Presence Of Zn Research Articles

A cocktail of Cu2+- and Zn2+-peptoid-based chelators can stop ROS formation for Alzheimer's disease therapy.

The formation of reactive oxygen species (ROS) in the brain is a major cause of neuropathologic degradation associated with Alzheimer's Disease (AD). It has been suggested that the copper (Cu)-amyloid-β (Aβ) peptide complex can lead to ROS formation in the brain. An external chelator for Cu that can extract Cu from the CuAβ complex should inhibit the formation of ROS, making Cu chelation an excellent therapeutic approach for AD. Such a chelator should possess high selectivity for Cu over zinc (Zn), which is also present within the synaptic cleft. However, such selectivity is generally hard to achieve in one molecule due to the similarities in the binding preferences of these two metal ions. As an alternative to monotherapy (where Cu extraction is performed using a single chelator), herein we describe a variation of combination therapy - a novel cocktail approach, which is based on the co-administration of two structurally different peptidomimetic chelators, aiming to target both Cu2+ and Zn2+ ions simultaneously but independently from each other. Based on rigorous spectroscopic experiments, we demonstrate that our peptidomimetic cocktail allows, for the first time, the complete and immediate inhibition of ROS production by the CuAβ complex in the presence of Zn2+. In addition, we further demonstrate the high stability of the cocktail under simulated physiological conditions and its resistance to proteolytic degradation by trypsin and report the water/n-octanol partition coefficient, initially assessing the blood-brain barrier (BBB) permeability potential of the chelators.

Delivery system for dexamethasone phosphate based on a Zn2+-crosslinked polyelectrolyte complex of diethylaminoethyl chitosan and chondroitin sulfate

Hybrid nano- and microparticles based on metal ion crosslinked biopolymers are promising carriers for the development of drug delivery systems with improved biopharmaceutical properties. In this work, dexamethasone phosphate-containing particles based on chondroitin sulfate and chitosan or diethylaminoethyl chitosan additionally crosslinked with Zn2+ were prepared. Depending on the polycation/polyanion ratio in the system, anionic and cationic polyelectrolyte complexes (PECs) were obtained. The anionic Zn2+-containing and Zn2+-free PECs had sizes of 154 and 180 nm and ζ-potentials of −22.4 and −27.5 mV, respectively. The cationic Zn2+-containing and Zn2+-free PECs had sizes of 242 and 362 nm and ζ-potentials of 22.4 and 24.7 mV, respectively. The presence of Zn2+ in the system significantly prolonged the release of dexamethasone phosphate from the hybrid polyelectrolyte particle. The resulting release profiles of dexamethasone phosphate were in agreement with the Peppas-Sahlin kinetic model, which considers the combined effects of Fickian diffusion and polymer chain relaxation on the drug release rate. It was shown that the prolongation of drug release was mainly due to swelling and relaxation of the Zn2+ crosslinked polymers. The developed particles exhibited good mucoadhesive properties and pronounced anti-inflammatory activity, making them attractive candidates for biomedical applications.

The crystal structures of Imine-Enamine ‘tautomerism’ in solid state and “turn on” sensing for Zn2+: spectroscopy, DFT and cell imaging studies

The crystallographically established ligand 2-((E)-(benzyl imino)methyl)-4-bromophenol (HL) (existing keto at 296 K and enol at 120 K in the solid state), which is in equilibrium of interconversion (ΔE) = 4.39Kcal) with its tautomer, showed weak emission in the excited state, due to the fact of PET but in the presence of Zn2+, PET was blocked and chelation-enhanced fluorescence (CHEF) was set up. It exhibits 'turn on' sensor with the coordination of Zn2+. Among various metal ions, the synthesised probe HL selectively detected Zn2+ and LOD was about to ∼ 1.63 µM. The Zn(II) coordinated complex and the relative stabilities of the tautomers of HL were thoroughly calculated by spectroscopic and computational studies. Furthermore, cell imaging was also performed to validate the sensing property as well as cyto-toxicity of the probe.

Topological Synthesis of 2D High-Entropy Multimetallic (Oxy)hydroxide for Enhanced Lattice Oxygen Oxidation Mechanism.

