In-depth characterization of phosphate intercalated Mg Al Layered double hydroxides and study of the PO4 release properties.

Slow-release fertilizers (SRFs) form the core of innovative strategies in sustainable agriculture. Layered Double Hydroxides (LDH), known for their high capacity to sequester plant nutrients, especially phosphate, are emerging as promising candidates for SRF synthesis. The phosphate release properties of MgAl LDH (with a targeted Mg/Al ratio of 2.0) intercalated with HPO42- anions were assessed in various aqueous environments. A comprehensive analysis, including in-depth chemical and structural characterizations (ICP-OES, XRD, PDF, 27Al NMR, 31P NMR, FTIR, SEM) of the as-prepared phase unveiled a more intricate composition than anticipated for a pure or ideal Mg2Al-HPO4 LDH, encompassing an excess of intercalated phosphate in conjunction with K+. Beyond the intercalated phosphate, solid state 31P NMR speciation identified multiple HxPO4(-3+x) environments, indicating a portion of the phosphate reacting with intralayer Mg2+ to form K-struvite. Additionally, some phosphates were adsorbed onto the surface of amorphous aluminum hydroxide, a side phase formed during MgAl coprecipitation. The phosphate release demonstrated rapid kinetics, occurring within 6 days. Moreover, the released phosphate increased significantly when reducing the Solid/Liquid (S/L) ratio (58%) and further increasing in the presence of carbonate ions (90%). The released phosphate varied from 12% to 90% under different release conditions, transitioning from water to a 3.33 mM NaHCO3 aqueous solution at a low S/L ratio (from 20 mg LDH per mL to 0.02 mg LDH per mL). The simultaneous release of K+, Mg2+, Al3+ indicated the complete dissolution of the K-struvite and partial dissolution of phosphate intercalated MgAl LDH. These results enhanced our understanding of the mechanism governing phosphate release from MgAl LDH, paving the way for potential phosphate recovery by LDH or for the development of LDH-based SRFs.

Zinc-Doped Bioactive Glass/Polycaprolactone Hybrid Scaffolds Manufactured by Direct and Indirect 3D Printing Methods for Bone Regeneration.

A novel organic-inorganic hybrid, based on SiO2-CaO-ZnO bioactive glass (BG) and polycaprolactone (PCL), associating the highly bioactive and versatile bioactive glass with clinically established PCL was examined. The BG-PCL hybrid is obtained by acid-catalyzed silica sol-gel process inside PCL solution either by direct or indirect printing. Apatite-formation tests in simulated body fluid (SBF) confirm the ion release along with the hybrid's bone-like apatite forming. Kinetics differ significantly between directly and indirectly printed scaffolds, the former requiring longer periods to degrade, while the latter demonstrates faster calcium phosphate (CaP) formation. Remarkably, Zn diffusion and accumulation are observed at the surface within the newly formed active CaP layer. Zn release is found to be dependent on printing method and immersion medium. Investigation of BG at the atomic scale reveals the ambivalent role of Zn, capable of acting both as a network modifier and as a network former linking the BG silicate network. In addition, hMSCs viability assay proves no cytotoxicity of the Zn hybrid. LIVE/DEAD staining demonstrated excellent cell viability and proliferation for over seven weeks. Overall, this hybrid material either non-doped or doped with a metal trace element is a promising candidate to be translated to clinical applications for bone regeneration.

Development of Dipeptide N-acetyl-L-cysteine Loaded Nanostructured Carriers Based on Inorganic Layered Hydroxides.

