface are significantly higher than those of purine nucleotides since the pyrimidine nucleotides bind less strongly to the clay than do the purine nucleotides. The differences in the binding is probably due to Van der Waals interactions between the purine bases and the clay surface. Differences in the basicity of the heterocyclic ring in the nucleotide have little effect on the oligomerization process.

Aluminum Silicates↗
PubMed1989

Effects of vegetation, a clay cap and environmental variables on 222Rn fluence rate from reclaimed U mill tailings.

We measured 222Rn fluence rate and several environmental variables on two plots with U mill tailings buried beneath 30 cm of overburden and 20 cm of topsoil. An additional 30 cm of clay covered the tailings on one plot and each plot was subdivided into bare soil and vegetated subplots. We used linear correlation, two-way ANOVA and stepwise multiple regression to analyze the effects of the plot characteristics and the environmental variables on 222Rn fluence rate. The most important effect on 222Rn fluence rates from these plots was the combination of a clay cap and a vegetated surface. The mean annual fluence rate from the plot having both of these characteristics (520 +/- 370 mBq m-2 s-1) was over three times that of the vegetated plot without a clay cap (170 +/- 130 mBq m-2 s-1) and 18 times that of the bare plot with a clay cap (29 +/- 13 mBq m-2 s-1). The interaction effect may have been due to the growth of roots in the moist clay and active transport of dissolved 222Rn to the surface in water. This speculation is supported by the observation that on vegetated plots with a clay cap, moisture in the clay enhanced the fluence rate.

Air Pollutants↗
PubMed2005

Effect of titanate-based surface on hydrophilicity and interlayer spacing of montmorillonite clay for polymer nanocomposites.

The fundamental scientific investigations on structure-property correlation of organo-clay are quite valuable in understanding the interface chemistry thus to design and engineer the most effective polymer-clay nanocomposites systems. Organo alkyl-titanate derivatives have been used as reagents for the surface modification of pristine montmorillonite clay platelets. Such surface modification is validated through coordinated characterization techniques that include X-ray photoelectron spectroscopy (XPS), contact angle measurements, X-ray diffraction (XRD) and thermo gravimetric analysis (TGA). By fine-tuning the surface characteristics (controlling the hydrophilicity); effective nanodispersion in polymers by intercalation or delamination can be accomplished. The titanate-coupling agent increased the water contact angle of the clay from 6 to 44 degrees denoting significant decrease in hydrophilicity. Similarly, XRD studies revealed the increased inter-gallery spacing from 9.8 to 12.7 A. The grafting of titanate modifier on to clay surface is quantified through XPS elemental analysis and co-related with TGA. This new surface-modification method provides an effective technique to convert the hydrophilic surface of the montmorillonite clay into organophillic for polymer-clay nanocomposites.

Aluminum Silicates↗
PubMedDate not supplied

Heavy metal interactions with phosphatic clay: sorption and desorption behavior.

Heavy metals produced and released during agricultural and industrial activities may pose a serious threat to the environment. This study investigated the effectiveness of phosphatic clay, a by-product of the phosphate mining industry, for immobilizing heavy metals (Pb(+2), Cd(+2), and Zn(+2)) from aqueous solutions. A batch equilibrium technique was adopted to evaluate metal sorption in the presence of 0.05 M KNO3 background electrolyte solution. The amounts of metals sorbed onto phosphatic clay decreased in the order Pb(+2) > Cd(+2) > Zn(+2). Desorption data suggest that a large fraction of metals sorbed onto phosphatic clay stayed intact under a wide variation in extracting solution pH (ranging from 3 to 10). Desorption rates were slowest for Pb followed by Cd and Zn. Only 8.1 to 23.1% of Pb, 8.4 to 45% of Cd, and 21.9 to 73.9% of Zn sorbed on phosphatic clay was mobilized by USEPA toxicity characteristic leaching procedure (TCLP) solutions at pH 2.93+/-0.05 and 4.93+/-0.05, respectively. Formation of fluoropyromorphite [Pb10(PO4)6(F2)], confirmed by scanning electron microscopy (SEM) and X-ray diffraction (XRD), after reaction of aqueous Pb with phosphatic clay suggested that precipitation remained the dominant mechanism for Pb removal from aqueous solution. In the case of aqueous Cd and Zn interaction with phosphatic clay, we are not able to confirm the formation of a new amorphous and/or crystalline phase on the basis of available information. Other possible sorption mechanisms for Cd and Zn may include sorption and coprecipitation. Thus, phosphatic clay may be an effective amendment for in situ immobilization of heavy metals in contaminated soils and sediments.