Owing to sluggish reaction kinetics and high potential, oxygen evolution reaction (OER) electrocatalysts face a trade-off between activity and stability. Herein, an innovative topological strategy is presented for preparing 2D multimetallic (oxy)hydroxide, including ternary CoFeZn, quaternary CoFeMnZn, and high-entropy CoFeMnCuZn. The key to the synthesis lies in using Ca-rich brownmillerite oxide as a precursor, which possesses inherent structural flexibility enabling tailored elemental adjustments and topologically transforms from a point-shared structure of metal-oxygen octahedrons into an edge-shared structure under alkaline conditions. The presence of Zn in the catalysts causes a shift in the center of the O2p band toward the Fermi level, resulting in more Co4+ species, which drive holes into oxygen ligands to promote intramolecular oxygen coupling. The triggered lattice oxidation mechanism is identified by detecting peroxo-like (O2 2-) negative species using tetramethylammonium chemical probe, along with 18O isotope labeling experiments. As a result, the catalyst demonstrates an overpotential of 267mV at 10 mA cm-2, ranking it among the top-performing non-Ni-based catalysts. Importantly, the catalysts also show high Fe-leaching resistance during OER compared to conventional NiFe and CoFe hydroxides/(oxy)hydroxides. The assembled zinc-air battery enables stable operation for over 225 h at a low charging voltage of 1.93V.

An Improved and Efficient Practical Process for the Synthesis of Enantiomerically Pure Solifenacin Succinate as an Antimuscarinic Agent

Background: Solifenacin succinate is an active pharmaceutical drug molecule that is extremely effective in treating overactive bladder symptoms, such as urine incontinence, urgency, and frequent urination. The free base is yellow oil, and the salt solifenacin succinate forms yellowish crystals that are extremely stable and effective. Solifenacin is a very active antagonist due to its potent muscarinic M3 receptor antagonist characteristics. Furthermore, solifenacin is effective in the treatment of bowel syndrome (IBS) by blocking M3 receptors and a broad spectrum of bowel dysfunction. Objective: The objective of this study was to develop a practical and highly efficient scalable synthesis of enantiomerically pure solifenacin as an antimuscarinic agent. Methods: In this work, the Zn(OTf)2 catalyst was used to develop a novel, environmentally benign, high-yielding, and robust protocol for the synthesis of enantiomerically pure solifenacin succinate. Results: The synthesis of enantiomerically pure solifenacin succinate was achieved in seven steps using commercially available phenylethylamine and benzoyl chloride as the starting materials. We carried out the reaction optimization by treatment of (S)-1-phenyl-3,4-dihydroisoquinoline-2(1H)- carbonyl chloride and (R)-(-)-3-Quinuclidinolin in the presence of Zn(OTf)2 catalyst. Furthermore, the solifenacin-free base was treated with succinic acid to afford its corresponding salt. The highlight of this protocol is the use of 20 mol% Zn(OTf)2 catalyst for the first time. The readily available starting materials, robustness, easy operation, high yield, and low cost make the approach more attractive and highly applicable. Conclusion: In summary, we developed a novel Zn(OTf)2-catalysed environmentally benign, highyielding, and robust protocol for the synthesis of enantiomerically pure solifenacin succinate. The proposed strategy is highly cost-effective and avoids the use of hazardous and unsafe sensitive, strong bases as well as tedious work-up procedures. Effective synthesis was achieved using readily available starting materials and reagents. Thus, the protocol is highly efficient, compatible, and commercially viable for the synthesis of important solifenacin products.

White Light Emission from Zn(II) and DMSO-Induced Copper Nanocluster Assembly.

An assembly of metal nanoclusters driven by appropriate surface ligands and solvent environment may engender entirely new photoluminescence (PL). Herein, we first synthesize histidine (His) stabilized copper nanoparticles (CuNPs) and, subsequently, copper nanoclusters (CuNCs) from it using 3-mercaptopropionic acid (MPA) as an etchant. The CuNCs originally emit bluish-green (λem=470 nm) PL with a low quantum yield (QY∼1.8 %). However, it transformed into a dual-emissive nanocluster assembly (Zn-CuNCs) in the presence of Zn(II) salt, having a distinct blue emission band (λem=420 nm) and a red emission band (λem=615 nm) with eight times QY (∼9.1 %) enhancement. The temperature-dependent emission spectra of Zn-CuNCs depicted that the blue emission band persists for all the temperature ranges (0-80 °C) while the red emission band vanishes at high temperatures (70-80 °C). Thus, the blue emission may originate from the locally excited state (LES) emission of the nanoclusters, while the red emission originates from through-space interaction (TSI) and Cu(I)…Cu(I) interaction within the assembly. Adding dimethyl sulfoxide (DMSO) further modifies the emission intensities; the red band was amplified four times, while the blue band was diminished by 2.5 times. The transmission electron microscopy (TEM) images unveiled that the Zn-CuNCs are a large assembly of tiny nanoclusters, which become more compact in DMSO. The blue emission possesses steady-state fluorescence anisotropy, while the red emission shows no anisotropy. Further, near-perfect white light emission(WLE) was rendered with CIE coordinates of (0.33, 0.32) by combining the dual emission of the Zn-CuNCs with the original green emission of the CuNCs.

