Interaction of ZnO Nanostructures with Proteins: In Vitro Fibrillation/Antifibrillation Studies and in Silico Molecular Docking Simulations

Protein amyloidosis is related to many neurological disorders. Nanoparticles (NPs) due to their small size can regulate both the polypeptide monomers/oligomers assembly into amyloid fibrils/plaques and the disintegration of the existent plaques. Herein, we have synthesized ZnO nanoflowers and polyol-coated ZnO NPs of relatively small size (40 nm) with cylindrical shape, through solvothermal and microwave-assisted routes, respectively. The effect of the different morphology of nanostructures on the fibrillation/antifibrillation process was monitored in bovine serum albumin (BSA) and human insulin (HI) by fluorescence Thioflavin T (ThT) measurements. Although both nanomaterials affected the amyloid formation mechanism as well as their disaggregation, ZnO nanoflowers with their sharp edges exhibited the greatest amyloid degradation rate in both model proteins (73% and 35%, respectively) and inhibited the most the insulin fibril growth, while restrained also the fibrillation process in the case of albumin solution. In silico molecular docking simulations on the crystal structure of BSA and HI were performed to analyze further the observed in vitro activity of ZnO nanostructures. The binding energy of ZnO NPs was found lower for BSA (−5.44), highlighting their ability to act as catalysts in the fibrillation process of albumin monomers

catena-Poly[[copper(II)-bis­[μ-bis­(pyridin-3-yl)methanone-κ2 N:N′]] bis­(tetra­fluorido­borate)]

In the title complex, {[Cu(C11H8N2O)2](BF4)2}n, the CuII ion is situated on an inversion centre and adopts an N4F2 octa­hedral coordination geometry with four N atoms from four different bis­(pyridin-3-yl)methanone ligands at the equatorial sites and two independent tetra­fluoridoborate anions weakly bonded at the axial sites via two F atoms [Cu⋯F = 2.613 (3) Å]. Chains with the bridging ligands are formed along the a axis. C—H⋯F inter­actions stabilize the structure. C—O⋯π inter­actions also occur

Nanocapsules of ZnO Nanorods and Geraniol as a Novel Mean for the Effective Control of Botrytis cinerea in Tomato and Cucumber Plants

Inorganic-based nanoparticle formulations of bioactive compounds are a promising nanoscale application that allow agrochemicals to be entrapped and/or encapsulated, enabling gradual and targeted delivery of their active ingredients. In this context, hydrophobic ZnO@OAm nanorods (NRs) were firstly synthesized and characterized via physicochemical techniques and then encapsulated within the biodegradable and biocompatible sodium dodecyl sulfate (SDS), either separately (ZnO NCs) or in combination with geraniol in the effective ratios of 1:1 (ZnOGer1 NCs), 1:2 (ZnOGer2 NCs), and 1:3 (ZnOGer2 NCs), respectively. The mean hydrodynamic size, polydispersity index (PDI), and ζ-potential of the nanocapsules were determined at different pH values. The efficiency of encapsulation (EE, %) and loading capacity (LC, %) of NCs were also determined. Pharmacokinetics of ZnOGer1 NCs and ZnOGer2 NCs showed a sustainable release profile of geraniol over 96 h and a higher stability at 25 ± 0.5 °C rather than at 35 ± 0.5 °C. ZnOGer1 NCs, ZnOGer2 NCs and ZnO NCs were evaluated in vitro against B. cinerea, and EC50 values were calculated at 176 μg/mL, 150 μg/mL, and > 500 μg/mL, respectively. Subsequently, ZnOGer1 NCs and ZnOGer2 NCs were tested by foliar application on B. cinerea-inoculated tomato and cucumber plants, showing a significant reduction of disease severity. The foliar application of both NCs resulted in more effective inhibition of the pathogen in the infected cucumber plants as compared to the treatment with the chemical fungicide Luna Sensation SC. In contrast, tomato plants treated with ZnOGer2 NCs demonstrated a better inhibition of the disease as compared to the treatment with ZnOGer1 NCs and Luna. None of the treatments caused phytotoxic effects. These results support the potential for the use of the specific NCs as plant protection agents against B. cinerea in agriculture as an effective alternative to synthetic fungicides

Tailoring Ca-Based Nanoparticles by Polyol Process for Use as Nematicidals and pH Adjusters in Agriculture

