Mechanical properties of the sodium montmorillonite interlayer intercalated with amino acids

Nanosized montmorillonite clay dispersed in small amounts in polymer results in polymer nanocomposites having superior engineering properties compared to those of the native polymer. These nanoinclusions are created by treating clay with an organic modifier which makes clay organophilic and results in intercalation or exfoliation of the montmorillonite. The modifiers used are usually long carbon chains with alkylammonium or alkylphosphonium cations. In this work, we have investigated the use of some alternative molecules which can act as modifiers for clay composites using clay for reinforcing a matrix of biopeptides or proteins. Such composites have potential applications in the fields of biomedical engineering and pharmaceutical science. In this work, the amino acids arginine and lysine are used as modifiers. The intercalation and mechanical behavior of the interlayer spacing with these amino acids as inclusions under compression and tension are studied using molecular dynamics simulations. Significant differences in the responses are observed. This work also provides an insight into the orientation and interaction of amino acids in the interlayer under different stress paths.     

Biocomposite films based on alginate and organically modified clay

Sodium alginate/sodium montmorillonite hybrid films were prepared by casting from the suspension of sodium alginate and different clay samples. Clay samples had been modified with a cationic surfactant, a cationic polymer, and a small polar molecule, respectively. Benzethonium chloride, polyethyleneimine and urea were used as clay modifiers. The composite films begin to disintegrate at a higher temperature and with less weight loss than the pure alginate films. This suggests an enhancement of the film thermal stability due to the modification of the alginate with clay samples.     

Binding of the protoxin and toxin proteins ofBacillus thuringiensis subsp.kurstaki on clay minerals

The equilibrium adsorption and binding of the delta-endotoxin proteins, i.e., the protoxins (M_r=132 kDa) and toxins (M_r=66 kDa), fromBacillus thuringiensis subsp.kurstaki were greater on montmorillonite than on kaolinite (five-fold more protoxin and three-fold more toxin were adsorbed on montmorillonite). Approximately two- to three-fold more toxin than protoxin was adsorbed on these clay minerals. Maximum adsorption occurred within 30 min (the shortest interval measured), and adsorption was not significantly affected by temperatures between 7° and 50°C. The proteins were more easily desorbed from kaolinite than from montmorillonite; they could not be desorbed from montmorillonite with water or 0.2% Na₂CO₃, but they could be removed with Tris-SDS (sodium dodecyl sulfate) buffer. Adsorption was higher at low pH and decreased as the pH increased. Adsorption on kaolinite was also dependent on the ionic nature of the buffers. The molecular mass of the proteins was unaltered after adsorption on montmorillonite, as shown by SDS-PAGE (polyacrylamide gel electrophoresis) of the desorbed proteins; no significant modifications occurred in their structure as the result of binding on the clay, as indicated by infrared analysis; and there was no significant expansion of the clay by the proteins, as shown by x-ray diffraction analysis. The bound proteins appeared to retain their insecticidal activity against the third instar larvae ofTrichoplusia ni.     

Biodegradable nanocomposites obtained by ball milling of pectin and montmorillonites

Two composites of apple peel pectin with 3% of either a natural or an organically modified montmorillonite clay, were prepared using a new alternative method, that relies on solid-state mixing at room temperature high energy ball milling(HEBM). This technique involves an efficient mixing of the organic and inorganic components by mechanical grinding. The milled powders were cast by water as films and characterized. The absence of the peak, corresponding to the basal spacing of the clay, in the X-ray diffractograms of the composite samples allowed us to suggest that the dispersion of the clay inside the pectin matrix takes place with the exfoliation of the clay sheets. The physical properties such as thermal degradation, elastic modulus, sorption and diffusion of water vapour and oxygen were analysed. It was found that they all were improved in the nanocomposites, in particular in the sample containing the natural sodium montmorillonite.     

