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1.
Inorg Chem ; 62(35): 14243-14251, 2023 Sep 04.
Article in English | MEDLINE | ID: mdl-37608779

ABSTRACT

The emergence of multidrug-resistant microbial pathogens poses a significant threat, severely limiting the options for effective antibiotic therapy. This challenge can be overcome through the photoinactivation of pathogenic bacteria using materials generating reactive oxygen species upon exposure to visible light. These species target vital components of living cells, significantly reducing the likelihood of resistance development by the targeted pathogens. In our research, we have developed a nanocomposite material consisting of an aqueous colloidal suspension of graphene oxide sheets adorned with nanoaggregates of octahedral molybdenum cluster complexes. The negative charge of the graphene oxide and the positive charge of the nanoaggregates promoted their electrostatic interaction in aqueous medium and close cohesion between the colloids. Upon illumination with blue light, the colloidal system exerted a potent antibacterial effect against planktonic cultures of Staphylococcus aureus largely surpassing the individual contributions of the components. The underlying mechanism behind this phenomenon lies in the photoinduced electron transfer from the nanoaggregates of the cluster complexes to the graphene oxide sheets, which triggers the generation of reactive oxygen species. Thus, leveraging the unique properties of graphene oxide and light-harvesting octahedral molybdenum cluster complexes can open more effective and resilient antibacterial strategies.


Subject(s)
Staphylococcal Infections , Staphylococcus aureus , Humans , Molybdenum/pharmacology , Reactive Oxygen Species , Anti-Bacterial Agents/pharmacology
2.
Biomater Res ; 26(1): 85, 2022 Dec 21.
Article in English | MEDLINE | ID: mdl-36539854

ABSTRACT

BACKGROUND: Engineered living materials (ELMs) combine living cells with non-living scaffolds to obtain life-like characteristics, such as biosensing, growth, and self-repair. Some ELMs can be 3D-printed and are called bioinks, and their scaffolds are mostly hydrogel-based. One such scaffold is polymer Pluronic F127, a liquid at 4 °C but a biocompatible hydrogel at room temperature. In such thermally-reversible hydrogel, the microorganism-hydrogel interactions remain uncharacterized, making truly durable 3D-bioprinted ELMs elusive. METHODS: We demonstrate the methodology to assess cell-scaffold interactions by characterizing intact alive yeast cells in cross-linked F127-based hydrogels, using genetically encoded ratiometric biosensors to measure intracellular ATP and cytosolic pH at a single-cell level through confocal imaging. RESULTS: When embedded in hydrogel, cells were ATP-rich, in exponential or stationary phase, and assembled into microcolonies, which sometimes merged into larger superstructures. The hydrogels supported (micro)aerobic conditions and induced a nutrient gradient that limited microcolony size. External compounds could diffuse at least 2.7 mm into the hydrogels, although for optimal yeast growth bioprinted structures should be thinner than 0.6 mm. Moreover, the hydrogels could carry whole-cell copper biosensors, shielding them from contaminations and providing them with nutrients. CONCLUSIONS: F127-based hydrogels are promising scaffolds for 3D-bioprinted ELMs, supporting a heterogeneous cell population primarily shaped by nutrient availability.

3.
Dalton Trans ; 51(16): 6264-6274, 2022 Apr 20.
Article in English | MEDLINE | ID: mdl-35377373

ABSTRACT

Double-layered nanosheets containing pH-cleavable polymer networks between two niobate layers were prepared by copolymerization of N-isopropylacrylamide and an acid-degradable crosslinker via surface-initiated atom transfer radical polymerization on the surface of hydrated interlayers (interlayer I) of K4Nb6O17·3H2O and subsequent exfoliation by the introduction of tetra-n-butylammonium (TBA) ions into anhydrous interlayers (interlayer II). Moreover, the double-layered nanosheets were converted into single-layered nanosheets by the cleavage of cross-linking points in polymer networks by lowering pH. Fourier transform infrared spectroscopy (FTIR) and thermogravimetry (TG) results showed that polymer networks were present, and nanosheets with a thickness of 10.8 ± 1.6 nm were observed by using an atomic force microscope (AFM) after exfoliation using TBA ions. The thickness of the nanosheets was decreased to 6.1 ± 0.9 nm by lowering the pH, and proton nuclear magnetic resonance (1H NMR) and UV-vis spectroscopy showed that the degradation of the cross-linkers proceeded, suggesting that the cleavage of the cross-linking points led to the conversion of double-layered nanosheets into single-layered nanosheets.

