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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 (Φ PSII ) 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 development of effective and ecofriendly agrochemicals, including bactericides, fungicides, insecticides, and nematicides, to control pests and prevent plant diseases remains a key challenge. Nanotechnology has provided opportunities for the use of nanomaterials as components in the development of anti-phytopathogenic agents. Indeed, inorganic-based nanoparticles (INPs) are among the promising ones. They may play an effective role in targeting and killing microbes via diverse mechanisms, such as deposition on the microbe surface, destabilization of cell walls and membranes by released metal ions, and the induction of a toxic mechanism mediated by the production of reactive oxygen species. Considering the lack of new agrochemicals with novel mechanisms of action, it is of particular interest to determine and precisely depict which types of INPs are able to induce antimicrobial activity with no phytotoxicity effects, and which microbe species are affected. Therefore, this review aims to provide an update on the latest advances in research focusing on the study of several types of engineered INPs, that are well characterized (size, shape, composition, and surface features) and show promising reactivity against assorted species (bacteria, fungus, virus). Since effective strategies for plant protection and plant disease management are urgently needed, INPs can be an excellent alternative to chemical agrochemical agents as indicated by the present studies.

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 EC 50 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.

Magnetic metal-organic frameworks (MMOFs) are gaining increased attention as emerging adsorbents/water remediation agents. Herein, a facile development of novel MMOFs comprised of coated ferrite nanoparticles (MNPs) and UiO-66 metal-organic framework is reported. In specific, coated Co- and Zn-doped ferrite magnetic nanoparticles were synthesized as building block while the metal-organic framework was grown in the presence of MNPs via a semi-self-assembly approach. The utilization of coated MNPs facilitated the conjugation and stands as a novel strategy for fabricating MMOFs with increased stability and an explicit structure. MMOFs were isolated with 13-25 nm crystallites sizes, 244-332 m 2 /g specific surface area (SSA) and 22-42 emu/g saturation magnetization values. Establishing the UiO-66 framework via the reported semi-self-assembly resulted in roughly 70% reduction in both magnetic properties and SSA, compared with the initial MNPs building blocks and UiO-66 framework, respectively. Nonetheless, the remaining 30% of the magnetization and SSA was adequate for successful and sufficient adsorption of two different pesticides, 2,4-Dichlorophenoxyacetic acid (2,4-D) and 2,4,5-Trichlorophenoxyacetic acid (2,4,5-T), while the recovery with a commercial magnet and reuse were also found to be effective. Adsorption and kinetic studies for all three MMOFs and both pesticides were performed, and data were fitted to Langmuir-Freundlich isotherm models.

Protein amyloidosis represents the main pathological hallmark of many incurable neurodegenerative disorders and protein misfolding diseases. Nanomaterials-based approaches give rise to diagnosis and/or prediction of these proteinopathies, with regards to the multifactorial nature of their pathogenesis. Herein, crystalline truncated hexagonal shaped naked ZnO nanoparticles (mean value 47.4 nm) have been solvothermally prepared and immobilized further with alizarin (Alzn) molecules (54%) to stand up to amyloidosis acting both as inhibitors and imaging agents, as well as antioxidants. Thioflavin-T (ThT) assay revealed that the resulted zinc oxide nanoparticles immobilized with alizarin (ZnO@Alzn NPs) inhibited in vitro insulin amyloids formation in a dose-dependent manner, while the kinetic mechanism of the phenomenon was recorded. In parallel, amyloid oligomers and plaques have been visualized by conventional optical microscopy upon protein co-incubation with ZnO@Alzn NPs, highlighting the imaging ability of the immobilized NPs. The antioxidant activity was monitored by 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay, through which it was shown that alizarin incorporation onto the inorganic core leads to the reduction of IC 50 values from 221 μg/mL to 167 μg/mL. The enhanced free radical scavenging effects of ZnO@Alzn compared to the naked-ZnO NPs, features their prospect to serve additional functions., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