A comparative study of the efficacy of alginate lyases in the presence of metal ions elevated in the cystic fibrosis lung milieu

Pseudomonas aeruginosa, a common cause of morbidity in cystic fibrosis, chronically infects the patient's lungs by forming an alginate-containing biofilm. Alginate lyases are polysaccharide lyases that lyse alginate and are, therefore, potential biofilm-disruptive agents. However, cystic fibrosis sputum contains high levels of metals such as iron and zinc. The efficacy of alginate lyases under these conditions of elevated metal concentrations has not been categorically determined. Here, we have assessed the enzyme activity of two exolytic and five endolytic alginate lyases in the presence of metal ions (Fe2+, Zn2+, Mn2+, Mg2+, Ca2+, Ni2+, Cu2+) elevated in the cystic fibrosis lung milieu. Several of these alginate lyases exhibited increased activity in the presence of Ca2+, and the polysaccharide lyase family 7 members studied here exhibited decreased activity in the presence of Zn2+. The enzyme activity of the PL7 alginate lyases from Cellulophaga algicola (CaAly/CaFLDAly) and Vibrio sp. (VspAlyVI) was not affected in the presence of a mix of all the above-mentioned metal ions at the elevated concentrations found in the cystic fibrosis lung milieu. Specific alginate lyases might, therefore, retain the ability to degrade the alginate-containing Pseudomonas biofilm in the presence of metal ions elevated in the cystic fibrosis lung milieu.

Cloning, Expression, and Characterization of a Metalloprotease from Thermophilic Bacterium Streptomyces thermovulgaris.

Proteases hydrolyze proteins and reduce them to smaller peptides or amino acids. Besides many biological processes, proteases play a crucial in different industrial applications. A 792 bp protease gene (nprB) from the thermophilic bacterium Streptomyces thermovulgaris was cloned and expressed in E. coli BL21 using pET 50b (+). Optimal recombinant protease expression was observed at 1 mM IPTG, 37 °C for 4 h. The resulting protease was observed in soluble form. The molecular mass estimated by SDS-PAGE and Western blot analysis of the protease (NprB) fused with His and Nus tag is ~70 KDa. The protease protein was purified by Ammonium sulfate precipitation and immobilized metal ion affinity chromatography. The optimum pH and temperature for protease activity using casein as substrate were 7.2 and 70 °C, respectively. The mature protease was active and retained 80% of its activity in a broad spectrum of pH 6-8 after 4 h of incubation. Also, the half-life of the protease at 70 °C was 4 h. EDTA (5 mM) completely inhibited the enzyme, proving the isolated protease was a metalloprotease. NprB activity was enhanced in the presence of Zn2+, Mn2+, Fe2+ and Ca2+, while Hg2+ and Ni2+ decreased its activity. Exposure to organic solvents did not affect the protease activity. The recombinant protease was stable in the presence of 10% organic solvents and surfactants. Further characterization showed that zinc-metalloprotease is promising for the detergent, laundry, leather, and pharmaceutical industries.