4.
ACS Omega ; 6(37): 23837-23845, 2021 Sep 21.
Article in English | MEDLINE | ID: mdl-34568663

ABSTRACT

An original route for the intercalation of a 1,1'-diethyl-2,2'-cyanine iodide (PIC) cationic dye, through the use of anionic surfactants as vector/carrier phases, within Mg-Al layered double hydroxide (LDH) was investigated. From the data acquired from complementary techniques (X-ray diffraction, infrared and UV-visible spectroscopies, thermogravimetry, and fluorimetry), it appears that both the intercalation and aggregation states of the cationic dye within the internal structure of LDH mainly depend on both the surfactant state (monomer form or spherical micelle) and its amount. The intercalation of PIC at a low molar ratio to the anionic surfactant leads to the formation of J-aggregates with singular fluorescence properties that mainly depend on the nature of the anionic surfactant used for the co-intercalation process. The results obtained in this study open new routes for the intercalation of cationic species, assisted by anionic surfactants, within LDHs.

5.
Dalton Trans ; 50(18): 6290-6296, 2021 May 14.
Article in English | MEDLINE | ID: mdl-33881080

ABSTRACT

Characteristics of a kaolinite-acetone intercalation compound prepared using a kaolinite N-methylformamide intercalation compound (Kaol-NMF) as an intermediate were obtained by a set of techniques with attention to suppressing evaporation and deintercalation of acetone. X-ray diffraction (XRD) with spectroscopic analyses, Fourier-transform infrared spectroscopy (FTIR) accompanied by solid-state 13C and 29Si nuclear magnetic resonance (NMR) spectroscopy with cross polarization (CP) and magic angle spinning (MAS) enable us to demonstrate full replacement of a pre-intercalated NMF monolayer with an acetone monolayer between the layers of kaolinite with an increase in the basal spacing from 1.08 nm (Kaol-NMF) to 1.12 nm. In addition, the appearance of an additional OH stretching band at 3630 cm-1 and the shift of the C[double bond, length as m-dash]O stretching band to a lower wavenumber, from 1714 to 1701 cm-1, in the FTIR spectrum, along with a downfield shift of the signal due to C[double bond, length as m-dash]O groups from 209 ppm, where a singlet was observed in the liquid-state 13C NMR spectrum of acetone in CDCl3, to 219 ppm in the 13C CP/MAS NMR spectrum, indicate hydrogen bond formation between interlayer hydroxyl groups of kaolinite and C[double bond, length as m-dash]O groups of the intercalated acetone molecules. These careful characterization studies provide information on an interaction between kaolinite and acetone under ambient conditions.

6.
Int J Biol Macromol ; 170: 375-389, 2021 Feb 15.
Article in English | MEDLINE | ID: mdl-33359804

ABSTRACT

A lignin sample was extracted from Eucalyptus grandis sawdust, by the Klason method, and used as adsorbent for the removal of methylene blue (MB) from aqueous solutions. By using a set of complementary analytical tools, the lignin appeared to be constituted of oxygenated functional groups and aromatic moieties, while showing a specific surface area of 20 m2 g-1 and polydisperse particles. Different experimental conditions with various solid to liquid ratio, pH, as well as other external experimental parameters were investigated for the removal of MB by the lignin sample. The experimental adsorption data at the equilibrium were properly fitted by Langmuir model, while adsorption kinetical isotherms were correctly adjusted by the pseudo-second order model. The MB removal by lignin was spontaneous involving physisorption mechanisms leading to a saturation of the adsorption sites with a maximum adsorbed amount of about 32 mg g-1. The data acquired in this study also emphasized the interests to use lignin as potential adsorbent in the light of its properties for the removal of cationic dyes, including MB, with possible recycling and reuse cycles of lignin without any significant loss of its properties.