N-acetyl-L-cysteine (NAC), a derivative of the L-cysteine amino acid, presents antioxidant and mucolytic properties of pharmaceutical interest. This work reports the preparation of organic-inorganic nanophases aiming for the development of drug delivery systems based on NAC intercalation into layered double hydroxides (LDH) of zinc-aluminum (Zn2Al-NAC) and magnesium-aluminum (Mg2Al-NAC) compositions. A detailed characterization of the synthesized hybrid materials was performed, including X-ray diffraction (XRD) and pair distribution function (PDF) analysis, infrared and Raman spectroscopies, solid-state 13carbon and 27aluminum nuclear magnetic resonance (NMR), simultaneous thermogravimetric and differential scanning calorimetry coupled to mass spectrometry (TG/DSC-MS), scanning electron microscopy (SEM), and elemental chemical analysis to assess both chemical composition and structure of the samples. The experimental conditions allowed to isolate Zn2Al-NAC nanomaterial with good crystallinity and a loading capacity of 27.3 (m/m)%. On the other hand, NAC intercalation was not successful into Mg2Al-LDH, being oxidized instead. In vitro drug delivery kinetic studies were performed using cylindrical tablets of Zn2Al-NAC in a simulated physiological solution (extracellular matrix) to investigate the release profile. After 96 h, the tablet was analyzed by micro-Raman spectroscopy. NAC was replaced by anions such as hydrogen phosphate by a slow diffusion-controlled ion exchange process. Zn2Al-NAC fulfil basic requirements to be employed as a drug delivery system with a defined microscopic structure, appreciable loading capacity, and allowing a controlled release of NAC.

Interleaved Electroactive Molecules into LDH Working on Both Electrodes of an Aqueous Battery-Type Device.

By selecting two electroactive species immobilized in a layered double hydroxide backbone (LDH) host, one able to act as a positive electrode material and the other as a negative one, it was possible to match their capacity to design an innovative energy storage device. Each electrode material is based on electroactive species, riboflavin phosphate (RF) on one side and ferrocene carboxylate (FCm) on the other, both interleaved into a layered double hydroxide (LDH) host structure to avoid any possible molecule migration and instability. The intercalation of the electroactive guest molecules is demonstrated by X-ray diffraction with the observation of an interlayer LDH spacing of about 2 nm in each case. When successfully hosted into LDH interlayer space, the electrochemical behavior of each hybrid assembly was scrutinized separately in aqueous electrolyte to characterize the redox reaction occurring upon cycling and found to be a rapid faradic type. Both electrode materials were placed face to face to achieve a new aqueous battery (16C rate) that provides a first cycle-capacity of about 7 mAh per gram of working electrode material LDH/FCm at 10 mV/s over a voltage window of 2.2 V in 1M sodium acetate, thus validating the hybrid LDH host approach on both electrode materials even if the cyclability of the assembly has not yet been met.

Fast and efficient shear-force assisted production of covalently functionalized oxide nanosheets.

HYPOTHESIS: While controlled and efficient exfoliation of layered oxides often remains a time consuming challenge, the surface modification of inorganic nanosheets is of outmost importance for future applications. The functionalization of the bulk material prior to exfoliation should allow the application of tools developped for Van der Waals materials to directly produce functionalized oxide nanosheets. EXPERIMENTS: The Aurivillius phase Bi2SrTa2O9 is functionalized by a linear aliphatic phosphonic acid via microwave-assisted reactions. The structure of the hybrid material and the coordination of the phosphonate group is scrutinized, notably by Pair Distribution Function. This functionalized layered oxide is then exfoliated in one hour in organic solvent, using high shear force dispersion. The obtained nanosheets are characterized in suspension and as deposits to check their chemical integrity. FINDINGS: The covalent functionalization decreases the electrostatic cohesion between the inorganic layers leading to an efficient exfoliation in short time under shearing. The functionalization of the bulk material is preserved on the nanosheets upon exfoliation and plays a major role to enable liquid-phase exfoliation and in the stability of the resulting suspensions. This strategy is very promising for the straighforward preparation of functionalized nanosheets, paving the way for versatile design of new (multi)functional hybrid nanosheets for various potential applications.

Outstanding chain-extension effect and high UV resistance of polybutylene succinate containing amino-acid-modified layered double hydroxides.