Zn-doped tubular graphene nitride for visible light and sacrificial-agent-free H2O2 photosynthesis in water

Graphitic carbon nitride (g-C3N4) has become a favored universal photocatalyst. Despite its numerous advantages, the photocatalytic efficiency of g-C3N4 is hindered by the substantial recombination of photoexcited charge carriers and holes. In this work, we demonstrate that Zn-doped tubular carbon nitride photocatalyst (Zn-tCN) can serve as highly efficient catalysts for H2O2 photosynthesis. Mechanism studies confirm that the presence of Zn in g-C3N4 prolongs the lifetimes of photogenerated carriers and inhibits their recombination, which triggers the reduction of O2 to reaction intermediates (O2−), as supported by in situ electron paramagnetic resonance (EPR) spectroscopy. More importantly, sacrificial agent experiments coupled with in situ EPR results confirmed that the reaction mechanism involves a concerted two-electron transfer process. The optimal catalyst displays a H2O2 productivity of 162.4μmol g–1h−1 under visible-light irradiation without a sacrificial agent, which is 11.7 times higher than that of pristine g-C3N4 (13.8μmol g–1h−1). This work proposes a synthetic strategy for the preparation of high-performance Zn-doped g-C3N4, which offers insights and perspectives for developing highly active photocatalysts and deepening the understanding of photocatalytic mechanisms.

Electrochemical, Structural, and Hyperspectral Imaging Investigation of Bifunctional Zn-Air Battery Gas-Diffusion Electrodes

Rechargeable Zinc-air batteries (RZAB) emerge as highly promising solutions for electrochemical energy storage (EES) applications. Nevertheless, a noteworthy drawback in the existing generation of these batteries lies in the air gas-diffusion electrode (GDE). This component grapples with issues related to both efficiency and durability. In response to this challenge, our research is concentrated on the creation of a novel GDE, accompanied by an in-depth examination of its electrochemical, structural, and compositional characteristics. The primary objective is to comprehensively assess the physico-chemical factors that exert an influence on its efficiency and durability. In the case of the present research, two different catalysts were chosen for the ORR (discharge) and OER (charge) electrocatalysis, namely α-MnO2 nanorods (NR) and Ni nanoparticles (NP), respectively. The GDEs were produced by applying a water-based catalyst ink, augmented with PTFE and C-black, through spray-coating onto a carbon paper support, which serves as the gas diffusion layer (GDL). Initially, the ideal proportion of OER/ORR catalyst was determined by conducting electrochemical tests on both the individual material (via RRDE studies) and the gas diffusion electrode using a rapid screening protocol. The material extracted from the GDEs, in pristine state and after ageing under operating conditions, was then characterized with electrochemical methods, SEM microscopy, HRTEM/SAED microscopy/electron diffraction, as well as with direct- and Fourier-space soft x-ray transmission microscopy (STXM) at the Mn, Ni and Zn L-edges. The electrochemical tests conducted in this study demonstrated a progressive improvement in performance as the nickel nanoparticle content increased, until a plateau is reached after 23% wt. Specifically, lower overpotentials were observed alongside increased cyclic stability for the combined ORR/OER processes. These assessments were conducted in two distinct electrolyte environments: pure KOH and KOH with the inclusion of Zn2+. The inclusion of Zn2+ aimed to replicate and understand the potential impact of anode chemistry on the cathode's overall performance. The investigation employed HRTEM and SAED analyses to meticulously monitor alterations in the crystal structure of the α-MnO2 electrocatalyst under diverse aging conditions. Notably, during ORR cycling, the manganese nanorods underwent amorphization. However, cyclic processes between oxygen OER and ORR revealed the recovering of the original crystalline phase. The introduction of Zn2+ into the system resulted in the formation of a partially amorphous Zn-Mn mixed oxide. To delve further into the nuanced changes, soft-X ray hyperspectral imaging, both in direct and Fourier space was employed. By spectral imaging at the Mn and Ni L-edges, we could assess the space-dependent valence alterations of Manganese and Nickel at different stages of aging with space resolution down to a few tens of nanometers. The integration of diverse analytical techniques, including electrochemical assessments, STXM, HRTEM/ SAED imaging, along with space-resolved structural analyses, has provided a comprehensive, molecular-level understanding of the performance and degradation of bifunctional ORR/OER electrocatalysts within the realistic context of gas diffusion electrodes. Of particular significance is the capability of this combined approach to meticulously trace and correlate the changes in the chemical state of the manganese ORR electrocatalyst. This shift, notably away from the optimal 3+/4+ mixed valence state, was observed in response to aging and Zn2+ contamination. The correlation of this chemical state drift with electrochemical conditions and the evolution of crystal structure adds a nuanced layer of insight into the intricate interplay of factors influencing the performance and degradation of these electrocatalysts. In particular, the control of the oxidative stress under OER, enabled by addition of Ni NPs, was correlated with preservation of α-MnO2 crystallinity, GDE operation in the presence of Zn2+ was proved to give rise to the formation of ZnMn2O4, poisoning the electrocatalyst. Lastly, the role of hydrophobicity of the active layer of the GDE was proven to be of crucial importance in the stability of the Mn-based catalyst, as PTFE-surrounded clusters were observed to be less affected by cycling with respect to others which clearly underwent electrolyte flooding. Figure 1