Subject(s)
Lignin/chemistry , Methylene Blue/chemistry , Water Purification/methods , Adsorption , Coloring Agents/chemistry , Eucalyptus/chemistry , Hydrogen-Ion Concentration , Kinetics , Lignin/isolation & purification , Plant Extracts/chemistry , Water , Water Pollutants, Chemical/chemistry , Wood
7.
RSC Adv ; 12(2): 753-761, 2021 Dec 22.
Article in English | MEDLINE | ID: mdl-35425126

ABSTRACT

The impact of inorganic nanosheets with various chemical compositions and properties at different concentrations on the rheological properties and the gelation formation of a thermo-responsive hydrogel was investigated. F127 Pluronic triblock copolymers, with the structure (EO)99(PO)65(EO)99 (EO: ethylene oxide and PO propylene oxide respectively), functionalized by dimethacrylate (F127-DMA) at a concentration of 25% was used in this study. After careful characterization by complementary techniques: transmission electron microscopy (TEM), atomic force microscopy (AFM), and X-ray diffraction of nanosheets derived from the peeling of layered materials (montmorillonite, organoclays and hexaniobate), the nanosheets were seen to be suitably dispersed in the hydrogels. The inclusion of hydrophobic nanosheets (i.e. those treated with the grafting of surfactants onto their surface: organoclays and hexaniobate) leads to a depression of the gelation temperature while the nanocomposites exhibit an enhancement of their elastic properties, as determined by rheological measurements. In contrast, the inclusion of hydrophilic nanosheet derived from raw montmorillonite engenders an opposite trend. The whole nanocomposites whose gelation temperature can be tuned by both the nature and concentration of the nanosheets were successfully photopolymerized allowing the formation of a 3D structure containing a large content of water. The results obtained in this study open new perspectives for possible uses of hydrogel-based nanocomposites as embedding matrixes for bio-organisms.

8.
Chemosphere ; 259: 127480, 2020 Nov.
Article in English | MEDLINE | ID: mdl-32634722

ABSTRACT

A Na+ exchanged montmorillonite clay (Na-Mt) and its organoclay derivatives prepared with benzyldimethyltetradecylammonium (BDTA) cationic and polyoxyethylene (20)oleyl-ether (Brij-O20) non-ionic surfactants were used for first time at our knowledge as adsorbents the removal diverse pharmaceuticals (PPs) from samples collected in a rural wastewater facility (town of Josnes in France). The selected facility showed a poor efficiency for the elimination of PPs that were permanently release to the environment. Although involving different interactional mechanisms, the whole adsorbents Na-Mt, nonionic Brij-Mt and cationic BDTA-Mt organoclays, could remove the entire PPs of various chemical nature in a low concentration regime (ng L-1), where electrostatic interactions mainly controlled the adsorption. Thus, the organic PPs cations were preferentially adsorbed onto Na-Mt and Brij0.4-Mt (with its dual hydrophilic-hydrophobic nature) while anionic PPs showed a bold affinity to BDTA-Mt. The hydrophobic environment generated by the intercalation of surfactants within the interlayer space of organoclays conferred a versatility for the adsorption of numerous PPs through weak molecular forces (Van der Waals and/or pi-pi interactions). The study confirmed the proper efficiency of the studied layered materials including organoclays and emphasized about their promising interests in water remediation strategy.


Subject(s)
Clay/chemistry , Pharmaceutical Preparations/chemistry , Waste Disposal, Fluid/methods , Adsorption , Bentonite/chemistry , Cations , France , Hydrophobic and Hydrophilic Interactions , Surface-Active Agents/chemistry , Wastewater/chemistry , Water/chemistry , Water Pollutants, Chemical/chemistry
9.
Langmuir ; 36(26): 7252-7258, 2020 Jul 07.
Article in English | MEDLINE | ID: mdl-32423209

ABSTRACT

Surface modification of niobate nanosheets in a double-Y-type microchannel was achieved for the first time using parallel flows of an aqueous dispersion of nanosheets derived from ion-exchangeable layered perovskite via delamination with a tetrabutylammonium hydroxide aqueous solution and a cyclohexane solution of oleyl phosphate. The surface modification was essentially completed within 4.6 s, and spectroscopic characterization (IR, solid-state 13C and 31P NMR) demonstrated the successful surface modification. The surface modification using a biphasic system in a vial using the same liquids required more than 4 h, indicating the extremely high efficiency of surface modification in the microchannel.