Polybutylene succinate (PBS) nanocomposite materials were prepared using a melt compounding process. The Mg2Al-based PBS nanocomposites, dispersed with inorganic-organic hybrid materials (layered double hydroxides, LDHs), were functionalized with the amino acids L-histidine (HIS) and L-phenylalanine (PHE). The rheological and anti-ultraviolet (anti-UV) properties were investigated and compared to filler-free PBS as well as LDH Mg2Al/nitrate as references. Both organo-modified LDHs exhibited a remarkable chain-extension effect for PBS with an outstanding increase in the zero-shear viscosity η0 for PBS-Mg2Al/PHE (two order of magnitude increase as compared to filler-free PBS). These results were compared to data found in the literature. Moreover, HIS and PHE anions embedded into the LDH structure can successfully prevent the chain scission reactions that usually occur during photo-ageing of PBS under UV radiation exposure. This highlights the outstanding performance of the LDH hybrid materials, and in particular, their application as a polymer chain extender and UV stabilizer for PBS, which can likely be extended to other biodegradable polymers.

Intercalation and structural aspects of macroRAFT agents into MgAl layered double hydroxides.

Increasing attention has been devoted to the design of layered double hydroxide (LDH)-based hybrid materials. In this work, we demonstrate the intercalation by anion exchange process of poly(acrylic acid) (PAA) and three different hydrophilic random copolymers of acrylic acid (AA) and n-butyl acrylate (BA) with molar masses ranging from 2000 to 4200 g mol-1 synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization, into LDH containing magnesium(II) and aluminium(III) intralayer cations and nitrates as counterions (MgAl-NO3 LDH). At basic pH, the copolymer chains (macroRAFT agents) carry negative charges which allowed the establishment of electrostatic interactions with the LDH interlayer and their intercalation. The resulting hybrid macroRAFT/LDH materials displayed an expanded interlamellar domain compared to pristine MgAl-NO3 LDH from 1.36 nm to 2.33 nm. Depending on the nature of the units involved into the macroRAFT copolymer (only AA or AA and BA), the intercalation led to monolayer or bilayer arrangements within the interlayer space. The macroRAFT intercalation and the molecular structure of the hybrid phases were further characterized by Fourier transform infrared (FTIR) and solid-state 13C, 1H and 27Al nuclear magnetic resonance (NMR) spectroscopies to get a better description of the local structure.

The effect of polymer solubilizing side-chains on solar cell stability.

The impact of side-chain variations on the photothermal stability of solar cells containing poly(benzodithiophene-diketopyrrolopyrrole) polymers are investigated in the absence of oxygen. Four different side-chains of benzodithiophene (BDT) are synthesized and copolymerized with diketopyrrolopyrrole (DPP) by Stille polymerization. The photothermal stability is measured as active layer blends with phenyl-C61-butyric acid methyl ester (PCBM) in encapsulated inverted photovoltaic cell architecture with zinc oxide and PEDOT: PSS as transport layers (ITO/ZnO/active layer/ PEDOT: PSS/Ag). Device degradation is correlated to the morphological behavior of the polymer:blend upon AM1.5 illumination (UV-visible light, 50 °C) and have been investigated by AFM, XRD, and UV-Vis. Once exposed to the light and to the temperature the BHJ stability is governed by two processes (i) PCBM crystallization and (ii) PCBM dimerization. Dimerization results in a rapid initial performance decrease followed by a more gradual decrease caused by a slower thermally activated crystallization. Depending on the blend morphology, dictated by the polymer's alkyl chain, the two processes occur to different extents thereby modulating the BHJ stability. Thus, of the polymer side-chains explored, linear alkyl side-chains stabilized the bulk heterojunction most effectively followed by no side-chain, alkoxy and branched side-chains. Lowering the concentration of fullerene in the active layer also reduces the rate of degradation across the polymers tested. This is a result of both the rate of crystallization and dimerization of fullerene being dependent on its concentration and the nature of the polymer side-chains. This approach appears to be a general strategy to increase the polymer:PCBM stability.

Adsorption of PolyCarboxylate Poly(ethylene glycol) (PCP) esters on Montmorillonite (Mmt): effect of exchangeable cations (Na+, Mg2+ and Ca2+) and PCP molecular structure.