The role of zinc addition on the microstructural evolution and mechanical properties of wire-arc directed energy deposited Mg-Gd-Y-(Zn)-Zr alloys

Wire-arc directed energy deposition (WA-DED) demonstrates significant potential in the rapid and free forming of high-strength magnesium rare-earth (Mg-RE) alloys. This highlights a growing demand for tailored wire alloy compositions to promote engineering applications of this technology. In this work, the role of zinc addition on WA-DED processed Mg-Gd-Y based alloys has been thoroughly investigated by utilizing Mg-6Gd-3Y-0.5Zr (wt.%, GW63K) and Mg-6Gd-3Y-0.5Zn-0.5Zr (wt.%, GWZ631K) alloy wires as model materials. The microstructure evolution of these two alloys during deposition and heat treatment is revealed by multi-scale microstructure characterization techniques. The influences of Zn addition on mechanical properties of these deposited alloys are investigated comparatively. Obtained results indicate that addition of Zn element into Mg-Gd-Y based alloys promotes phase transformation between eutectic phases and long period stacking order (LPSO) phases during the WA-DED deposition process owing to the multiple thermal cycling. More importantly, the addition of Zn element increases the tendency of solidification shrinkage of the deposited metal. During high-temperature solid solution treatment, the presence of Zn is conducive to improving the thermal stability of the as-deposited grain boundaries and thus suppressing grain coarsening. After optimized T6 treatments, the strength of GW63K alloys increases to 374±7MPa, and is obviously higher than that (315±6MPa) of GWZ631K alloys. The addition of Zn element weakens the precipitation strengthening effect. This can be attributed to the formation of LPSO phases, which consumes a substantial amount of RE elements, and in turn decreases the density of aging precipitated nanoscale β´ phases. This work promotes the understanding of the non-equilibrium solidified microstructure evolution of multi-component Mg-RE alloys and guides the optimization of alloy composition of WA-DED specific wire materials.

From biodiversity to bioresources: evaluation of potentialities in mycoremediation of fungal bioresources isolated from an Italian decommissioned military site

Military sites, both active and decommissioned, are rarely studied and may represent a source of fungal bioresources with potential applications for the remediation of co-contaminated soils. The aims of this study were both deepening the knowledge on fungal communities of a decommissioned military site and identifying indigenous bioresources showing potentialities for downstream mycoremediation applications. The culturable fractions of soil fungal communities of an Italian decommissioned military site were isolated from six representative sampling plots. In addition, the fungal community of the rhizosphere of Plantago lanceolata was also isolated. α and β diversity indices were used to analyze biodiversity data of the isolated fungal communities. A polycyclic aromatic hydrocarbons (PAHs) enrichment microplate experiment in the presence of Zn, Pb, and Zn-Pb co-contamination was conducted, followed by in vitro functional traits screenings, to select the isolates with the best potential for future mycoremediation applications. Globally 101 taxa, accounting for a total of 546 strains, were isolated from the samples. The enrichment results highlighted several fungal species showing the ability to use PAHs as nutritional source, even in the co-presence of potentially toxic elements. Finally, the analysis of their functional traits revealed their potential for biotechnological applications in soil detoxification.