Absorption↗
PubMed2003

[Removal of different species of red tide organisms with an effective clay-complex system].

An effective clay-complex system was composed on the base of clay by added other two components A and B. Different red tide species, such as Scrippsiella trochoidea, Amphidinium carterae and Heterosigma akashiwo, were coagulated by this clay-complex system, and the optimum conditions for removal red tide organisms were obtained by means of orthogonal test. The results showed that clay was the most important factors in this complex system to coagulate these three organisms. The removal efficiency on three species was in order of Scrippsiella trochoidea > Amphidinium carterae > Heterosigma akashiwo. At the same time, a preliminary study of mortality rate on Penaeus japonicus (length between 1.0 to 1.5 cm) was conducted with this system, and the result of toxic test revealed that the mortality of aquaculture shrimp in control group (nothing added) reached to 80% after 96 h, however, while that of other three groups which added clay and other two components A and B, was below 40%. Thus, it implied that the addition of clay would be harmless to Penaeus japonicas. Furthermore, suitable concentration of components A and B was not harmful for the aquaculture shrimp, but increased the removal efficiency of red tide organisms. The preliminary results showed that this clay-complex system would be available in the removal of red tide organisms in filed.

Aluminum Silicates↗
PubMed2002

Surface modification of montmorillonite on surface Acid-base characteristics of clay and thermal stability of epoxy/clay nanocomposites.

In this work, the effect of surface treatments on smectitic clay was investigated in surface energetics and thermal behaviors of epoxy/clay nanocomposites. The pH values, X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FT-IR) were used to analyze the effect of cation exchange on clay surface and the exfoliation phenomenon of clay interlayer. The surface energetics of clay and thermal properties of epoxy/clay nanocomposites were investigated in contact angles and thermogravimetric analysis (TGA), respectively. From the experimental results, the surface modification of clay by dodecylammonium chloride led to the increases in both distance between silicate layers of about 8 A and surface acid values, as well as in the electron acceptor component (gamma(+)(s)) of surface free energy, resulting in improved interfacial adhesion between basic (or electron donor) epoxy resins and acidic (electron acceptor) clay interlayers. Also, the thermal stability of nanocomposites was highly superior to pure epoxy resin due to the presence of the well-dispersed clay nanolayer, which has a barrier property in a composite system.

Journal Article↗
PubMed1979

Smectite clays in Mars soil: evidence for their presence and role in Viking biology experimental results.

Various chemical, physical and geological observations indicate that smectite clays are probably the major components of the Martian soil. Satisfactory ground-based chemical simulation of the Viking biology experimental results was obtained with the smectite clays nontronite and montmorillonite when they contained iron and hydrogen as adsorbed ions. Radioactive gas was released from the medium solution used in the Viking Labeled Release (LR) experiment when interacted with the clays, at rates and quantities similar to those measured by Viking on Mars. Heating of the active clay (mixed with soluble salts) to 160 degrees C in CO2 atmosphere reduced the decomposition activity considerably, again, as was observed on Mars. The decomposition reaction in LR experiment is postulated to be iron-catalyzed formate decomposition on the clay surface. The main features of the Viking Pyrolytic Release (PR) experiment were also simulated recently (Hubbard, 1979) which the iron clays, including a relatively low '1st peak' and significant '2nd peak'. The accumulated observations on various Martian soil properties and the results of simulation experiments, thus indicate that smectite clays are major and active components of the Martian soil. It now appears that many of the results of the Viking biology experiments can be explained on the basis of their surface activity in catalysis and adsorption.

Chemical Phenomena↗
PubMed2005

Monte Carlo and molecular dynamics simulations of methane in potassium montmorillonite clay hydrates at elevated pressures and temperatures.

The structure and dynamics of methane in hydrated potassium montmorillonite clay have been studied under conditions encountered in sedimentary basin and compared to those of hydrated sodium montmorillonite clay using computer simulation techniques. The simulated systems contain two molecular layers of water and followed gradients of 150 bar km(-1) and 30 K km(-1) up to a maximum burial depth of 6 km. Methane particle is coordinated to about 19 oxygen atoms, with 6 of these coming from the clay surface oxygen. Potassium ions tend to move away from the center towards the clay surface, in contrast to the behavior observed with the hydrated sodium form. The clay surface affinity for methane was found to be higher in the hydrated K-form. Methane diffusion in the two-layer hydrated K-montmorillonite increases from 0.39 x 10(-9) m2 s(-1) at 280 K to 3.27 x 10(-9) m2 s(-1) at 460 K compared to 0.36 x 10(-9) m2 s(-1) at 280 K to 4.26 x 10(-9) m2 s(-1) at 460 K in Na-montmorillonite hydrate. The distributions of the potassium ions were found to vary in the hydrates when compared to those of sodium form. Water molecules were also found to be very mobile in the potassium clay hydrates compared to sodium clay hydrates.

