Layered Double Hydroxide Clay Research Articles

Integrated study of antiretroviral drug adsorption onto calcined layered double hydroxide clay: experimental and computational analysis

This study focused on the efficacy of a calcined layered double hydroxide (CLDH) clay in adsorbing two antiretroviral drugs (ARVDs), namely efavirenz (EFV) and nevirapine (NVP), from wastewater. The clay was synthesized using the co-precipitation method, followed by subsequent calcination in a muffle furnace at 500 °C for 4 h. The neat and calcined clay samples were subjected to various characterization techniques to elucidate their physical and chemical properties. Response surface modelling (RSM) was used to evaluate the interactions between the solution’s initial pH, adsorbent loading, reaction temperature, and initial pollutant concentration. Additionally, the adsorption kinetics, thermodynamics, and reusability of the adsorbent were evaluated. The results demonstrated that NVP exhibited a faster adsorption rate than EFV, with both reaching equilibrium within 20–24 h. The pseudo-second order (PSO) model provided a good fit for the kinetics data. Thermodynamics analysis revealed that the adsorption process was spontaneous and exothermic, predominantly governed by physisorption interactions. The adsorption isotherms followed the Freundlich model, and the maximum adsorption capacities for EFV and NVP were established to be 2.73 mg/g and 2.93 mg/g, respectively. Evaluation of the adsorption mechanism through computational analysis demonstrated that both NVP and EFV formed stable complexes with CLDH, with NVP exhibiting a higher affinity. The associated adsorption energies were established to be −731.78 kcal/mol for NVP and −512.6 kcal/mol for EFV. Visualized non-covalent interaction (NCI) graphs indicated that hydrogen bonding played a significant role in ARVDs-CLDH interactions, further emphasizing physisorption as the dominant adsorption mechanism.

Molecular Antioxidants Maintain Synergistic Radical Scavenging Activity upon Co-Immobilization on Clay Nanoplatelets.

Unbalanced levels of reactive oxygen species (ROS) result in oxidative stress, affecting both biomedical and industrial processes. Antioxidants can prevent ROS overproduction and thus delay or inhibit their harmful effects. Herein, activities of two molecular antioxidants (gallic acid (GA), a well-known phenolic compound, and nicotinamide adenine dinucleotide (NADH), a vital biological cofactor) were tested individually and in combination to assess possible synergistic, additive, or antagonistic effects in free radical scavenging and in redox capacity assays. GA was a remarkable radical scavenger, and NADH exhibited moderate antioxidant activity, while their combination at different molar ratios led to a synergistic effect since the resulting activity was superior to the sum of the individual GA and NADH activities. Their coimmobilization was performed on the surface of delaminated layered double hydroxide clay nanoplatelets by electrostatic interactions, and the synergistic effect was maintained upon such a heterogenization of these molecular antioxidants. The coimmobilization of GA and NADH expands the range of their potential applications, in which separation of antioxidant additives is important during treatments or manufacturing processes.

Adsorption of Phenol from Wastewater Using Calcined Magnesium-Zinc-Aluminium Layered Double Hydroxide Clay

The presence of priority and emerging aromatic-based pollutants in water sources is of growing concern as they are not bioavailable and are present in reuse plant feed streams. These pollutants have known mutagenic and carcinogenic effects and must therefore be removed. Adsorption has been widely accepted as a suitable remediation technology due to its simplicity. Clay-based adsorbents have attracted significant attention due to their low cost, environmentally benign properties and regeneration potential. The present work focused on the thermal modification of a commercial Layered Double Hydroxide (LDH) clay and its subsequent effectiveness as an adsorbent in the removal of phenol from wastewater. Calcination of the neat clay resulted in the formation of metal oxides with varying phases and crystallinity depending on the treatment temperature. The BET surface area increased by 233% upon calcination at 500 °C. The highest phenol removal (85%) was observed in the clay calcined at 500 °C compared to 10% for the neat clay. Optimization studies revealed a maximum adsorption capacity of 12 mg/g at an adsorbent loading of 10 g/L at pH 7. Phenol adsorption was postulated to occur via a two-stage intercalation and surface adsorption mechanism. The equilibrium data were best fitted on the Freundlich isotherm model which describes heterogeneous adsorption. The adsorption kinetics followed a pseudo-second-order kinetic model with rate constants of 4.4 x 10−3 g/mg.h for the first 12h and 6.1 x 10−3 g/mg.h thereafter.