10.
Chemosphere ; 239: 124730, 2020 Jan.
Article in English | MEDLINE | ID: mdl-31726518

ABSTRACT

The impact of electrolytes on the adsorption of emerging pollutants: pharmaceuticals onto layered materials: a raw clay mineral and its nonionic and cationic organoclay derivatives was studied. The selected pharmaceuticals: amoxicillin, norfloxacin, sulfamethoxazole, metoprolol, carbamazepine, and trimethoprim show different electric charges: zwitterionic, anionic, cationic and neutral and hydrophobic character (different LogP). Without any salts, the set of complementary data obtained by UV and infrared spectroscopies, X-ray diffraction points out the importance of the electric charge which represents a key parameter in both the spontaneity and feasibility of the adsorption. In contrast, the hydrophobicity of the analytes plays a minor role but determines the magnitude of the adsorbed amount of pharmaceuticals onto organoclays. With a dual hydrophilic and hydrophobic behavior, nonionic organoclay appears to be the most polyvalent material for the removal of the pharmaceuticals. In the presence of electrolytes (NaCl at a concentration of 1 × 10-2 mol L-1), both nonionic and cationic organoclays show a decrease of their efficiencies, whereas the adsorption is particularly enhanced for Na-Mt except for the cationic species (trimethoprim and metoprolol). Thus, in realistic experimental conditions close to those of natural effluents, raw clay mineral appears as the most appropriate sorbent for the studied pharmaceuticals while it raises the question of the usefulness of organoclays in water remediation strategy.


Subject(s)
Electrolytes/chemistry , Environmental Restoration and Remediation/methods , Pharmaceutical Preparations/analysis , Soil Pollutants/analysis , Soil/chemistry , Water Pollutants, Chemical/analysis , Adsorption , Amoxicillin/analysis , Amoxicillin/chemistry , Carbamazepine/analysis , Carbamazepine/chemistry , Cations/analysis , Hydrophobic and Hydrophilic Interactions , Metoprolol/analysis , Metoprolol/chemistry , Norfloxacin/analysis , Norfloxacin/chemistry , Pharmaceutical Preparations/chemistry , Soil Pollutants/chemistry , Sulfamethoxazole/analysis , Sulfamethoxazole/chemistry , Trimethoprim/analysis , Trimethoprim/chemistry , Water/chemistry , Water Pollutants, Chemical/chemistry , X-Ray Diffraction
11.
Langmuir ; 35(42): 13553-13561, 2019 Oct 22.
Article in English | MEDLINE | ID: mdl-31538790

ABSTRACT

A kaolinite-tetrabutylphosphonium bromide (TBPBr) intercalation compound (Kaol-TBPBr) was prepared from kaolinite providing inorganic aluminosilicate layers and TBPBr as intercalated salts between the layers through the use of an intermediate, a kaolinite-dimethylsulfoxide (DMSO) intercalation compound (Kaol-DMSO). The experimental data through complementary techniques, including X-ray diffraction, Fourier transform infrared spectroscopy, solid-state 13C and 29Si nuclear magnetic resonance (NMR) spectroscopy with cross polarization and magic angle spinning, inductively coupled plasma emission spectrometry, and ion chromatography, indicate complete removal of DMSO and intercalation of TBPBr with an increase in the basal spacing from 1.12 nm (Kaol-DMSO) to 1.53 nm (Kaol-TBPBr). In contrast to a similar intercalation compound, a kaolinite-tetrabutylammonium bromide (TBABr) intercalation compound (Kaol-TBABr) with a basal spacing of 1.51 nm, Kaol-TBPBr displayed interesting features such as enhanced thermal stabilities as well as bold resistance against several solvents. Kaol-TBPBr withstood thermal decomposition of the organic species over 100 °C much better than Kaol-TBABr. When Kaol-TBPBr and Kaol-TBABr were refluxed in methanol, ethanol, acetone, or toluene for 1 day, Kaol-TBPBr preserved the expanded kaolinite layers, while the Kaol-TBABr structure completely collapsed due to the release of TBABr. Thus, with these particular and unique features of Kaol-TBPBr, organophosphonium salts appear to be promising guest species for intercalation chemistry of kaolinite.