This study deals with the adsorption of PolyCarboxylate Poly(ethylene glycol) esters (PCP) superplasticizers on Na-, Mg- and Ca-saturated Montmorillonite (Mmt) clays. The interactions have been examined through different experimental methods: adsorption isotherms, zeta potential measurements and sedimentation experiments. It was found that PCP adsorption depends both on the architecture of PCP molecules and the nature of cation located on the interlayer exchange sites of the Montmorillonite. Whatever the PCP, a larger amount was adsorbed on Na-Mont than on Mg-Mont or Ca-Mont. This indicates the occurrence of two adsorption mechanisms: (i) a superficial adsorption via electrostatic interactions between the carboxylate groups of PCP and positively charged sites on clay surfaces, (ii) intercalation of ether units of the PCP grafts in the interlayer space by displacement of water molecules coordinated to the exchangeable cations. Furthermore, despite the weak negative values of the zeta potential, the addition of PCP promotes the stability of the suspensions which is attributed to steric repulsion acting between particles.

Photostability and photobactericidal properties of porphyrin-layered double hydroxide-polyurethane composite films.

The photostability and photobactericidal properties of PdTPPC (Pd(ii)-5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin)-Zn2Al/PU (polyurethane) composite films have been studied in order to investigate their applicability as new photodynamic surfaces. These films comprise a PdTPPC porphyrin photosensitizer intercalated between the lamella of Zn2Al layered double hydroxide and dispersed (1 wt%) into a polyurethane matrix. The study of the photophysical behaviour shows that the Zn2Al LDH host enhances the chemical stability of the PdTPPC guest by minimizing photobleaching and quenching aggregation effects. The singlet oxygen production under irradiation of PdTPPC-Zn2Al/PU composite films is confirmed by the observation of an O2(1Δg) emission band centered at 1274 nm. Furthermore, the value of the rate constant kq for the PdTPPC phosphorescence quenching by oxygen kq = (8.2 ± 0.3) 10-2 s-1 Pa-1 indicates a slow diffusion of oxygen into and out of the PU polymer. In a second step, accelerating light ageing tests are conducted to determine the effect of singlet oxygen production on the chemical and mechanical stability of the PU matrix. Oxygen uptake experiments coupled with ATR-IR measurements indicate the probable formation of hydroxylated photoproducts but with no detrimental effects on the microstructure and the viscoelastic properties of the PU matrix as evidenced by dynamical mechanical analysis. Finally, in vitro preliminary antimicrobial tests show that PdTPPC-Zn2Al/PU composite films are able to inhibit S. aureus growth with no release of PdTPPC biocide from the PdTPPC-Zn2Al/PU composite film. We also observe a total inhibition of P. aeruginosa growth suggesting an efficacy against biofilm formation.

Structural insight into iodide uptake by AFm phases.

The ability of cement phases carrying positively charged surfaces to retard the mobility of (129)I, present as iodide (I(-)) in groundwater, was investigated in the context of safe disposal of radioactive waste. (125)I sorption experiments on ettringite, hydrotalcite, chloride-, carbonate- and sulfate-containing AFm phases indicated that calcium-monosulfate (AFm-SO(4)) is the only phase that takes up trace levels of iodide. The structures of AFm phases prepared by coprecipitating iodide with other anions were investigated in order to understand this preferential uptake mechanism. X-ray diffraction (XRD) investigations showed a segregation of monoiodide (AFm-I(2)) and Friedel's salt (AFm-Cl(2)) for I-Cl mixtures, whereas interstratifications of AFm-I(2) and hemicarboaluminate (AFm-OH-(CO(3))(0.5)) were observed for the I-CO(3) systems. In contrast, XRD measurements indicated the formation of a solid solution between AFm-I(2) and AFm-SO(4) for the I-SO(4) mixtures. Extended X-ray absorption fine structure spectroscopy showed a modification of the coordination environment of iodine in I-CO(3) and in I-SO(4) samples compared to pure AFm-I(2). This is assumed to be due to the introduction of stacking faults in I-CO(3) samples on one hand and due to the presence of sulfate and associated space-filling water molecules as close neighbors in I-SO(4) samples on the other hand. The formation of a solid solution between AFm-I(2) and AFm-SO(4), with a short-range mixing of iodide and sulfate, implies that AFm-SO(4) bears the potential to retard (129)I.