Factors affecting growth of Bdellovibrio on Rhizobium

The extent of decline in the population density of Rhizobium sp. exposed to Bdellovibrio was markedly reduced in the presence of montmorillonite, kaolinite or vermiculite but not by a soil clay fraction. Increasing levels of montmorillonite reduced the numbers of vibrios that appeared in a two-membered culture and allowed for greater survival of the rhizobia. Bdellovibrio and not Rhizobium sp. was retained when mixed with the three clay minerals, but no appreciable retention was evident with the soil clay fraction. Suspensions of colloidal soil organic matter protected the hosts from parasitism, although aqueous extracts of soil did not affect the relationship. Cells from old Rhizobium sp. cultures were attacked only after a lag phase, but rhizobia that had been stored were more rapidly lysed than cells tested immediately after removal from the growth medium. The possible significance of these findings to the survival of rhizobia in soils containing Bdellovibrio is discussed.     

Modification of the interaction betweenEscherichia coli and bacteriophage in saline sediment

The effects of sorption phenomena on the interaction between a parasite and its host bacterium have been investigated using anEscherichia coli-bacteriophage-saline sediment system. The sediment contained organic matter and a high proportion of clay, predominantly montmorillonoid. BothE. coli and phage remained firmly sorbed to saline sediments or montmorillonite, but were rapidly desorbed following dilution of the electrolyte below a critical concentration. This desorption coincided with the dispersal of sediment colloids.Escherichia coli was protected from phage attack by the presence of sediment, montmorillonite, or organic matter at salinty levels both above and below this critical point for dispersal and desorption. Evidence is presented indicating thatE. coli is protected from phage attack at low electrolyte concentrations by an envelope of sorbed colloidal materials around the cell, whereas at high electrolyte concentrations protection results both from the colloid envelope around the cells as well as from the sorption of cells and phages to solid particles. The protection ofE. coli and possibly other fecal bacteria may result in their accumulation in saline sediments, producing a possible health hazard in estuaries and lagoons if the bacteria are desorbed following dilution as a result of heavy rainfall.     

Solute binding curves for (two polymer + solute)-complex systems. I. "One-solute-stack" systems

The matrix method is used for calculating the grand partition function for the reaction: 2 polymer + solute = complex. The homogeneous polymers are assumed to have two types of sites within each nucleotide unit: sites for the polymer–polymer association, i.e., (p-p) sites; sites for polymer–solute association i.e., (p-s) sites. The respective binding parameters, P and F , and nearest-neighbor interaction parameters, W and S , are assumed independent. Complications due to ring entropy are avoided by rest riding the model to one-solute-stack systems, which are physically realizable when the reciprocal of the solute cooperativity parameter is much larger than the number of nucleotides in the polymer. The 4 × 4 generating matrix is shown to be a tensor product of two 2 × 2 matrices, each the generating matrix of a particular type of site. The scalar product of the 4 × 4 matrix is shown to be equivalent to the scalar product of a 2 × 2 matrix in the weak interaction limit, W ≈ 0. Calculations are presented for the general case which restricts the (p-s) association to occur only with (p-p) associated nucleotide units. The nature of the binding curve in relation to partitioning the total interaction energy (F + P + S + W ) among the parameters is discussed. Also presented is a criterion for neglecting possible states in the calculation of the grand partition function.     

Molecular Atomistic Simulations of Clay Swelling in Water Dispersions

An atomistic model has been constructed for a dimeric montmorillonite type clay aggregate. The solid was supposed to be dispersed in water. The surrounding aqueous phase was modified from pure water to either salt or polymer solution, and finally represented by a mixed solution containing electrolytes and polyols. A combined energy minimisation procedure followed by a 100 ps real time molecular dynamic simulation was performed on each amorphous cell modelling the solid dispersion. 3D periodic boundary conditions were established to ensure fluid spatial continuity and the calculations proceeded at room temperature. Sodium, potassium and calcium chlorides were tested as shale swelling inhibition additives. The lower hydration energy cation K⁺ was the most effective swelling inhibitor. The adsorption of poly(propylene glyco)s to the ideal smectite surface was also studied. Their tendency to remain adsorbed was associated with the irreversibility of the polymer adsorption process. The conformational changes obtained for organic molecules were responsible for the final orientation of the clay sheets. So it was possible to conclude from qualitative observations that intramolecular interactions may determine a clay dispersion–agglomeration transition by modifying the system entropy. Finally, it was also concluded that specific combinations of additives could enhance their individual capabilities by synergistic effects, determining the effectiveness for some water-based mud formulations. This revised version was published online in June 2006 with corrections to the Cover Date.     