A ratiometric, turn-on fluorosensor for specific detection of Zn2+ ions

A potentially active fluorescent chemosensor (E)-2-(((2-(1H-benzo[d]imidazol-2-yl)phenyl)imino)methyl)-5-(diethylamino)phenol (BMDP) is developed by the condensation of 2-(2-aminophenyl)-1H-benzimidazole and 4-(diethylamino)salicylaldehyde. It shows an exceptional ratiometric fluorescence behavior when exposed to Zn2+ ions and the photoluminescence color is changed from blue to cyan under the exposure of a 365 nm UV light which is also strongly evident from the color chromaticity diagram. The exceptional ratiometric fluorescence behavior in the presence of Zn2+ ions is found to be due to the chelation-enhanced fluorescence (CHEF). The 1:1 stoichiometry of BMDP and Zn2+ ions in Zn2+ ions chelated BMDP complex is confirmed through Job’s plot analysis. Remarkably, Cd2+ does not interfere with the selective ratiometric fluorescence behavior induced by Zn2+ ions. The lowest detection limit and quantification limit are estimated to be 28 nM and 92 nM respectively. The cyan fluorescence of the Zn2+ ions chelated BMDP complex is interestingly reversed to the original BMDP in the presence of ethylenediamine tetraacetic acid (EDTA). At the molecular level, this can be thought of as a complimentary “INHIBIT” logic gate. Furthermore, it is possible to utilize the probe for on-site identification in test strips with improved Zn2+ ions selectivity. We have also used a smartphone-based method to demonstrate the usefulness of BMDP for the immediate quantification and detection of Zn2+ ions. In light of this, probe BMDP is a trustworthy fluorescence probe for on-site monitoring that can accurately identify Zn2+ ions even when some other metals and anions compete.

Evaluating the impact of ZnO doping on electrical and thermal properties of calcium-aluminosilicate oxynitride glass-ceramics

This study aimed to investigate the impact of ZnO content on the structure, thermal, and electrical properties of oxynitride glass-ceramic(s) within the Ca–Al–Si–O–N (CASON) system. The base glass had the composition of Ca7Al14Si17O52N7, with ZnO additions ranging from 3 to 15 % by weight. A pristine Ca7Al14Si17O52N7 glass was successfully prepared by melt-quenching technique followed by converted into glass-ceramic by incorporating various amounts of ZnO using the field-assisted sintering technique. XRD and FESEM analysis confirmed that increasing the amount of Zn increases the crystallinity in the glass matrix. The observed crystalline phases were formed mostly from ZnO and showed higher conductivity than the remaining dielectric matrix. IR spectra confirmed the presence of bands correlated with the presence of Zn and suggested the progressive depolymerization of the silicate-aluminate network as a consequence of increasing Zn content. Density values varied between 2.75 and 2.94 gcm−3 and increased with increasing the Zn content in the glass-ceramic. The thermal expansion and thermal conductivity values increased and decreased, respectively, with the increase of Zn content in the matrix. The electrical properties of the samples were investigated using impedance spectroscopy over a wide range of frequencies (10 mHz to 1 MHz) and temperatures (153 K–623 K). The results showed that in the glass without ZnO and glass-ceramic(s) with a small addition of ZnO, the conductivity is mainly dominated by the transfer of oxygen ions and, to a small extent, by the presence of electronic conductivity. As the ZnO content increases, continuous conduction paths are formed between the ZnO crystallites, and the electrical conductivity increases rapidly and becomes dominated by electron transfer.

TEM beam-induced generation of Zn nanocrystals from a polymer-encapsulated Zn(II) complex

A novel Zn(II) complex viz., [Zn(phen)(DTT)] (1) where DTT = 4-methyl-1,2-benzenedithiolate and phen = 1,10-phenanthroline was synthesized and characterized. The X-ray crystal structure of 1 indicated its dimeric nature with a distorted square pyramidal geometry around Zn(II). 1 was encapsulated within triblock P123 polymer to develop the micelle ZnMS. Dynamic light scattering data indicated the self-assembly of 1 with P123 in an aqueous solution with a low-dispersity parameter (0.63 ± 0.02). ZnMs on TEM beam irradiation (200 keV) generated Zn nanocrystals of size 90–150 nm. Energy-dispersive X-ray spectroscopy data indicated the presence of Zn, S, and O in the nanocrystals.

A solid-state sensor based on nanosilica/methylcellulose composite and chromoionophore 8-carboxamidoquinoline derivative as an optode pellet for Zinc(II) ion