12.
Nanomaterials (Basel) ; 9(4)2019 Apr 02.
Article in English | MEDLINE | ID: mdl-30986971

ABSTRACT

This study proves that the new developed zinc-doped hydroxyapatite (ZnHAp) colloids by an adapted sol-gel method can be widely used in the pharmaceutical, medical, and environmental industries. ZnHAp nanoparticles were stabilized in an aqueous solution, and their colloidal dispersions have been characterized by different techniques. Scanning Electron Microscopy (SEM) was used to get information on the morphology and composition of the investigated samples. Energy-dispersive X-ray spectroscopy (EDX) analysis confirmed the elemental compositions of ZnHAp colloidal dispersions. The homogeneous and uniform distribution of constituent elements (zinc, calcium, phosphorus, oxygen) was highlighted by the obtained elemental mapping results. The X-ray diffraction (XRD) results of the obtained samples showed a single phase corresponding to the hexagonal hydroxyapatite. The characteristic bands of the hydroxyapatite structure were also evidenced by Fourier-transform infrared spectroscopy (FTIR) analysis. For a stability assessment of the colloidal system, ζ-potential for the ZnHAp dispersions was estimated. Dynamic light scattering (DLS) was used to determine particles dispersion and hydrodynamic diameter (DHYD). The goal of this study was to provide for the first time information on the stability of ZnHAp particles in solutions evaluated by non-destructive ultrasound-based technique. In this work, the influence of the ZnHAp colloidal solutions stability on the development of bacteria, such as Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus), was also established for the first time. The antimicrobial activity of ZnHAp solutions was strongly influenced by both the stability of the solutions and the amount of Zn.

13.
Langmuir ; 35(20): 6594-6601, 2019 May 21.
Article in English | MEDLINE | ID: mdl-30955334

ABSTRACT

Oleyl phosphate-modified HLaNb2O7· xH2O nanosheets (OP_HLaNb nanosheets) were prepared via phase transfer from an aqueous phase, comprising a dispersion of HLaNb2O7· xH2O (HLaNb) nanosheets, formed through the intercalation of tetrabutylammonium ion (TBA+) in the interlayer space of HLaNb and subsequent delamination, to a cyclohexane phase containing oleyl phosphate (OP, a mixture of monoester and diester). The modification of HLaNb nanosheets with OP was essentially completed within 3 days at a pH value of 2 or 4. Both infrared and solid-state 13C cross-polarization and magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectra of the OP_HLaNb nanosheets showed the presence of OP and/or related species and TBA+ on the HLaNb nanosheet surface. The solid-state 31P MAS NMR spectra of OP_HLaNb nanosheets exhibited new signals at -2 and 0 ppm, the former of which indicates the formation of Nb-O-P bonds. These whole data set obtained by complementary techniques clearly point out the modification of the HLaNb nanosheet surface by OP moieties causing a phase transfer. OP_HLaNb nanosheets showed higher dispersibility in cyclohexane than the OP_HLaNb_interlayer nanosheets, which were prepared via stepwise substitution reactions in the interlayers of HLaNb to achieve surface modification with OP and subsequent exfoliation in cyclohexane. The presence of TBA+ on the HLaNb nanosheets and the use of a liquid-liquid biphasic system were likely to improve the dispersibility. These results show that the preparation of OP-modified HLaNb nanosheets which could be well-dispersed in the cyclohexane phase was successful because of the use of a liquid-liquid biphasic system.