Journal Article↗
PubMed2005

Modeling of copper(II) and lead(II) adsorption on kaolinite-based clay minerals individually and in the presence of humic acid.

The aim of this study is to explain how clay minerals adsorb heavy metals individually and in the presence of humic acid, and to model heavy metal adsorption specifically based on surface-metal binary and surface-metal-ligand ternary complexation. The adsorption of Cu(II) and Pb(II) on kaolinite-based clay minerals has been modeled by the aid of the FITEQL3.2 computer program using single- and double-site binding models of the Langmuir approach. Potentiometric titrations and adsorption capacity experiments were carried out in solutions containing different concentrations of the inert electrolyte NaClO4; however, the modeling of binary and ternary surface complexation was deliberately done at high ionic strength (0.1 M electrolyte) for eliminating adsorption onto the permanent negatively charged sites of kaolinite. A "two-site, two pKa" model was adapted, and as for the two surface sites responsible for adsorption, it may be arbitrarily assigned that [triple bond]S1OH sites represent silanol and organic functional groups such as carboxyl having pKa values close to that of silanol, and [triple bond]S2OH sites represent aluminol and organic functional groups such as phenolics whose pKa values are close to that of aluminol, as all the studied clays contained organic carbon. Copper(II) showed a higher adsorption capacity and higher binding constants, while lead(II), being a softer cation (in respect to HSAB theory) preferred the softer basic sites with aluminol-phenol functional groups. Heavy metal cations are assumed to bind to the clay surface as the sole (unhydrolyzed) M(II) ion and form monodentate surface complexes. Cu(II) and Pb(II) adsorption in the presence of humic acid was modeled using a double-site binding model by the aid of FITEQL3.2, and then the whole system including binary surface-metal and surface-ligand and ternary surface-metal-ligand complexes was resolved with respect to species distributions and relevant stability constants. Electrostatic effects were accounted for using a diffuse layer model (DLM) requiring minimum number of adjustable parameters. Metal adsorption onto clay at low pH increased in the presence of humic acid, and the metal adsorption vs pH curves of metal-kaolinite-humic acid suspensions were much steeper (and distinctly S shaped) compared to the wider pH-gradient curves observed in binary clay-metal systems. The clay mineral in the presence of humic acid probably behaved more like a chelating ion-exchanger sorbent for heavy metals rather than being a simple inorganic ion exchanger.

Journal Article↗
PubMed2006

Adsorption of hydrocarbons on organo-clays--implications for oil spill remediation.

Organo-clays synthesised by the ion exchange of sodium in Wyoming Na-montmorillonite (SWy-2-MMT) with three surfactants: (a) octadecyltrimethylammonium bromide (ODTMA), formula C(21)H(46)NBr; (b) dodecyldimethylammonium bromide (DDDMA), formula C(22)H(48)BrN; and (c) di(hydrogenated tallow)dimethylammonium chloride were tested for hydrocarbon adsorption. Using diesel, hydraulic oil, and engine oil an evaluation was made of the effectiveness of the sorbent materials for a range of hydrocarbon products that are likely to be involved in land-based oil spills. It was found that the hydrocarbon sorption capacity of the organo-clays depended upon the materials and surfactants used in the organo-clay synthesis. Greater adsorption was obtained if the surfactant contained two or more hydrocarbon long chains. Extensive utilisation of chemometrics principally with the aid of MCDM methods, produced models which consistently ranked the organo-clays well above any of the competitors including commercial benchmark materials. Thus, the use of organo-clays for cleaning up oil spills is feasible due to its many desirable properties such as high hydrocarbon sorption and retention capacities, hydrophobicity. The negative effects of the use of organo-clays for oil-spill cleanup are the cost, the biodegradability, and recyclability of the organo-clays.

Journal Article↗
PubMed2004

Characterization of interlayer Cs+ in clay samples using secondary ion mass spectrometry with laser sample modification.