Zinc is known to play a central role in the immune system that creates a resistance barrier against viral infection. A naked-eye zinc(II) (Zn2+) ion sensor of 2-oxo-2-(quinolin-8-ylamino)acetic acid (OQAA) as a recognition probe was designed and synthesized. By inserting functional groups of amide and carboxylic acid into a conjugated molecule of 8-aminoquinoline, Zn2+ ion (borderline acid) coordinated favorably with aromatic nitrogen atoms (borderline bases) and N-amide. Characterization of OQAA was done by FTIR, 1H NMR, 13C NMR, UV–vis, and ESI-MS. The Zn2+ ion chemosensor was fabricated by immobilizing OQAA chromogenic ionophore onto a nanosilica/methylcellulose (Si/MC) composite pellet to form a solid-state pellet sensor. A distinguishable color change from pale light-yellow to yellowish-brown of the optode pellet was observed in the presence of Zn2+ ions. Optimization of the pellet-based Zn2+ ion sensor was carried out with a fiber optic reflectance spectrophotometer at 0.25 M OQAA in tris buffer (pH 7.4). The optical fiber sensor demonstrated a linear reflectance response between 0.8 M and 2.4 M Zn2+ ion (R²=0.9741) at λmax=635 nm with a limit of detection (LOD) of 3.6 × 10−2 M and response time of 5 min. The reflectance sensor exhibited good selectivity towards Zn2+ ion over other competitive heavy metals e.g., iron(II) (Fe2+), nickel(II) (Ni2+), cobalt(II) (Co2+), copper(II)(Cu2+) and cadmium(Cd2+) ions. Additionally, the proposed Zn2+ ion sensor showed high shelf-life stability of 75 days operational duration with 80.0 % initial optical response remaining. The quick, easy, and uncomplicated preparation of the OQAA-modified Si/MC (OQAA-Si/MC) composite pellet novel material gave a reproducible reflectance signal towards the determination of Zn2+ ion concentration with a low relative standard deviation (RSD) obtained at ∼1.0 % (n=12), and was reusable three times for assay of Zn2+ ion (RSD=1.3 %). The optical chemosensor imparts remarkable color change towards the analysis of Zn2+ ions, and could offer direct and fast in-situ visual inspection of Zn2+ ion levels in complex samples without an instrument.

MgCa-Based Alloys Modified with Zn- and Ga-Doped CaP Coatings Lead to Controlled Degradation and Enhanced Bone Formation in a Sheep Cranium Defect Model.

Mg-based biodegradable metallic implants are gaining increased attraction for applications in orthopedics and dentistry. However, their current applications are hampered by their high rate of corrosion, degradation, and rapid release of ions and gas bubbles into the physiological medium. The aim of the present study is to investigate the osteogenic and angiogenic potential of coated Mg-based implants in a sheep cranial defect model. Although their osteogenic potential was studied to some extent, their potential to regenerate vascularized bone formation was not studied in detail. We have studied the potential of magnesium-calcium (MgCa)-based alloys modified with zinc (Zn)- or gallium (Ga)-doped calcium phosphate (CaP) coatings as a strategy to control their degradation rate while enhancing bone regeneration capacity. MgCa and its implants with CaP coatings (MgCa/CaP) as undoped or as doped with Zn or Ga (MgCa/CaP + Zn and MgCa/CaP + Ga, respectively) were implanted in bone defects created in the sheep cranium. MgCa implants degraded faster than the others at 4 weeks postop and the weight loss was ca. 50%, while it was ca. 15% for MgCa/CaP and <10% in the presence of Zn and Ga with CaP coating. Scanning electron microscopy (SEM) analysis of the implant surfaces also revealed that the MgCa implants had the largest degree of structural breakdown of all the groups. Radiological evaluation revealed that surface modification with CaP to the MgCa implants induced better bone regeneration within the defects as well as the enhancement of bone-implant surface integration. Bone volume (%) within the defect was ca. 25% in the case of MgCa/CaP + Ga, while it was around 15% for undoped MgCa group upon micro-CT evaluation. This >1.5-fold increase in bone regeneration for MgCa/CaP + Ga implant was also observed in the histopathological examination of the H&E- and Masson's trichrome-stained sections. Immunohistochemical analysis of the bone regeneration (antiosteopontin) and neovascularization (anti-CD31) at the defect sites revealed >2-fold increase in the expression of the markers in both Ga- and Zn-doped, CaP-coated implants. Zn-doped implants further presented low inflammatory reaction, notable bone regeneration, and neovascularization among all the implant groups. These findings indicated that Ga- and Zn-doped CaP coating is an important strategy to control the degradation rate as well as to achieve enhanced bone regeneration capacity of the implants made of Mg-based alloys.