Adsorption of Phenol from Wastewater Using Modified Layered Double Hydroxide Clay

Phenol and its derivatives are some of the organic pollutants found in wastewater and they pose health risks to human beings and animals if left untreated. This work investigates the use of modified Layered Double Hydroxide clay as an adsorbent for removal of phenol from wastewater. High exchange capacities, capability to be modified with surfactants and through calcination, and the ability to regenerate are some of the properties of the clay reported in literature which make it an ideal adsorbent for phenol removal from wastewater. Modification of neat clay with silane increased the adsorption percentage from 6 % to 19 %, however the extent of adsorption was reduced from 87 % to 35 % when calcined clay was coated with a silane material. Calcination of the clay increased its BET surface area from 8.71 m2/g to 29.74 m2/g. The adsorption kinetics were best fitted by the pseudo second order model. The equilibrium isotherms which best fitted the adsorption data were the Freundlich isotherm and the Three Parameter Langmuir-Freundlich isotherm. The maximum adsorption capacity of 59.1 mg/g was observed using the Three Parameter Langmuir-Freundlich isotherm.

Making Molecules with Clay: Layered Double Hydroxides, Pentopyranose Nucleic Acids and the Origin of Life.

A mixture of sugar diphosphates is produced in reactions between small aldehyde phosphates catalysed by layered double hydroxide (LDH) clays under plausibly prebiotic conditions. A subset of these, pentose diphosphates, constitute the backbone subunits of nucleic acids capable of base pairing, which is not the case for the other products of these LDH-catalysed reactions. Not only that, but to date no other polymer found capable of base pairing—and therefore information transfer—has a backbone for which its monomer subunits have a plausible prebiotic synthesis, including the ribose-5-phosphate backbone subunit of RNA. Pentose diphosphates comprise the backbone monomers of pentopyranose nucleic acids, some of the strongest base pairing systems so far discovered. We have previously proposed that the first base pairing interactions were between purine nucleobase precursors, and that these were weaker and less specific than standard purine-pyrimidine interactions. We now propose that the inherently stronger pairing of pentopyranose nucleic acids would have compensated for these weaker interactions, and produced an informational polymer capable of undergoing nonenzymatic replication. LDH clays might also have catalysed the synthesis of the purine nucleobase precursors, and the polymerization of pentopyranose nucleotide monomers into oligonucleotides, as well as the formation of the first lipid bilayers.

Natural rubber/cis-1,4-polybutadiene nanocomposites: Vulcanization behavior, mechanical properties, and thermal stability

Natural rubber/cis-1,4-polybutadiene (NR/BR) blends with two types of layered nanofillers, montmorillonite (MMT) and layered double hydroxide (LDH), both in pristine and organically modified forms are produced and investigated. Faster curing is found for all the NR/BR blends, except for the one containing the unmodified MMT. This effect can be attributed to the groups placed in the interlayer regions of the clays; more precisely to ammonium groups for the organo-MMTs and to OH groups for LDHs. Mechanical properties and thermal stability of rubber compounds are investigated. It has been demonstrated that the performance of the final nanocomposite is significantly affected by the kind of clay. Particularly, the organo-MMTs provoke an improvement of the mechanical properties and increase the thermal stability of about 4–5° C in respect to the pure NR/BR matrix. On the contrary, the poor compatibility of unmodified MMT and of LDH clays with the rubber blend is evident and no enhancement on the composite performance has been observed. POLYM. ENG. SCI., 2013. © Society of Plastics Engineers