In the current study, coated copper nanoparticles with polyethylene glycol 8000 (Cu@PEG NPs) and copper-doped zinc oxide nanoparticles with diethylene glycol (Cu-doped ZnO@DEG NPs) have been synthesized via solvothermal and microwave-assisted process, physicochemical characterized, and studied as nano-fungicides and nano-nematicides. Spheroidal Cu-doped ZnO@DEG NPs and urchin-like Cu@PEG NPs have been isolated with average crystallite sizes of 12 and 21 nm, respectively. The Cu doping (11.3 wt%) in ZnO lattice (88.7 wt%) was investigated by Rietveld refinement analysis and confirmed by X-ray Diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS). The Cu-doped ZnO@DEG and Cu@PEG NPs revealed a growth inhibition of fungi Botrytis cinerea (B. cinerea) and Sclerotinia sclerotiorum (S. sclerotiorum) and nematode paralysis of Meloidogyne javanica in a dose-dependent manner. Cu-doped ZnO@DEG NPs were more effective against M. javanica (EC 50  = 2.60 μg/mL) than the Cu@PEG NPs (EC 50  = 25 μg/mL). In contrast, the antifungal activity was approximately similar for both NPs, with EC 50 values at 310 and 327 μg/mL against B. cinerea, respectively, and 260 and 278 μg/mL against S. sclerotiorum, respectively. Lettuce (Lactuca sativa) plants were inoculated with S. sclerotiorum or M. javanica and sprayed with either Cu-doped ZnO@DEG NPs or Cu@PEG NPs. The antifungal effect was evaluated based on a disease index (DI), and nematicidal activity was assessed based on the total number of galls and nematode females per root gram. NPs successfully inhibited the growth of both pathogens without causing phytotoxicity on lettuce. The DI were significantly decreased as compared to the positive control (DI = 5.2), estimated equal to 1.7, 2.9 and 2.5 for Cu@PEG NPs, Cu-doped ZnO@DEG NPs and the chemical control (KOCIDE 2000), respectively. The reduction in galling and population of M. javanica ranged from 39.32% to 32.29%, statistically like chemical control. The treatment of lettuce plants with Cu-doped ZnO@DEG NPs increased the leaf net photosynthetic value at 4.60 and 6.66 μmol CO 2 -2  s -1 in plants inoculated with S. sclerotiorum and M. javanica, respectively, as compared to the control (3.00 μmol CO 2 -2  s -1 ). The antioxidant capacity of NPs treated lettuce plants was evaluated as 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging activity in leaf extracts. Plants inoculated with S. sclerotiorum and sprayed with Cu-doped ZnO@DEG and Cu@PEG NPs, exhibited a 34.22% and 32.70% increase in antioxidant capacity, respectively, higher than the control. Similarly, an increase in antioxidant capacity was measured (39.49 and 37.36%) in lettuce inoculated with M. javanica and treated with Cu-doped ZnO@DEG and Cu@PEG NPs, respectively. Moreover, an increase of phenolic compounds in lettuce leaf tissue treated with NPs was measured as compared to the control. Overall, foliar applied Cu and Cu-doped ZnO NPs could be a promising tool to control phytopathogenic fungi and nematodes contributing to sustainability of agri-food sector., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

In the present study, the bioactive substance geraniol was tested in vitro and in planta against B. cinerea on cucumber plants, and the changes in the metabolic profile of cucumber plants inoculated with the pathogen and/or treated with geraniol were monitored by a novel LC-QTOF-MS method employing target and suspect screening. The aforementioned treatments were also studied for their impact on membrane lipid peroxidation calculated as malondialdehyde (MDA) content. Additionally, geraniol-loaded nanoemulsions (GNEs) were synthesized and tested against B. cinerea as an integrated formulation mode of geraniol application. The EC 50 values calculated for geraniol and GNEs against B. cinerea were calculated at 235 μg/mL and 105 μg/mL, respectively. The in planta experiment on cucumber plants demonstrated the ability of geraniol and GNEs to significantly inhibit B. cinerea under greenhouse conditions. The LC-QTOF-MS analysis of the metabolic profile of the cucumber plants treated with geraniol demonstrated an increase in the concentration levels of myricetin, chlorogenic acid, and kaempferol rhamnoside, as compared to control plants and the presence of B. cinerea caused an increase in sinapic acid and genistein. These compounds are part of important biosynthetic pathways mostly related to responses against a pathogen attack.