The remarkable progress in nanotechnology has extended the application of inorganic nanoparticles (NPs) in the agriculture sector, as both economically sustainable and environmentally sound alternatives. Root knot nematodes are undoubtedly a foremost problem of agriculture, and research strives to develop effective materials to tackle this issue. Herein, the microwave-assisted selective polyol synthesis of different compositions of Ca-based NPs, Ca(OH)2, Ca(OH)2/CaCO3, and CaCO3 is reported and the products were evaluated as nematicides and pH adjusters. Two precursors (CaCl2 and Ca(NO3)2) and three polyols (1,2-propylene glycol (PG), tetraethylene glycol (TEG), polyethylene glycol (PEG 8000)) that differ in their redox potential have been utilized to provide selectivity over composition. On the basis of the utilized polyols, NPs are produced as inorganic/organic hybrid formulations with a biocompatible organic coating that provides increased colloidal stability and controlled release of active components. Characterization of NPs has been carried out by XRD, TGA, FTIR, TEM, and pH-metry. Each composition exhibited different pH changing ability, an essential feature for agrochemical applications. The in vitro nematicidal activity of Ca(OH)2, Ca(OH)2/CaCO3, and CaCO3NPs was evaluated on second stage juveniles (J2) of two Meloidogyne species (Meloidogyne incognita and Meloidogyne javanica) based on nematode paralysis experiments. Results unveiled nematicidal activity for all evaluated Ca-based NPs, while Ca(OH)2 and CaCO3 NPs appeared to be the most and the least effective ones, respectively. The nematicidal effect appears to be boosted by the release of [OH]- anions, as indicated by pH-metric measurements, displaying the crucial role of [OH]- anions in their nematicidal activity

Leaf age-dependent effects of foliar-sprayed CuZn nanoparticles on photosynthetic efficiency and ROS generation in <i>Arabidopsis thaliana</i>

Young and mature leaves of Arabidopsis thaliana were exposed by foliar spray to 30 mg L&minus;1 of CuZn nanoparticles (NPs). The NPs were synthesized by a microwave-assisted polyol process and characterized by dynamic light scattering (DLS), X-ray diffraction (XRD), and transmission electron microscopy (TEM). CuZn NPs effects in Arabidopsis leaves were evaluated by chlorophyll fluorescence imaging analysis that revealed spatiotemporal heterogeneity of the quantum efficiency of PSII photochemistry (&Phi;PS&Iota;&Iota;) and the redox state of the plastoquinone (PQ) pool (qp), measured 30 min, 90 min, 180 min, and 240 min after spraying. Photosystem II (PSII) function in young leaves was observed to be negatively influenced, especially 30 min after spraying, at which point increased H2O2 generation was correlated to the lower oxidized state of the PQ pool. Recovery of young leaves photosynthetic efficiency appeared only after 240 min of NPs spray when also the level of ROS accumulation was similar to control leaves. On the contrary, a beneficial effect on PSII function in mature leaves after 30 min of the CuZn NPs spray was observed, with increased &Phi;PS&Iota;&Iota;, an increased electron transport rate (ETR), decreased singlet oxygen (1O2) formation, and H2O2 production at the same level of control leaves.An explanation for this differential response is suggested

(2-Pyrid­yl)[5-(2-pyridyl­carbon­yl)-2-pyrid­yl]methanone

In the centrosymmetric title compound, C17H11N3O2, the dihedral angle between the central and pendant pyridyl rings is 50.29 (9)°. In the crystal, mol­ecules stack along the a axis by π–π inter­actions between the pyridine rings with centroid–centroid distances of 3.845 (2) Å. The N atom and one of the C atoms of the central ring are disordered by symmetry

Impact of Coated Zinc Oxide Nanoparticles on Photosystem II of Tomato Plants

Zinc oxide nanoparticles (ZnO NPs) have emerged as a prominent tool in agriculture. Since photosynthetic function is a significant measurement of phytotoxicity and an assessment tool prior to large-scale agricultural applications, the impact of engineered irregular-shaped ZnO NPs coated with oleylamine (ZnO@OAm NPs) were tested. The ZnO@OAm NPs (crystalline size 19 nm) were solvothermally prepared in the sole presence of oleylamine (OAm) and evaluated on tomato (Lycopersicon esculentum Mill.) photosystem II (PSII) photochemistry. Foliar-sprayed 15 mg L−1 ZnO@OAm NPs on tomato leaflets increased chlorophyll content that initiated a higher amount of light energy capture, which resulted in about a 20% increased electron transport rate (ETR) and a quantum yield of PSII photochemistry (ΦPSII) at the growth light (GL, 600 μmol photons m−2 s−1). However, the ZnO@OAm NPs caused a malfunction in the oxygen-evolving complex (OEC) of PSII, which resulted in photoinhibition and increased ROS accumulation. The ROS accumulation was due to the decreased photoprotective mechanism of non-photochemical quenching (NPQ) and to the donor-side photoinhibition. Despite ROS accumulation, ZnO@OAm NPs decreased the excess excitation energy of the PSII, indicating improved PSII efficiency. Therefore, synthesized ZnO@OAm NPs can potentially be used as photosynthetic biostimulants for enhancing crop yields after being tested on other plant species