Slow vapor‐phase desorption of toluene from several ion‐exchanged montmorillonites

The sorption and desorption of volatile compounds from soils and clays exhibit a wide range of kinetics. While much of the sorptive interaction is very rapid, a certain fraction of volatile compounds that enter soil and clays are only slowly desorbed. It is generally believed that the formation of this recalcitrant or slowly desorbing fraction of volatile organic compounds (VOCs) in soils is due to the diffusion of compounds to poorly accessible sorption sites. However, the exact nature of these sites is in doubt. In montmorillonite, there are two likely possibilities for formation of the recalcitrant fraction: sites between the clay lamella and sites within clay particle aggregates. Because montmorillonite may be an important fraction of many soils, we have explored the formation of slowly desorbing toluene on a montmorillonite clay that was ion exchanged with five different ions (K⁺, Na⁺, Ca²⁺, Mg²⁺, and Fe³⁺) to form mineralogically similar clays with varying interlamellar spacing. The recalcitrant fraction was quantified for varying sorption and desorption times. The type of ion exchanged into the clay appears to have an important influence on the formation of a recalcitrant fraction.     

Ultrahigh-throughput screening system for directed polymer binding peptide evolution

Accumulation of plastics in the environment became a geological indicator of the Anthropocene era. An effective reduction of long-lasting plastics requires a treatment with micro-organisms that release polymer-degrading enzymes. Polymer binding peptides function as adhesion promoters and enable a targeted binding of whole cells to polymer surfaces. An esterase A-based Escherichia coli cell surface display screening system was developed, that enabled directed evolution of polymer binding peptides for improved binding strength to polymers. The E. coli cell surface screening system facilitates an enrichment of improved binding peptides from a culture broth through immobilization of whole cells on polymer beads. The polypropylene (PP)-binding peptide liquid chromatography peak I (LCI) was simultaneously saturated at five positions (Y29, D31, G35, E42, and D45; 3.2 million variants) and screened for improved PP-binding in the presence of the anionic surfactant sodium dodecylbenzenesulfonate (LAS; 0.25 mM). The cell surface system enabled efficient screening of the generated LCI diversity (in total ~10 million clones were screened). Characterization of identified LCI binders revealed an up to 12-fold improvement (eGFP-LCI-CSD-3: E42V/D45H) in PP-binding strength in the presence of the surfactant LAS (0.125 mM). The latter represents a first whole cell display screening system to improve adhesion peptides which can be used to direct and to immobilize organisms specifically to polymer surfaces (e.g., PP) and novel applications (e.g., in targeted plastic degradation).     

Novel non-exfoliated clay-nanocomposite materials by in situ co-polymerisation of intercalated monomers: a combinatorial discovery approach

We report the synthesis and qualitative testing of a novel class of clay nanocomposite meterials made by the in situ copolymerisation of small intercalating monomer molecules using combinatorial-style diversity methods. Initial screening was undertaken by treating montmorillonite clay films with combinations of selected additives in aqueous solution. The treated films were assessed for their stability in a qualitative manner based on their response to water. The mechanical stength of these films was also assessed qualitatively. Promising “lead” formulations showed no signs of water-induced swelling and/or exfoliation, while also being flexible and hard. In addition, the interlamellar d-spacings in the treated clay films were measured using X-ray diffraction, where possible; the value of the d-spacing in the treated clays was found to vary significanlty, from 12.7–17.7?Å. The lead formulations were then tested on bulk montmorillonite clay, confirming that the thin film behaviour was representative of that of the bulk. Direct analysis of the treated clays by mass spectrometry using both FAB and MALDITOF did not provide any useful information. However, when the clays were subjected to extraction using chloroform, clear evidence of higher relative moleclar mass species was forthcoming, confirming that polymersation of the additives was occurring. Further supporting evidence was obtained by solid-state NMR anlaysis of treated iron-free (laponite) clay samples, which also revealed extensive polymerisation of the monomers used. Comparison of these data with the results of some simple molecular modelling studies indicates that polymerisation is indeed occurring within the clay galleries.     