The application of layered double hydroxide clay (LDH)-poly(lactide-co-glycolic acid) (PLGA) film composites for the controlled release of antibiotics

Many sites of bacterial infection such as in-dwelling catheters and orthopedic surgical sites require local rather than systemic antibiotic administration. However, currently used controlled release vehicles, such as polymeric films, release water-soluble antibiotics too quickly, whereas nonporous bone cement, used in orthopedics, release very little drug. The purpose of this study was to investigate the use of nanoparticulates composed of layered double hydroxide clays to bind various antibiotics and release them in a controlled manner. Mg-Al (carbonate) layered double hydroxides were synthesized and characterized using established methods. These clay particles were suspended in solutions of the antibiotics tetracycline, doxorubicin (DOX), 5-fluorouracil, vancomycin (VAN), sodium fusidate (SF) and antisense oligonucleotides and binding was determined following centrifugation and quantitation of the unbound fraction by UV/Vis absorbance or HPLC analysis. Drug release from layered double hydroxide clay/drug complexes dispersed in polymeric films was measured by incubation in phosphate-buffered saline (pH 7.4) at 37°C using absorbance or HPLC analysis. Antimicrobial activity of drug released from film composites was determined using zonal inhibition studies against S. epidermidis. All drugs bound to the clay particles to various degrees. Generally, drugs released with a large burst phase of release (except DOX) with little further drug release after 4days. Dispersion of drug/clay complexes in poly(lactic-co-glycolic acid) films resulted in a reduced burst phase of release and a slow continuous release for many weeks with effective antimicrobial amounts of VAN and SF released at later time points. Layered double hydroxide clays may be useful for controlled release applications at sites requiring long-term antibiotic exposure as they maintain the drug in a non-degraded state and release effective amounts of drug over long time periods. LDH clay/drug complexes are amenable to homogenous dispersion in polymeric films where implant coating may be optimal or required.

Stability of free and mineral-protected nucleic acids: Implications for the RNA world

Using molecular dynamics simulations we study the structural stability of three different nucleic acids intercalated within a magnesium aluminium layered double hydroxide (LDH) mineral, at varying degrees of hydration, and free in aqueous solution. The nucleotides investigated are ribose nucleic acid (RNA), deoxyribose nucleic acid (DNA) and peptide nucleic acid (PNA), all in duplex form. Our simulations show that DNA has enhanced Watson–Crick hydrogen-bonding when intercalated within the LDH clay interlayers, compared with intercalated RNA and PNA, whilst the reverse trend is found for the nucleic acids in bulk water. The tendency for LDH to alter the stability of the three nucleic acids persists for higher temperature and pressure conditions. The uncharged protein backbone of PNA is found to have a detrimental effect on the overall stability of the duplex, as it experiences a greatly reduced electrostatic interaction with the charged LDH sheets compared to RNA and DNA. Assuming an RNA world, in which RNA preceded the DNA/protein world, at some point in time DNA must have taken over the role as the information storage molecule from RNA. These results suggest that a mineral based origin of life may have favoured DNA as the information-storage biomolecule over potentially competing RNA and PNA, providing a route to modern biology from the RNA world.

Drug intercalation in layered double hydroxide clay: Application in the development of a nanocomposite film for guided tissue regeneration

It has been proposed that localized and controlled delivery of alendronate and tetracycline to periodontal pocket fluids via guided tissue regeneration (GTR) membranes may be a valuable adjunctive treatment for advanced periodontitis. The objectives of this work were to develop a co-loaded, controlled release tetracycline and alendronate nanocomposite plasticized poly(lactic-co-glycolic acid) (PLGA) film that would form a suitable matrix supporting osteoblast proliferation and differentiation. Alendronate release was successfully controlled, with complete suppression of the burst phase of release by intercalation of alendronate anions in magnesium/aluminum layered double hydroxide (LDH) clay nanoparticles and dispersed in the PLGA film matrix. Tetracycline, loaded as free drug into the film together with alendronate–LDH clay complex released more rapidly than alendronate, but showed evidence of intercalation in the LDH clay particles. The dual drug loaded nanocomposite films were biocompatible with osteoblasts and after 5 week incubations, significant increase in alkaline phosphatase activity and bone nodule formation were observed.

