Probing capping mechanisms and polymer matrix loading of biogenic vaterite CaCO3-Ag hybrid through X-ray photoelectron spectroscopy (XPS).

Despite extensive research in the literature, the synthesis of silver nanoparticles (AgNPs) via capping mechanisms remains incompletely understood. This study employs a mechanistic approach to unravel the underlying molecular interactions driving the capping process of biogenic vaterite CaCO3-Ag and explores their interactions with different polymer matrices. X-ray photoelectron spectroscopy (XPS) was used to reveal the capping mechanisms, surface composition alterations, and vaterite polymorph transitions. The oxidation states of AgNPs exhibited distinct changes under different capping agents. The Ag3d spin-orbit splitting profiles revealed the coexistence of Ag+ and Ag0 within CaCO3-Ag, with a significant presence of Ag0 when poly(sodium 4-styrene sulfonate) was employed as the capping agent. Conversely, the use of carboxy methyl cellulose as the capping agent resulted in Ag+ dominance. XPS analysis illuminated the transformation of CaCO3 polymorphs from calcite to vaterite structure, which remained stable following embedding within polymer matrices. Integrating CaCO3-Ag microspheres into polymer matrices and investigating their surface characteristics represents a strategic step toward tailoring material properties for potential applications in active packaging and biomedicine.

Biogenic Vaterite Calcium Carbonate-Silver/Poly(Vinyl Alcohol) Film for Wound Dressing.

Vaterite, a spherical polymorph of CaCO3, shows potential as a carrier for the stable and controlled release of silver nanoparticles (AgNPs), preventing their aggregation or loss of efficacy during application. Furthermore, the embedding of CaCO3-Ag in a poly(vinyl alcohol) (PVA) matrix helps effectively encapsulate and protect the CaCO3-Ag microspheres and provides mechanical stability for better contact with the wound surface. This article focuses on the fabrication of an antimicrobial and biocompatible absorbent film embedded with precipitated biogenic vaterite CaCO3-Ag microspheres. The impact of vaterite CaCO3-Ag on the physical, chemical, nanomechanical, biocompatibility, and antimicrobial properties of the PVA films was investigated. The morphology study revealed a bilayer film structure with an inactive and active surface containing homogeneously distributed vaterite CaCO3-Ag. The X-ray photoelectron spectroscopy (XPS) analysis of the spin-orbit splitting in the Ag 3d5/2 and Ag 3d3/2 peaks indicated the presence of both metallic and ionic states of silver in vaterite CaCO3-Ag prior to its incorporation into the PVA polymer matrix. However, upon embedding in the PVA matrix, a subsequent transformation to solely ionic states was observed. The nanomechanical properties of PVA improved, and the reduced modulus and hardness increased to 14.62 ± 5.23 and 0.64 ± 0.29 GPa, respectively. The films demonstrate a significant activity toward Gram-negative Escherichia coli bacteria. The release of AgNPs was studied in both open and closed systems at pH 6, mimicking the pH environment of the wound, and it demonstrated a dependency on the type of capping agent used for synthesis and loading of AgNPs. The results further revealed the biocompatibility of the prepared films with human dermal fibroblast cells at a concentration of ≤5 mg/mL, making them applicable and functional for wound dressing applications.

Tuning polymorphs of precipitated calcium carbonate from discarded eggshells: effects of polyelectrolyte and salt concentration.

Biowaste eggshells are a valuable source of calcium carbonate suitable for various applications. In this study, spherical vaterite and calcite calcium carbonate polymorphs have been synthesised from discarded eggshells by the precipitation technique at ambient temperature. The influence of initial salt concentration with different polyelectrolytes such as ethylene glycol (EG), polyethylene glycol (PEG, 600 and 6000), and poly(sodium 4-styrenesulfonate) (PSS) at various w/v% concentrations on the polymorph crystal formation of precipitated calcium carbonate (PCC) particles was studied. The results indicated that PCC crystals with spherical, star-shaped and yarn shaped morphologies can be obtained based on the concentration of calcium ions and the presence of different polyelectrolyte solution. At low salt molar concentration, PEG-6000 and PSS polyelectrolytes were found to promote the formation of spherical vaterite calcium carbonate particles with particle mean diameters of 5.05 µm and 2.17 µm, respectively. Furthermore, silver nanoparticles were also loaded into the PCC particles in situ, and the surface area significantly increased from 2.2813 m2 g-1 in untreated ground eggshells to 30.4632 m2 g-1 in PCC particles in the presence of PSS and silver colloid solution. The EDS mapping revealed the average wt% of silver atoms loaded in PCC particles in the presence of PSS polyelectrolyte was lower (1.44 wt%) than in the presence of PEG-6000 (4.27 wt%) due to the silver encapsulation possibility during the core-shell formation, as confirmed by SEM images. The silver nanoparticle-loaded PCC particles in this study can be incorporated into the polymer matrix and employed for antimicrobial food packaging or wound dressing application.

Biocompatibility and biodegradability of filler encapsulated chloroacetated natural rubber/polyvinyl alcohol nanofiber for wound dressing.