Binding of adenine and adenine-related compounds to the clay montmorillonite and the mineral hydroxylapatite

The first living things may have consisted of no more than RNA or RNA-like molecules bound to the surfaces of mineral particles. A key aspect of this theory is that these mineral particles have binding sites for RNA and its prebiotic precursors. The object of this study is to explore the binding properties of two of the best studied minerals, montmorillonite and hydroxylapatite, for possible precursors of RNA. The list of compounds investigated includes purines, pyrimidines, nucleosides, nucleotides, nucleotide coenzymes, diaminomaleonitrile and aminoimidazole carbox-amide. Affinities for hydroxylapatite are dominated by ionic interactions between negatively charged small molecules and positively charged sites in the mineral. Binding to montmorillonite presents a more complex picture. These clay particles have a high affinity for organic ring structures which is augmented if they are positively charged. This binding probably takes place on the negatively charged faces of these sheet-like clay particles. Additional binding sites on the edges of of these sheets have a moderate affinity for negatively charged molecules.Small molecules that bind to these minerals sometimes bind independently to sites on the minerals and sometimes bind cooperatively with favorable interactions between the bound molecules.     

Influence of clay mineral type and organic matter content on the uptake of239Pu and241Am by plants

Summary The uptake of²³⁹Pu and²⁴¹Am from different clay mineral-organic matter-sand mixtures simulating contrasting soil types was examined in growth chamber experiments. The mixtures represented various combinations of organic matter (0, 5 and 10%), kaolinite (11 type) and montomorillonite (21 type) clay minerals, each at the levels of 5, 10 and 25%, and purified quartz sand (as filler).Results indicated a marked reduction in uptake of both²³⁹Pu and²⁴¹Am with increase in organic matter as well as clay content of the mixtures. The Pu Concentration Ratios (CRs) ranged from (2.5–7.0)×10^–3 in the case of kaolinite-organic matter mixtures, and from (0.9–5.5)×10^–3 in the case of montmorillonite-organic matter mixtures. The corresponding values of Am Concentration Ratios (CRs) obtained were (1.9–725.4)×10^–3 in the case of kaolinite-organic matter mixtures, and between (0.7–3.5)×10^–3 for the montmorillonite-organic matter mixtures.Reduction in the uptake of²⁴¹Am with increasing clay content was more pronounced in the montmorillonite clay-organic matter mixtures as compared to that in the case of kaolinite-organic matter mixtures. While similar qualitative reduction in²³⁹Pu CRs with increasing clay content was observed, the reduction was less marked than in the case of²⁴¹Am. The values for Am CRs were higher than the corresponding Pu CRs in kaolinite based mixtures whereas in the case of montmorillonite-organic matter mixtures Pu CRs exceeded the Am CRs.Increasing organic matter content and its interaction with both kaolinite and montmorillonite clay minerals were found to be equally effective in reducing the uptake of²³⁹Pu as well as²⁴¹Am by plants.     

RESPONSE OF PERIPHYTON COMMUNITIES TO CLAY AND PHOSPHATE LOADING IN A SHALLOW RESERVOIR1

Enclosures in a small piedmont reservoir in the southeastern United States were used to determine the effects of loading by phosphate and two clay sediments on periphyton community structure and production during the summer growing season. The experimental design included replicated controls and the following treatments added at 2-to 3-day intervals: phosphate (PHOS), kaolinite (KAOL), montmorillonite (MONT), kaolinite with phosphate (K+P), and montmorillonite with phosphate (M+P). Periphyton were sampled from polyethylene strips of the same material as the enclosure walls, suspended at depths of 0.5 m and 2.0 m to assess treatment effects on shallow (epilimnetic) vs. deep (hypolimnetic) communities. Colonization after 40 days was sparse, dominated in biovolume by blue-green algae in all but the epilimnion of controls, in which small gelatinous green algae and chrysophyte flagellates were abundant. The biovolume of shallow periphyton after 79 days was lowest in KAOL and MONT, intermediate in controls and PHOS, and greatest in clay + P. Hence, P enrichment alleviated the deleterious effects of clay on periphyton production, and clay + P appeared to act synergistically in stimulating benthic algal growth. Periphyton biovolume was comparable among shallow and deep controls, PHOS, and treatments with the rapidly settling kaolinite. Lowest biovolume occurred at depth in treatments with montmorillonite under extreme light attenuation imposed by the suspended, finely particulate clay. The relative contribution of blue-green algae to total periphyton production was highest in clay + P treatments and lowest in controls. Heterotrophic dinoflagellates increased in the shallow periphyton under clay loading, and in the deep communities under PHOS and M + P. Periphyton contributed only 20–32% of total mesocosm productivity in controls, PHOS, and KAOL, increasing to about 40% in MONT, and to 72–91% of the total in M + P and K + P. The data indicate that benthic microalgae can represent a major proportion of the primary production in shallow reservoirs under high phosphate and sediment loading.     