Ultraviolet laser irradiation was used to greatly enhance the secondary ion mass spectrometry (SIMS) detection of Cs(+) adsorbed to soil consisting of clay and quartz. Imaging SIMS showed that the enhancement of the Cs(+) signal was spatially heterogeneous: the intensity of the Cs(+) peak was increased by factors up to 100 for some particles but not at all for others. Analysis of standard clay samples exposed to Cs(+) showed a variable response to laser irradiation depending on the type of clay analyzed. The Cs(+) abundance was significantly enhanced when Cs(+)-exposed montmorillonite was irradiated and then analyzed using SIMS, which contrasted with the behavior of Cs(+)-exposed kaolinite, which displayed no Cs(+) enhancement. Exposed illitic clays displayed modest enhancement of Cs(+) upon laser irradiation, intermediate between that of kaolinite and montmorillonite. The results for Cs(+) were rationalized in terms of adsorption to interlayer sites within the montmorillonite, which is an expandable phyllosilicate. In these locations, Cs(+) was not initially detectable using SIMS. Upon irradiation, Cs(+) was thermally redistributed, which enabled detection using SIMS. Since neither the illite nor the kaolinite is an expandable clay, adsorption to inner-layer sites does not occur, and either modest or no laser enhancement of the Cs(+) signal is observed. Laser irradiation also produced unexpected enhancement of Ti(+) from illite and kaolinite clays that contained small quantities of Ti, which indicates the presence of microscopic titanium oxide phases in the clay materials.

Journal Article↗
PubMed2001

Potential contributions of smectite clays and organic matter to pesticide retention in soils.

Soil organic matter (SOM) is often considered the dominant sorptive phase for organic contaminants and pesticides in soil-water systems. This is evidenced by the widespread use of organic-matter-normalized sorption coefficients (K(OM)) to predict soil-water distribution of pesticides, an approach that ignores the potential contribution of soil minerals to sorption. To gain additional perspective on the potential contributions of clays and SOM to pesticide retention in soils, we measured sorption of seven pesticides by a K-saturated reference smectite clay (SWy-2) and SOM (represented by a muck soil). In addition, we measured the adsorption of atrazine by five different K-saturated smectites and Ca-saturated SWy-2. On a unit mass basis, the K-SWy-2 clay was a more effective sorbent than SOM for 4,6-dinitro-o-cresol (DNOC), dichlobenil, and carbaryl of the seven pesticides evaluated, of which, DNOC was sorbed to the greatest extent. Atrazine was sorbed to a similar extent by K-SWy-2 and SOM. Parathion, diuron, and biphenyl were sorbed to a greater extent by SOM than by K-SWy-2. Atrazine was adsorbed by Ca-SWy-2 to a much lesser extent than by K-SWy-2. This appears to be related to the larger hydration sphere of Ca(2+) (compared to that of K(+)) which shrinks the effective size of the adsorption domains between exchangeable cations, and which expands the clay layers beyond the apparently optimal spacing of approximately 12.2 A for sorption of aromatic pesticide structures. Although a simple relation between atrazine adsorption by different K-smectites and charge properties of clay was not observed, the highest charge clay was the least effective sorbent; a higher charge density would result in a loss of adsorption domains. These results indicate that for certain pesticides, expandable soil clays have the potential to be an equal or dominant sorptive phase when compared to SOM for pesticide retention in soil.

Absorption↗
PubMed2005

Modulation of the genotoxicity of pesticides reacted with redox-modified smectite clay.

Pesticides are toxic agents intentionally released into the environment; their use raises public health and environmental concerns. In recent years there has been much attention to the biotic degradation of pesticides. Abiotic mechanisms in the soil can contribute to pesticide degradation yet the toxicological impact of such degradation is unclear. This study combines for the first time an investigation into abiotic mechanisms of degradation coupled with toxicological endpoints in mammalian cells. The genotoxicity of three commonly used agricultural pesticides was assessed before and after exposure to redox-modified clay minerals. The objectives of the study were to determine the genotoxicity of 2,4-dichlorophenoxy acetic acid (2,4-D), dicamba, and oxamyl, using single cell gel electrophoresis with Chinese hamster ovary (CHO) cells, and to determine the effect of the iron oxidation state in clay minerals (ferruginous smectite SWa-1) on the genotoxic potency of the pesticides. 2,4-D alone or following reaction with redox-modified clays did not induce DNA damage in CHO cells. Oxamyl alone induced a concentration-dependent increase in genomic DNA damage; however, its genotoxicity declined after reaction with reduced clay minerals. Dicamba was not genotoxic when directly analyzed. When dicamba was reacted with reduced clay, a concentration-dependent increase in genomic DNA damage was observed. This is the first reported case of a pesticide being converted into a genotoxin after exposure to redox-modified smectites. These data introduce a new paradigm on the interaction between redox-modified clays and pesticide-related environmental genotoxicity.