Immobilization of collagenase in inorganic hybrid nanoflowers with enhanced stability, proteolytic activity, and their anti-amyloid potential

Organic-inorganic hybrid nanomaterials are considered as promising immobilization matrix for enzymes owing to their markedly enhanced stability and reusability. Herein, collagenase was chosen as a model enzyme to synthesize collagenase hybrid nanoflowers (Col-hNFs). Maximum collagenase activity (155.58 μmol min−1 L−1) and encapsulation yield (90 %) were observed in presence of Zn(II) ions at 0.05 mg/mL collagenase, 120 mM zinc chloride and PBS (pH 7.5). Synthesized Col-Zn-hNFs were extensively characterized by scanning electron microscopy (SEM), energy dispersive X-ray (EDX), X-ray diffraction (XRD), Fourier transform infrared (FTIR), circular dichroism (CD), fluorescence spectroscopy, dynamic light scattering (DLS) and zeta potential measurements. SEM images showed flower-like morphology with average size of 5.1 μm and zeta potential of −14.3 mV. Col-Zn-hNFs demonstrated superior relative activity across wide pH and temperature ranges, presence of organic solvents and surfactants as compared to its free form. Moreover, Col-Zn-hNFs exhibited excellent shelf life stability and favorable reusability. Col-Zn-hNFs showed the ability to suppress and eradicate fully developed insulin fibrils in vitro (IC50 = 2.8 and 6.2 μg/mL, respectively). This indicates a promising inhibitory potential of Col-Zn-hNFs against insulin amyloid fibrillation. The findings suggest that the utilization of Col-Zn-hNFs as a carrier matrix holds immense potential for immobilizing collagenase with improved catalytic properties and biomedical applications.

Enhanced structural, vibrational, and dielectric properties of (Ba0·95Ca0.05) (Ti0.95Zr0.05)1-x(Zn1/3Nb2/3)xO3 ceramics

The (Ba0·95Ca0.05) (Ti0·95Zr0.05)1-x(Zn1/3Nb2/3)xO3 BCZTxZN compounds, were created using the widely adopted solid-state method. To assess the impact of (Zn, Nb: ZN) co-substitution ions we studied the structural, vibrational, and dielectric characteristics of BCZT. The phase purity was validated by conducting Rietveld refinement of XRD data, indicating the coexistence of orthorhombic and tetragonal phases at ambient temperature in the (Ba0·95Ca0.05) (Ti0·95Zr0.05)0.975(Zn1/3Nb2/3)0.025O3 (BCZT25ZN) composition. Furthermore, Raman spectroscopy confirmed the observed transitions. The presence of Zn2+ and Nb5+ ions resulted in a decrease in cell parameters and cell volume. The real part of the dielectric constant and the tangent loss (tan δ) exhibited values of approximately 3380 and 0.031, respectively, for the sample (Ba0·95Ca0.05)(Ti0·95Zr0.05)0.95(Zn1/3Nb2/3)0.05O3 (BCZT50ZN), obtained by substituting ZN in Ba0·95Ca0·05Ti0·95Zr0·05O3. Incorporation of ZN into Ba0·95Ca0·05Ti0·95Zr0·05O3 presents promising prospects for using the material in various device applications, including energy storage capacitors, sensors, and actuators.

One-pot microwave-assisted approach of polydiacetylene/zinc oxide nanocomposite for reversible thermochromic

This study introduces a new technique to fabricate the reversible poly(PCDA/ZnO) nanocomposites thermochromism. Our preparation process is the solution-mixing method, which is supported by microwave synthesis time instead of ultrasonic bath or stirrer. The presence of ethanol molecules in aqueous media in the solution-mixing method induces dipolar polarization. In addition, the presence of Zn2+ leaking out of the ZnO can produce ionic polarization. These factors affect the shape of poly(PCDA/ZnO) nanocomposites based on their thermochromic properties. The optical properties of poly(PCDA/ZnO) nanocomposite were determined through UV-Vis absorption spectroscopy. The morphology of this nanocomposite was examined by scanning electron microscopy, and its crystallinity was investigated by X-ray diffraction. The inter-intrachain interaction was confirmed by infrared spectroscopy. In addition, the poly(PCDA/ZnO) nanocomposite embedding PVA was prepared. The reversible theromochromic properties of poly(PCDA/ZnO) nanocomposites demonstrated a higher color transition temperature with increasing microwave synthesis time. It is an important observation to understand the effect of microwave synthesis time on the morphology and reversible thermochromism of the poly(PCDA/ZnO) nanocomposite