Cadmium Sorption Characteristics of Soil Amendments and its Relationship with the Cadmium Uptake by Hyperaccumulator and Normal Plants in Amended Soils

In order to select appropriate amendments for cropping hyperaccumulator or normal plants on contaminated soils and establish the relationship between Cd sorption characteristics of soil amendments and their capacity to reduce Cd uptake by plants, batch sorption experiments with 11 different clay minerals and organic materials and a pot experiment with the same amendments were carried out. The pot experiment was conducted with Sedum alfredii and maize (Zea mays) in a co-cropping system. The results showed that the highest sorption amount was by montmorillonite at 40.82 mg/g, while mica was the lowest at only 1.83 mg/g. There was a significant negative correlation between the n value of Freundlich equation and Cd uptake by plants, and between the logarithm of the stability constant K of the Langmuir equation and plant uptake. Humic acids (HAs) and mushroom manure increased Cd uptake by S. alfredii, but not maize, thus they are suitable as soil amendments for the co-cropping S. alfredii and maize. The stability constant K in these cases was 0.14–0.16 L/mg and n values were 1.51–2.19. The alkaline zeolite and mica had the best fixation abilities and significantly decreased Cd uptake by the both plants, with K ≥ 1.49 L/mg and n ≥ 3.59.     

The Roles of Structural Order and Intermolecular Interactions in Determining Ionization Energies and Charge‐Transfer State Energies in Organic Semiconductors

The energy landscape in organic semiconducting materials greatly influences charge and exciton behavior, which are both critical to the operation of organic electronic devices. These energy landscapes can change dramatically depending on the phases of material present, including pure phases of one molecule or polymer and mixed phases exhibiting different degrees of order and composition. In this work, ultraviolet photoelectron spectroscopy measurements of ionization energies (IEs) and external quantum efficiency measurements of charge‐transfer (CT) state energies (E_CT) are applied to molecular photovoltaic material systems to characterize energy landscapes. The results show that IEs and E_CT values are highly dependent on structural order and phase composition. In the sexithiophene:C₆₀ system both the IEs of sexithiophene and C₆₀ shift by over 0.4 eV while E_CT shifts by 0.5 eV depending on molecular composition. By contrast, in the rubrene:C₆₀ system the IE of rubrene and C₆₀ vary by ≤ 0.11 eV and E_CT varies by ≤ 0.04 eV as the material composition varies. These results suggest that energy landscapes can exist whereby the binding energies of the CT states are overcome by energy offsets between charges in CT states in mixed regions and free charges in pure phases.     