The removal of radioactive contaminants from aquifers is a matter of great concern. In this paper, coated copper-based nanoparticles (Cu-based NPs) were investigated as sorbent materials to remove uranium and thorium from low-level wastes, and especially from water, considering the influences of temperature, time, concentration, and pH. Cu-based NPs were derived through a hydrothermal synthesis from copper nitrate degradation in the presence of the bifunctional with COOH-terminated PEG, TEG as well as PEG 8000. The characterization was undertaken using XRD, TEM, TG/DTG, FTIR, and SEM-EDS. Isotherm models such as Langmuir and Freundlich were applied, while kinetic data were successfully reproduced by the pseudo-second-order equation and thermodynamic parameters were calculated. To investigate the removal mechanisms, UV-fluorescence and X-ray photoelectron spectroscopy were used. In the case of uranium, the predominant mechanism includes the formation of surface complexes, followed by extensive reduction (65%) of U(VI) to less soluble U(IV) while in the case of thorium, surface precipitation dominates. Copper nanoparticles exhibited significant U(VI) uptake capacity resulting in a decrease of the U-concentration below the acceptable limit of 30 μg/L and can be successfully applied in water treatment technology., Competing Interests: Declaration of competing interest In this paper the removal of radionuclides uranium and thorium from water was investigated using new synthesized coated copper-based nanoparticles (Cu-based NPs). No funding sources are declared., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Inorganic nanoparticles (INPs) have dynamically emerged in plant protection. The uptake of INPs by plants mostly depends on the size, chemical composition, morphology, and the type of coating on their surface. Herein, hybrid ensembles of glycol-coated bimetallic CuZn and ZnO nanoparticles (NPs) have been solvothermally synthesized in the presence of DEG and PEG, physicochemically characterized, and tested as nano-fungicides. Particularly, nanoflowers (NFs) of CuZn@DEG and ZnO@PEG have been isolated with crystallite sizes 40 and 15 nm, respectively. Organic coating DEG and PEG (23% and 63%, respectively) was found to protect the NFs formation effectively. The CuZn@DEG and ZnO@PEG NFs revealed a growth inhibition of phytopathogenic fungi Botrytis cinerea and Sclerotinia sclerotiorum in a dose-dependent manner with CuZn@DEG NFs being more efficient against both fungi with EC 50 values of 418 and 311 μg/mL respectively. Lettuce ( Lactuca sativa) plants inoculated with S. sclerotiorum were treated with the NFs, and their antifungal effect was evaluated based on a disease index. Plants sprayed with ZnO@PEG NFs showed a relatively higher net photosynthetic (4.70 μmol CO 2 m -2 s -1 ) and quantum yield rate (0.72) than with CuZn@DEG NFs (3.00 μmol CO 2 m -2 s -1 and 0.68). Furthermore, the penetration of Alizarin Red S-labeled NFs in plants was investigated. The translocation from leaves to roots through the stem was evident, while ZnO@PEG NFs were mainly trapped on the leaves. In all cases, no phytotoxicity was observed in the lettuce plants after treatment with the NFs.