The Effect of Fused 12-Membered Nickel Metallacrowns on DNA and their Antibacterial Activity

The synthesis, characterization and the biological study of a series of Ni(ll)2(carboxylato)2 [12- MCNi(II)N(shi)2(pko)2-4][12-MCNi(ii)N(sh03(pko)-4] (CH3OH)3(H3O) fused 12-membered metallacrowns with 10 metal ions and commercial available herbicides or anti-inflammatory drugs as carboxylato ligands are reported. All the compounds have a mixed ligand composition with salicylhydroxamic acid and di-2-pyridylketonoxime as chelate agents. The compounds construct metallacrown cores {[12-MCNi(n)N(sj02(pko)2-4][12-MCNi(ll)N(shO3(pko)-4]}2+ following the pattern [-Ni-O-N-]4. The neutral decanuclear [Ni(II)(A)]2[12-MCNi(II)N(shi)2(pko)2-4][12-MCNi(II)N(pko)3(pko)-4] fused metallacrown, consists of two [12-MCM(ox)N(ligand)-4] units the {Ni(ll)(A)[12-MCNi(II)N(shi)2(pko)2-4]} and {Ni(II)(A)[12-MCNi(II)N(shi)3(pko)-4]} with 1+ and 1- charge, respectively. Each metallacrown unit has four ring Ni(II) ions and one additional encapsulated Ni(II) ion in planar arrangement. The anionic unit is bonded with cationic one creating binuclear moieties. The herbicide or antiiflammatory carboxylato ligands are bridging the central octahedral nickel atom with a ring metal ion in a bindetate fashion. The effect on DNA and their antibacterial activity was examined. The changes in the mobility can be attributed to the altered structures of the pDNA treated with Ni(II) complexes. Evaluating the data of the antibacterial activity of the compounds tested, we can conclude that nickel complexes present strong antibacterial activity

Structure Differentiation of Hydrophilic Brass Nanoparticles Using a Polyol Toolbox

Nano-brasses are emerging as a new class of composition-dependent applicable materials. It remains a challenge to synthesize hydrophilic brass nanoparticles (NPs) and further exploit them for promising bio-applications. Based on red/ox potential of polyol and nitrate salts precursors, a series of hydrophilic brass formulations of different nanoarchitectures was prepared and characterized. Self-assembly synthesis was performed in the presence of triethylene glycol (TrEG) and nitrate precursors Cu(NO3)2·3H2O and Zn(NO3)2·6H2O in an autoclave system, at different temperatures, conventional or microwave-assisted heating, while a range of precursor ratios was investigated. NPs were thoroughly characterized via X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), transmition electron microscopy (TEM), Fourier-transform infrared (FTIR) spectroscopy, dynamic light scattering (DLS), and ζ-potential to determine the crystal structure, composition, morphology, size, state of polyol coating, and aqueous colloidal stability. Distinct bimetallic α-brasses and γ-brasses, α-Cu40Zn25/γ-Cu11Zn24, α-Cu63Zn37, α-Cu47Zn10/γ-Cu19Zn24, and hierarchical core/shell structures, α-Cu59Zn30@(ZnO)11, Cu35Zn16@(ZnO)49, α-Cu37Zn18@(ZnO)45, Cu@Zinc oxalate, were produced by each synthetic protocol as stoichiometric, copper-rich, and/or zinc-rich nanomaterials. TEM sizes were estimated at 20–40 nm for pure bimetallic particles and at 45–70 nm for hierarchical core/shell structures. Crystallite sizes for the bimetallic nanocrystals were found ca. 30–45 nm, while in the case of the core-shell structures, smaller values around 15–20 nm were calculated for the ZnO shells. Oxidation and/or fragmentation of TrEG was unveiled and attributed to the different fabrication routes and formation mechanisms. All NPs were hydrophilic with 20–30% w/w of polyol coating, non-ionic colloidal stabilization (−5 mV < ζ-potential < −13 mV) and relatively small hydrodynamic sizes (<250 nm). The polyol toolbox proved effective in tailoring the structure and composition of hydrophilic brass NPs while keeping the crystallite and hydrodynamic sizes fixed