Intercalation of Perylenediimide Dye into LDH Clays: Enhancement of Photostability

Intercalation of perylenediimide dye into a host layer of layered double hydroxide (LDH) by the anion-exchange method is studied. N,N′-Bis(4-benzosulfonic acid)perylene-3,4,9,10-tetracarboxylbisimide disodium salt (PRSA) has been synthesized and intercalated into the perchlorate form of ZnAl-, CoAl-, and NiAl−LDH. LDH composite with well-defined morphology has been prepared. XRPD and FT-IR investigation show successful intercalation of PRSA, and the interlayer distances are 32.5 A for ZnAl−LDH−PRSA, 30.0 A for CoAl−LDH−PRSA, and 31.2 A for NiAl−LDH−PRSA. These values support the presence of monolayer arrangement of intercalated PRSA molecules in the composite and also indicate vertical orientation of PRSA molecules with the basal plane of LDH. Photophysical properties of these intercalated composites have been measured with UV−vis spectroscopy, photoluminescence spectroscopy, and confocal laser scanning microscopy. The results indicate that the PRSA molecules are stacked in J-type aggregation in the inter...

Hydrophobic Modification of Layered Clays and Compatibility for Epoxy Nanocomposites

Recent studies on the intercalation and exfoliation of layered clays with polymeric intercalating agents involving poly(oxypropylene)-amines and the particular uses for epoxy nanocomposites are reviewed. For intercalation, counter-ionic exchange reactions of clays including cationic layered silicates and anionic Al-Mg layered double hydroxide (LDH) with polymeric organic ions afforded organoclays led to spatial interlayer expansion from 12 to 92 Å (X-ray diffraction) as well as hydrophobic property. The inorganic clays of layered structure could be modified by the poly(oxypropylene)amine-salts as the intercalating agents with molecular weights ranging from 230 to 5,000 g/mol. Furthermore, natural montmorillonite (MMT) clay could be exfoliated into thin layer silicate platelets (ca. 1 nm thickness) in one step by using polymeric types of exfoliating agents. Different lateral dimensions of MMT, synthetic fluorinated Mica and LDH clays had been cured into epoxy nanocomposites. The hydrophobic amine-salt modification resulting in high spacing of layered or exfoliation of individual clay platelets is the most important factor for gaining significant improvements of properties. In particular, these modified clays were reported to gain significant improvements such as reduced coefficient of thermal expansion (CTE), enhanced thermal stability, and hardness. The utilization of these layered clays for initiating the epoxy self-polymerization was also reported to have a unique compatibility between clay and organic resin matrix. However, the matrix domain lacks of covalently bonded crosslink and leads to the isolation of powder material. It is generally concluded that the hydrophobic expansion of the clay inter-gallery spacing is the crucial step for enhancing the compatibility and the ultimate preparation of the advanced epoxy materials.

Effect of application of a high magnetic field on the microstructure of Fe substituted layered double hydroxide clay for a magnetic application

In this study, the synthesis of Fe substituted layered double hydroxide (LDH) clays with unique layered structures, Mg∕Fe-LDH, was attempted by a coprecipitation method, and subsequent decomposition behaviors on in situ heat treatments under a high magnetic field were investigated for these LDH clays. Specifically, the evaluations of microstructure of Mg∕Fe-LDH were in detail carried out after in situ heat treatments with a high magnetic field of 10T. As a result, it was found that the thermal decomposition behaviors of Mg∕Fe-LDH on in situ heat treatments under the exposure of 10T were significantly different from the ones under 0T and the formation of magnesioferrite (MgFe2O4) with a spinel-type structure was enhanced by the application of a high magnetic field. Furthermore, there were some distinct differences between the morphologies of MgFe2O4 prepared between under 0 and 10T that were caused by the anisotropic magnetic susceptibility of MgFe2O4. Applying in situ heat treatment under 10T to the decomposition of Mg∕Fe-LDH led to the successful synthesis of nanosized MgFe2O4 at lower temperatures.