14.
J Environ Manage ; 232: 117-130, 2019 Feb 15.
Article in English | MEDLINE | ID: mdl-30471545

ABSTRACT

Mine soils often contain metal(loid)s that may lead to serious environmental problems. Phytoremediation, consisting in covering the soil with specific plants with the possible addition of amendments, represents an interesting way of enhancing the quality of mine soils by retaining contaminants and reducing soil erosion. In order to study the effect of an assisted phytoremediation (with willow and ryegrass) on the properties of soil pore water (SPW), we investigated the impact of amendment with biochar (BC) combined with the planting of willow and ryegrass on the behavior of several metal(loid)s (Pb, Zn, Ba, As, and Cd) in a mine soil. Data on the physicochemical parameters and concentrations of the different metal(loid)s in both SPW and in plant tissues of willow and ryegrass highlight the importance of BC for SPW properties in terms of reductions in soluble concentrations of Pb and Zn, although there was no effect on the behavior of As and Cd. BC also increased soluble concentrations of Ba, probably related to ion release by the BC. By improving major ions available in mine soil, BC improved the lifetime of plants and enhanced their growth. Plant development did not appear to significantly affect the physicochemical parameters of SPW. Willow and ryegrass growing on soil with BC incorporated Cd and Ba into their tissues. The influence of plants on the behavior of metal(loid)s was noticeable only for ryegrass growing in soil with 2% BC, where it modified the behavior of Pb and Ba.


Subject(s)
Lolium , Metals, Heavy , Salix , Soil Pollutants , Cadmium , Charcoal , Lead , Soil , Water , Zinc
15.
ACS Omega ; 3(11): 15332-15342, 2018 Nov 30.
Article in English | MEDLINE | ID: mdl-30556002

ABSTRACT

A Na-smectite clay mineral (Na-Mt) was exchanged with two concentrations of benzyldimethyltetradecyl ammonium chloride cationic surfactant up to one time the cation exchange capacity. Nonionic organoclay was prepared with polyoxyethylene (20) oleyl ether (Brij-O20) nonionic surfactant at one concentration. The resulting organoclays displayed lateral layer organization of the surfactants within their interlayer space.. The adsorption properties of these organoclays and the starting raw clay mineral were evaluated for three extensively used antibiotic pharmaceutical products: the amoxicillin (AMX), the sulfamethoxazole (SMX), and the trimethoprim (TRI), recognized as recalcitrant compounds to conventional water treatments and to display a complex behavior for different pH and temperature experimental conditions. Besides showing short half-life time with possible degradation by UV radiation, these antibiotics associated with mineral phases cause serious environmental issues of which the toxic effect can be exacerbated in the presence of other chemical compounds. From the set of data obtained by complementary techniques: UV and Fourier transform infrared spectroscopy, high-performance liquid chromatography coupled with mass spectrometry, and X-ray diffraction, it appears that the nonionic organoclay shows its versatility for the adsorption of individual molecules as well as a pool of antibiotics. The mixing of the three antibiotics showing different electric charged species (cations, anions, and zwitterions) mimics the natural context drives to a deep modification of the adsorption behavior onto the different materials that can act as possible carrier mineral phases in aquatic environment. These competition effects can be measured through the significant decrease of the K F Freundlich constants for AMX in the presence of other molecules (or electrolytes), whereas TRI and SMX, by their possible association, create a synergistic effect that favors their adsorption on the whole layered materials.

16.
Materials (Basel) ; 11(11)2018 Nov 07.
Article in English | MEDLINE | ID: mdl-30405033

ABSTRACT

Contamination of water with heavy metals such as lead is a major worldwide problem because they affect the physiological functions of living organisms, cause cancer, and damage the immune system. Hydroxyapatite, (Ca5(PO4)3OH) is considered one of the most effective materials for removing heavy metals from contaminated water. The hydroxyapatite nanopowders (N-HAp) obtained by a co-precipitation method were used in this research to determine the effectiveness in removing lead ions from contaminated solutions. In this study, we have investigated the structure and morphology of N-HAp nanopowders using X-ray diffraction (XRD), electronic transmission microscopy (TEM), and scanning electron microscopy (SEM). The structure information was also obtained by spectroscopy measurements. The Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy measurements revealed the presence of peaks corresponding to the phosphate and hydroxyl groups. The ability of N-HAp nanopowders to adsorb lead ions from aqueous solutions were established. The results of the kinetic and equilibrium studies on the removal of Pb (II) from aqueous solution revealed that the adsorption of lead (II) cations is due to the surface reaction with the hydroxyl terminal groups on the adsorbent and the combination of the positive charges of the metal cations with the negative charges on the adsorbent surfaces. These observations could validate the use of these ceramic nanopowders in ecological remediation strategies.