Uptake of cobalt and cesium by microalgal- and cyanobacterial-clay mixtures

Accumulation of cobalt and cesium by the microalga Scenedesmus obliquus and the cyanobacterium Synechocystis PCC 6803 has been characterized at metal concentrations ranging from 1–100 µM in the presence of three clay minerals, montmorillonite, illite, and kaolinite. The majority of metal uptake over a 4 h period consisted of rapid binding to the clay mineral-cell aggregates, and was unaffected by incubation in the dark or by the presence of the metabolic inhibitor carbonyl cyanide-3-chlorophenyl hydrazone (CCCP). This was followed by a slower, energy-dependent uptake of metal by the cell components of the mixtures, which was inhibited by incubation in the dark or in the presence of CCCP. The initial phase of uptake by the clay mineral-cell mixtures and mixture components alone conformed to a Freundlich adsorption isotherm, the order of uptake for both cobalt and cesium being montmorillonite-cells > illite-cells > kaolinite-cells. S. obliquus-clay mineral mixtures accumulated more cobalt and cesium than Synechocystis PCC 6803-clay mineral mixtures. On a dry weight basis, clay minerals alone accumulated greater amounts of metals than clay mineral-cell mixtures, which accumulated more than the cells alone. However, when the same data was expressed as amount of metal adsorbed per unit surface area, S. obliquus, in most cases, adsorbed greater amounts of cobalt and cesium than the clay minerals or Synechocystis PCC 6803. As the proportion of clay in a cell-clay mineral mixture was increased, the amount of metal accumulated also increased. Reduced accumulation of cobalt and cesium by cell-clay mineral mixtures, exhibited by equal amounts of the individual components added together, indicated that the formation of clay-cell aggregates had masked some of the binding sites normally available to metal ions. Accumulation of cobalt and cesium by all clay mineral-cell mixtures was dependent on the external pH and NaCl concentration, and decreased with decreasing pH and increasing external NaCl concentration. Offprint requests to: G. M. Gadd.     

Effect of Inhibitors on the Montmorillonite Clay-Catalyzed Formation of RNA: Studies on the Reaction Pathway

The Langmuir adsorption isotherms of the phosphoroimidazolides of adenosine (ImpA) and uridine (ImpU), dA^5'ppdA and N⁶, N⁶-dimethyladenine binding on montmorillonite are consistent with their forming a monolayer on the clay surface. This suggests the condensation of ImpA and ImpU to oligomers proceeds on the surface of the clay and not in groups of monomers stacked on the clay surfaces. The binding and reactions of ImpU and ImpA on montmorillonite are blocked by N⁶, N⁶-dimethyladenine and dA^5'ppdA. dA^5'ppdA is a better inhibitor of oligomer formation than N⁶, N⁶-dimethyladenine because both adenine rings of dA^5'ppdA bind to the clay surface and block adjacent catalytic sites. An upper limit of 5–10 × 10¹⁵catalytic sites on 50 mg of clay was estimated from the binding of ImpU and the inhibition of oligomer formation by dA^5'ppdA.     

Acid phosphatase interactions with organo-mineral complexes: influence on catalytic activity

The influence of montmorillonite intercalated with representatives of three major classes of biological molecules-lysine (amino acid), –glucose (carbohydrate) and rhamnolipid (lipid) on the catalytic activity of acid phosphatase was investigated. In comparison to pure clay, the presence of the organic intercalates preserves residual activity at extreme pH values of 3 and 11 and temperatures as low as 10°C. Thermodynamic parameters of free energy, enthalpy and entropy, suggest that catalytic activity on the lysine and rhamnolipid intercalated surfaces is more spontaneous and favorable than that of pure clay. Michaelis-constants (K _m values) and maximum reaction velocities (V _max values) were determined and confirmed the enhancement of activity on the organo-mineral surfaces. The catalytic reaction product was measured as a function of time and the data fitted to equations describing the behavior of first and second order rates of reaction. All processes apart from the glucose-intercalated clay (second order) could be described by first order reactions. Catalytic activity was generally less on the glucose-mineral surface compared to the other organo-mineral surfaces and the pure clay. However, when all surfaces were saturated with acid phosphatase the glucose complex exhibited the highest level of catalytic activity.     

Thermal properties and flammability of polylactide nanocomposites with aluminum trihydrate and organoclay

Biodegradable polylactide (PLA) nanocomposites with aluminum trihydrate (ATH) and modified montmorillonite (MMT) were prepared via direct melt compounding using a twin-screw micro extruder. The exfoliated and intercalated structures of clay in the matrix were observed by TEM and XRD. The thermal oxidative degradation temperature and activation energy of the PLA/ATH/MMT nanocomposite determined by thermogravimetric analysis are higher than that without addition of ATH and organoclay. The incorporation of layered silicates into the PLA/ATH composite results in further stabilization throughout the degradation step. The V-0 rating (UL94 V) of the PLA nanocomposite has been achieved, and the melt dripping was reduced during combustion. Results showed that high loading of the conventional flame retardant ATH yielded brittle PLA composites; however, replacing a portion of the ATH with modified MMT in the PLA matrix improved this result.