Effect of low doses of 14 MeV neutrons on polymers.

The structural modifications of polymers irradiated with 14 MeV neutrons were studied. Two elastomers, a polypropylene-type polymer and poly(ethylene oxide) were exposed to low doses of fast neutrons in the range of 0.3-14 Gy. The radiation damages were observed at the molecular scale by infrared spectroscopy. The morphological changes were investigated by steric exclusion chromatography, insoluble fraction measurements, differential scanning calorimetry and X-ray diffraction. It was found that neutrons provoked oxidation processes accompanied by modifications in the polymer architecture, including chain scissions, crosslinking reactions and changes in the crystallinity. Moreover, the conventional antioxidants were shown to be inefficient in inhibiting the aging of the polymers. These results also suggest that the radiation damages could be used successfully for dosimetry applications using an easily implementable protocol.

Intercalation chemistry in a LDH system: anion exchange process and staging phenomenon investigated by means of time-resolved, in situ X-ray diffraction.

Using time-resolved, in situ energy-dispersive X-ray diffraction (EDXRD), the formation of interstratified LDH structures, with alternate interlayer spaces occupied by different anions, have been demonstrated during anion exchange reactions. Novel hybrid LDH nanostructures can thus be prepared, combining the physicochemical properties of two intercalated anions plus those of the LDH host. A general trend is that inorganic-inorganic anion exchange reactions occur in a one-step process while inorganic-organic exchanges may proceed via a second-stage intermediate, suggesting that staging occurs partly as a result of organic-inorganic separation. Yet, other influencing parameters must be considered such as LDH host composition, LDH affinity for different anions and LDH particle size as well as extrinsic parameters like the reaction temperature. Hence, a correlation between the occurrence of staging phenomenon and the difficulty of the exchange of the initial anion is observed, suggesting that staging is needed to overcome the energy barrier in the case of the exchange by organic anions. Notwithstanding the LiAl(2) system, staging has mainly been observed with Zn(2)Cr LDH host so far, a peculiar LDH composition with a unique Zn/Cr ratio of two and a local order of the cations within the hydroxide layers. The formation of a higher order-staged intermediate than stage two, observed during the exchange reaction of CO(3)(2-) or SO(4)(2-) anions with Zn(2)Cr-tartrate, is in favour of a Daumas-Herold model although this model implies a bending of LDH layers. The analysis of the X-ray powder diffraction pattern of Zn(2)Cr-Cl/tartrate second-stage intermediate, isolated almost as a pure phase during the exchange of Cl(-) with tartrate anions in Zn(2)Cr LDH, indicates a disorder in the stacking sequence and a relative proportion of the two kinds of interlayers slightly different from 50/50. Besides, the microstructural analysis of the XRD pattern reveals a great reduction of the stacking thickness during the anion exchange process but with no change of the in-plane coherent length, therefore no in-plane deformation of LDH host layers. Finally, the anion exchange properties of Zn(2)Cr-Cl/tartrate, investigated by means of EDXRD, show highly selective anion-exchange reactions, leading to the formation of new second-stage intermediates that cannot be prepared starting from the mono-intercalated Zn(2)Cr-Cl. This "Zn(2)Cr-Cl/tartrate approach" might constitute a new route for the synthesis of various mixed organic-inorganic anions-exchanged forms of LDH.

Zn2Al layered double hydroxides intercalated and adsorbed with anionic blue dyes: a physico-chemical characterization.