Odd−Even Effect of the Methylene Chain Number in the Template Polymerization of α,β-Diacetylenecarboxylates Incorporated in Layered Double Hydroxide Clay

The present investigation reports on the significant differences observed in the efficiency of the polymerization depending on the odd- or even-numbered methylene chains of diacetylenecarboxylates, CH3(CH2)(m-1)C[triple bond]C-C[triple bond]C(CH2)(n-1)CO2- (mono-[m,n]), incorporated in layered double hydroxide (LDH) clay. Upon gamma-ray irradiation of the diacetylenecarboxylates, or mono-[m,n], in LDH clay, polymer hybrids or poly-[m,n]/LDH, which exhibited coloring from light orange to violet, were obtained. The color of the poly-[m,n]/LDH hybrids was strongly dependent on the extent of the polymerization degrees. Moreover, the polymerization degrees were controlled by the number of methylene spacers n between the carboxyl and diacetylene groups. An odd-numbered n for the methylene chain of mono-[m,n] was found to be the determining factor in the efficient polymerization of these self-assembling aggregates within the interlayers of LDH clay.

Identification and geochemical modeling of processes controlling leaching of Cr(VI) and other major elements from chromite ore processing residue

Chromite ore processing residue (COPR) contains very high levels of chromium as Cr(III) and Cr(VI) and has a pH of ∼11.5 to 12. Millions of tonnes of COPR have in the past been deposited in urban areas. We have studied the factors that control leaching of Cr(VI), Ca, Al, Si, and Mg from COPR by means of batch experiments, mineralogical characterization of COPR via X-ray powder diffraction and scanning electron microscopy, and chemical equilibrium modeling. Batch experiments at a range of pH values and two liquid:solid ratios showed that mineral solubility control exists for aqueous concentrations of Cr(VI) above pH 10. Calculations indicate that the solid phases that control the solubility of Cr(VI) at pH values above 11 are Cr(VI)-substituted hydrogarnet (Ca 3Al 2(H 4O 4,CrO 4) 3) and Cr(VI)-hydrocalumite (Ca 4Al 2(OH) 12CrO 4·6 H 2O), a layered double-hydroxide clay with chromate anions held in the interlayers. In the pH range 9.5 to 11, the description of the Cr(VI) concentration in solution was strongly improved by the incorporation in the model of Cr(VI)-ettringite (Ca 6Al 2(OH) 12(CrO 4) 3·26 H 2O), which precipitates as a secondary phase when hydrocalumite dissolves. The proposed model for leaching of COPR at high pH includes Cr(VI)-bearing hydrogarnet, Cr(VI)-hydrocalumite, Cr(VI)-ettringite, brucite, calcite, Ca 2Al 2(OH) 10·3 H 2O, CaH 2SiO 4, and gehlenite hydrate (Ca 2Al 2(OH) 6SiO 8H 8·H 2O). The model accurately predicts the concentrations of Cr(VI), Ca, Al, Si, and Mg in solution in the pH range 10 to 12 as well as the pH-buffering behavior. Below pH 8, a decrease in the Cr(VI) concentration in solution is observed, which may be attributed to sorption of chromate onto freshly precipitated Al and Fe hydroxide surfaces. Sulfate and carbonate show the same type of behavior as chromate. The chemistry of COPR shows similarities with cement and high-pH municipal waste incinerator bottom ash.