The novel biodegradable films of chloroacetated natural rubber/polyvinyl alcohol (CNR/PVA) (55/45 wt%) non-woven nanofiber films encapsulated with kaolin and starch (2.5 and 5 wt%) were produced successfully by green electrospinning technique. The effect of fillers with different content on the physical, chemical, mechanical, biocompatibility and biodegradation properties of CNR/PVA nanofiber films were investigated. The higher crystallinity obtained in CNR/PVA encapsulate with 2.5 wt% kaolin and nanofibers were formed with the maximum diameter distribution and mean value of 40-160 nm and 94.15 ±â€¯54.19 nm respectively. DSC and DMA revealed the kaolin can improve the interfacial adhesion between CNR and PVA and contribute to enhancing the chemical interactions. The mechanical properties improved upon encapsulation of starch and kaolin and more favourable nanofibers with smaller diameter obtained using kaolin rather than starch. The cytotoxicity results revealed the viability of the prepared nanofiber films with human dermal fibroblast cell. Furthermore, the incorporation of starch and kaolin accelerated the degradation rate and the highest enzymatic degradation obtained with 2.5 wt% of starch. The prepared nanofiber films have the potential to be applied for the skin tissue engineering scaffold applications.

An experimental and theoretical study on the interaction of DNA and BSA with novel Ni2+, Cu2+ and VO2+ complexes derived from vanillin bidentate Schiff base ligand.

In this investigation, the structure of bidentate N,N-Schiff base ligand of vanillin, (E)-4-(((2-amino-5-nitrophenyl)imino)methyl)-2-methoxyphenol (HL) was determined by single crystal X-ray diffraction. The interaction of new [CuL2], [NiL2] and [VOL2] complexes with DNA and BSA was explored through UV-Vis and fluorescence spectroscopy. The electronic spectra changes displayed an isosbestic point for the complexes upon titration with DNA. The Kb values for the complexes [CuL2], [NiL2] and [VOL2] were 2.4×105, 1.9×105 and 4.2×104, respectively. [CuL2] complex was bound more toughly than [NiL2] and [VOL2] complexes. These complexes had a significant interaction with Bovine Serum Albumin (BSA) and the results demonstrated that the quenching mechanism was a static procedure. Also, the complexes interacted with BSA by more than one binding site (n>1). Finally, the theoretical studies were performed using the docking method to calculate the binding constants and recognize the binding site of the DNA and BSA with the complexes. The ligand and complexes including Ni2+, Cu2+ and VO2+ ions were colonized by fungal growth.

Immobilization of cobalt(III) Schiff base complexes onto Montmorillonite-K10: Synthesis, experimental and theoretical structural determination.

The [Co(naphophen)(PPh3)(OH2)]ClO4 and [Co(naphophen)(PBu3)(OH2)]BF4 (where naphophen=bis(naphthaldehyde)1,2-phenylenediimine) complexes were synthesized and chracterized by FT-IR, UV-Vis, (1)H NMR, (13)C NMR spectroscopy and elemental analysis techniques. The coordination geometry of the synthesized complexes were determined by X-ray crystallography. Cobalt (III) complexes have six-coordinated pseudo-octahedral geometry in which the O(1), O(2), N(1) and N(2) atoms of the Schiff base forms the equatorial plane. These complexes showed a dimeric structure via hydrogen bonding between the phenolate oxygen and the hydrogens of the coordinated H2O molecule. The theoretical calculations were also performed to optimize the structure of the complexes in the gas phase to confirm the structures proposed by X-ray crystallography. In addition, UV-Visible and IR spectra of complexes were calculated and compared with the corresponding experimental spectra to complete the experimental structural identification. The synthesized complexes were incorporated onto the Montmorillonite-K10 nanoclay via simple ion-exchange reaction. The structure and morphology of the obtained nanohybrids were identified by FT-IR, XRD, TGA/DTA, SEM and TEM techniques. Based on the XRD results of the new nanohybrid materials, the Schiff base complexes were intercalated in the interlayer spaces of clay. SEM and TEM micrographs of the clay/complex shows that the resulting hybrid nanomaterials has layer structures.

Novel nanohybrids of cobalt(III) Schiff base complexes and clay: synthesis and structural determinations.

The [Co(Me(2)Salen)(PBu(3))(OH(2))]BF4 and [Co(Me(2)Salen)(PPh(3))(Solv)]BF(4), complexes were synthesized and characterized by FT-IR, UV-Vis, (1)H NMR spectroscopy and elemental analysis techniques. The coordination geometry of [Co(Me(2)Salen)(PPh(3))(H(2)O)]BF(4) was determined by X-ray crystallography. It has been found that the complex is containing [Co(Me(2)Salen)(PPh(3))(H(2)O)]BF(4) and [Co(Me(2)Salen)(PPh(3))(EtOH)]BF(4) hexacoordinate species in the solid state. Cobalt atom exhibits a distorted octahedral geometry and the Me(2)Salen ligand has the N2O2 coordinated environment in the equatorial plane. The [Co(Me(2)Salen)(PPh(3))(H(2)O)]BF(4) complex shows a dimeric structure via hydrogen bonding between the phenolate oxygen and hydrogens of coordinated H2O molecule. These complexes were incorporated into Montmorillonite-K10 nanoclay. The modified clays were identified by FT-IR, XRD, EDX, TGA/DTA, SEM and TEM techniques. According to the XRD results of the new nanohybrid materials, the Schiff base complexes are intercalated in the interlayer spaces of the clay. SEM and TEM micrographs show that the resulting hybrid nanomaterials have layer structures. Also, TGA/DTG results show that the intercalation reaction was taken place successfully.