Three different anionic blue organic dyes have been intercalated into the structure of Zn(2)Al layered double hydroxides, using the co-precipitation method at constant pH. Using the same synthetic procedure, Zn(2)Al-Cl has been prepared and used as an adsorptive phase to retain the blue dyes from an aqueous solution. All the organic/inorganic (O/I) hybrid LDH compounds were analyzed by X-ray powder diffraction (XRPD), thermal analysis (TG/DTA), elemental analysis, solid state (13)C nuclear magnetic resonance (CPMAS (13)C NMR), and Fourier transform infrared spectroscopy (FTIR). In the adsorption experiments, Gibbs free energy DeltaG values for the temperatures in a range between 10 and 40 degrees C were found to be negative, which indicates that the nature of adsorption is spontaneous and shows the affinity of LDH material towards the blue anionic dyes. Additionally a decrease in DeltaG values at higher temperature further indicates that this process is even more favorable at these conditions. The enthalpy DeltaH values were between physisorption and chemisorption, and it may be concluded that the process was a physical adsorption enhanced by a chemical effect, characterized by a combined adsorption/intercalation reaction, making these O/I assemblies reminiscent of the Maya blue.

Organic inorganic dye filler for polymer: blue-coloured layered double hydroxides into polystyrene.

A series of blue dye molecules, Evans blue (EB), Chicago sky blue (CB), Niagara blue (NB) were incorporated by direct co-precipitation within the galleries of negatively charge layered double hydroxide (LDH). The materials of cation composition Zn/Al = 2 lead to well-defined organic inorganic assemblies. The molecular arrangement of the interleaved dye molecule is proposed by 1D electronic density projection along the stacking direction for the hydrothermally treated samples with alternatively a highly inclined orientation of EB and CB and a parallel-bilayer arrangement for NB. Blue coloured LDH assemblies were subsequently dispersed into polystyrene (PS). It was found that the hybrid fillers do not interfere in the radical polymerization of styrene, giving rise to similar molecular weight and polydispersity than filler free PS, while higher glass transition temperatures were obtained for the nanocomposites. This was consistent with the rheological behaviour with the observation for LDH/NB filler based nanocomposite of shear thinning exponent different from zero, underlining frictional interaction between filler and PS chain. The absorption maximum slightly blue-shifted for the hybrid filler in comparison to the corresponding organic dye was found unmodified for the PS nanocomposite, thus giving rise to blue coloured plastic films, reminiscent somehow of the blue Maya effect.

Staging during anion-exchange intercalation into [LiAl2(OH)6]Cl.yH2O: structural and mechanistic insights.

A series of experiments has been performed to seek more insight into the staging process that occurs during anion-exchange intercalation of some organic carboxylates and phosphonates into the layered double hydroxide [LiAl2(OH)6]Cl.yH2O. High resolution transmission electron microscopy has been employed to gain additional insight into the second-stage intermediates, providing strong evidence that the Rüdorff model of staging is applicable. Small-angle X-ray scattering was used to study the very early stages of the intercalation of succinate into [LiAl2(OH)6]Cl.yH2O: it was observed that the only species present during the reaction were the host, a second-stage intermediate and the first-stage product. The influence of temperature and solvent on the reaction mechanism was investigated. Staging was observed only at low temperatures (T<60 degrees C), and found to be confined largely to aqueous systems. Reactions performed in a 95:5 (v/v) mixture of water and a second non-aqueous solvent such as ethanol, acetone, THF or formamide proceeded via a second-stage intermediate, whereas for those undertaken in 50:50 (v/v) mixtures a direct transformation from host to product was usually observed.

Self-assembly and characterization of layered double hydroxide/DNA hybrids.

The purpose of this study was to control the fabrication of new labile supramolecular assemblies by formulating associations of DNA molecules with inorganic layered double hydroxides (LDHs). The results show that LDH/DNA hybrids synthesized by a coprecipitation route involving the in situ formation of LDHs around DNA molecules acting as templates were characterized by a lamellar organization, with DNA molecules sandwiched between hydroxide layers, exhibiting a regular spacing of 1.96 nm. Our results indicate that labile complexes resulting from the association of nucleic acids and inorganic materials can be obtained not only by anion exchange but also by a direct self-assembly route.