2,4-Dichlorophenoxyacetic Acid↗
PubMed2005

Sorption of Cesium on smectite-rich clays from the Bohemian Massif (Czech Republic) and their mixtures with sand.

Sorption is an important process for the transport of radionuclides through backfill materials in a radioactive waste underground repository. Within this study, sorption of Cs on selected Czech clay materials and their mixtures with sand was investigated by batch tests. The experiments were performed under oxic conditions at 25 degrees C. Synthetic groundwater as a liquid phase and unconditioned clays (as they were provided by their producer) were used to reach the natural conditions as close as possible. Distribution ratios (Rds) of Cs for all selected clays rise with increase of the clay fraction in clay/sand mixtures in agreement with previous works studying sorption behaviour of such mixtures. The rise of Rds is from 10(2) cm3 g(-1) for mixtures with 80% of sand to 10(3) cm3 g(-1) for pure clays. There are significant differences between natural and technologically modified clays.

Adsorption↗
PubMed2006

Catalytic activity of hammerhead ribozymes in a clay mineral environment: implications for the RNA world.

The hypothesized RNA-based world would have required the presence of a protected environment in which RNA, or an RNA-like molecule, could originate and express its biological activity. Recent studies have indicated that RNA molecules adsorbed/bound on clay minerals are able to persist in the presence of degrading agents, to interact with surrounding molecules, and to transmit the information contained in their nucleotide sequences. In this study, we assessed the ability of RNA molecules with catalytic activity to perform a specific reaction in a mineral environment. For this purpose, we investigated the self-cleavage reaction of the hammerhead ribozyme of the Avocado Sun Blotch Viroid (ASBVd), both in the monomeric and in dimeric forms. The monomeric transcript was tightly bound on the clay mineral montmorillonite to form a stable complex, while the behaviour of the dimeric transcript was studied in the presence of the clay particles in the reaction mixture. The results indicated that the hammerhead ribozyme was still active when the monomeric transcript was adsorbed on the clay surface, even though its efficiency was reduced to about 20% of that in solution. Moreover, the self-cleavage of clay-adsorbed molecule was significantly enhanced ( approximately four times) by the presence of the 5' reaction product. The self-cleavage reaction of the dimeric transcript in the presence of montmorillonite indicated that the mineral particles protected the RNA molecules against aspecific degradation and increased the rate of cleavage kinetics by about one order of magnitude. These findings corroborate the hypothesis that clay-rich environments would have been a good habitat in which RNA or RNA-like molecules could originate, accumulate and undergo Darwinian evolutionary processes, leading to the first living cells on Earth.

Adsorption↗
PubMed2005

Preparation of a novel PEG-clay hybrid as a DDS material: dispersion stability and sustained release profiles.

An advanced hybrid drug carrier has been developed using porous nanocrystals of a swelling clay mineral conjugated with a block copolymer containing poly(ethylene glycol) and polyamine segments. Synthetic hectorite (Laponite) modified with (alpha-acetal-poly(ethylene glycol)-block-[poly(2-(N,N-dimethylamino) ethyl methacrylate)] (Acetal-PEG-b-PAMA) produced a homogeneous dispersion of organic-inorganic hybrid in an aqueous solution, which showed flocculation-resistive properties with an elevated ionic strength. The zeta-potential measurement revealed that nonionic PEG brush layers are formed on the surface of the clay nanocrystals since negative charge of the clay surface was completely neutralized by the positive charge of the cationic PAMA segment and the entire surface charge is successfully shielded by the effect of nonionic PEG segment in the block copolymer. This charge neutralization is in good agreement with the dispersion stability in solutions of high ionic strength. The average particle size of the PEG-modified hybrid particle was estimated to be 120 nm by a dynamic light scattering (DLS) method. When pyrene was used as the model compound of hydrophobic drug, it was incorporated into the nanopore in the clay mineral without showing any remarkable expansion of the basal spacings. Fluorescence spectra and powder X-ray diffraction patterns demonstrated that pyrene molecules are captured in an amorphous state in the range of low pyrene content (<5%), while excimer formation was seen at the higher pyrene concentration (>5%). The PEG-clay hybrid act as a carrier for sustained release of hydrophobic substances due to the high affinity (K = 1.52 x 10(4)) between the drug and clay surface.

Algorithms↗