17.
J Phys Chem A ; 122(48): 9326-9337, 2018 Dec 06.
Article in English | MEDLINE | ID: mdl-30383382

ABSTRACT

The adsorption sites of Cs on montmorillonite clays were investigated by theoretical 133Cs chemical shift calculations, 133Cs magic-angle-spinning nuclear magnetic resonance (MAS NMR) spectroscopy, and X-ray diffraction under controlled relative humidity. The theoretical calculations were carried out for structures with three stacking variations in the clay layers, where hexagonal cavities formed with Si-O bonds in the tetrahedral layers were aligned as monoclinic, parallel, alternated; with various d-spacings. After structural optimization, all Cs atoms were positioned around the center of hexagonal cavities in the upper or lower tetrahedral sheets. The calculated 133Cs chemical shifts were highly sensitive to the tetrahedral Al (AlT)-Cs distance and d-spacing, rather than to the Cs coordination number. Accordingly, three peaks observed in our theoretical spectra were interpreted to be adsorbed Cs around the center of hexagonal cavity with or without AlT and on the surface in the open nanospace. In a series of 133Cs MAS NMR spectral changes for partial Cs substituted samples, the Cs atoms are preferentially adsorbed at sites near AlT for low Cs substituted montmorillonites. The presence of nonhydrated Cs was also confirmed in partially Cs substituted samples, even after being hydrated under high relative humidity.

18.
Materials (Basel) ; 11(8)2018 Aug 03.
Article in English | MEDLINE | ID: mdl-30081467

ABSTRACT

The present study demonstrates the effectiveness of hydroxyapatite nanopowders in the adsorption of zinc in aqueous solutions. The synthesized hydroxyapatites before (HAp) and after the adsorption of zinc (at a concentration of 50 mg/L) in solution (HApD) were characterized using X-ray diffraction (XRD), and scanning and transmission electron microscopy (SEM and TEM, respectively). The effectiveness of hydroxyapatite nanopowders in the adsorption of zinc in aqueous solutions was stressed out through ultrasonic measurements. Both Langmuir and Freundlich models properly fitted on a wide range of concentration the equilibrium adsorption isotherms, allowing us to precisely quantify the affinity of zinc to hydroxyapatite nanopowders and to probe the efficacy of hydroxyapatite in removal of zinc ions from aqueous solutions in ultrasonic conditions.

19.
Materials (Basel) ; 11(5)2018 Apr 24.
Article in English | MEDLINE | ID: mdl-29695049

ABSTRACT

The research conducted in this study presented for the first time results of physico-chemical properties and in vitro antimicrobial activity of hydroxyapatite plant essential oil against Gram-positive bacteria (methicillin-resistant Staphylococcus aureus (MRSA) and S. aureus 0364) and Gram-negative bacteria (Escherichia coli ATCC 25922). The samples were studied by scanning electron microscopy (SEM) and Fourier transform infrared (FTIR) spectroscopy to determine the morphology and structure of the nanocomposites of hydroxyapatite coated with basil (HAp-B) and lavender (HAp-L) essential oils (EOs). The values of the BET specific surface area (SBET), total pore volume (VP) and pore size (DP) were determined. The results for the physico-chemical properties of HAp-L and HAp-B revealed that lavender EOs were well adsorbed on the surface of hydroxyapatite, whereas basil EOs showed a poor adsorption on the surface of hydroxyapatite. We found that the lavender EOs hydroxyapatite (HAp-L) exhibited a very good inhibitory growth activity. The value of the minimum inhibitory concentration (MIC) related to growth bacteria was 0.039 mg/mL for MRSA, 0.02 mg/mL for S. aureus and 0.039 mg/mL E. coli ATCC 25922. The basil EO hydroxyapatite (HAp-B) showed poor inhibition of bacterial cell growth. The MIC value was 0.625 mg/mL for the HAp-B sample in the presence of the MRSA bacteria, 0.313 mg/mL in the presence of S. aureus and 0.078 mg/mL for E. coli ATCC 25922.

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