Magneto-fluorescent nanocomposites have been recognized as an emerging class of materials displaying great potential for improved magnetic hyperthermia assisted by optical imaging. In this study, we have designed a series of hybrid composites that consist of zinc doped Zn x Fe 3-x O 4 ferrites functionalized by polyethylene-glycol (PEG8000) and an orange-emitting platinum complex [Pt(phen)Cl 2 ]. Experimental and theoretical studies on the optimization of their magnetically-mediated heating properties were conducted. PEG was assembled around particles' surface by two different approaches; in situ and post-PEGylation. PEGylation ensured the optimal distance between the magnetic core and Pt(ii)-complex to maintain significant luminescence in the composite. The successful inclusion of the complex to the organic matrix was confirmed by a variety of spectroscopic techniques. A theoretical model was developed, based on linear response theory, in order to examine the composites' power losses dependence on their properties. Within this model, inter-particle interactions were quantified by inserting a mean dipolar energy term in the estimation of Néel relaxation time, and consequently, the size and concentration that maximize power loss were derived (20 nm and 4 mg mL -1 ). Moreover, a decrease in the anisotropy of nanoparticles resulted in an increase in specific loss power values. Theoretical estimations are validated by experimental data when heating aqueous dispersions of composites in 24 kA m -1 , 765 kHz AMF for various values of concentration and size. Magnetic hyperthermia results showed that the theory-predicted values of optimum concentration and size delivered the maximum-specific loss power which was found equal to 545 W g -1 . By the present approach, a quantitative link between the particles' dipolar interactions and their heating properties is established, while opening new perspectives to nanotheranostic applications.

Alzheimer's disease (AD) is the most prevalent cause of dementia linked to the accumulation of amyloid-beta (Aβ) plaques-fibrils that impair cognitive functions. Magnetic nanoparticles (MNPs) are emerging as promising tools for the crusade against AD owning to appropriate biocompatibility and facile functionalization that can lead to theranostic agents. Herein, the fabrication of a multimodal (magnetic resonance imaging (MRI), fluorescence imaging, and drug carrier) magnetic nanoemulsion (MNE) is reported as an AD theranostic candidate. Initially zinc ferrite MNPs of high saturation magnetization (129 emu g -1 ) were synthesized through a modified microwave-assisted polyol process. Memantine (a registered AD drug) was labeled with fluorescein (Mem-Flu) and encapsulated with the MNPs in sodium dodecyl sulfate micelles to form the MNE. Small hydrodynamic size (107), high encapsulation (77.5%) and loading efficiencies (86.1%) and sufficient transverse relaxivity (48.7 mM -1 s -1 ) were achieved through the design while sustained release of Mem-Flu was unveiled by in zero-order, first-order, Higuchi and Korsmeyer-Peppas pharmacokinetic models. Moreover, the MNE acquired fluorescence imaging ability of Aβ 1-42 peptide monomers and/or plaques-fibrils via the fluorescein labeling of Memantine. A novel inorganic-organic hybrid multimodal AD theranostic candidate is presented.

The goal of the present study was to examine the effects of ZnO NPs and CuO NPs on Cornu aspersum land snail, enlightening their cytotoxic profile. ZnO NPs and CuO NPs were synthesized and thoroughly characterized. Α series of concentrations of either ZnO NPs or CuO NPs were administered in the feed of snails for 20 days. Thereafter, neutral red retention assay was conducted, in order to estimate NRRT50 values. Subsequently, snails were fed with NPs concentrations slightly lower than the concentrations that were corresponding to the NRRT50 values, i.e. 3 mg·L -1 ZnO NPs and 6 mg·L -1 CuO NPs, for 1, 5, 10 and 20 days. Both NPs agglomerates were detected in hemocytes by Transmission Electron Microscopy. Moreover, both effectors resulted to toxicity in the snails' hemocytes. The latter was shown by changes in the NRRT50 values, increased reactive oxygen species (ROS) production, lipid peroxidation, DNA integrity loss, protein carbonyl content, ubiquitin conjugates and cleaved caspases conjugates levels compared to the untreated animals. Although ZnO NPs exhibited higher toxicity, as indicated by the NRRT50 values, both NPs affected similarly a wide range of the cellular parameters mentioned above. The latter parameters could constitute sensitive biomarkers in biomonitoring studies of terrestrial environment against nanoparticles., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Water pollution by heavy metals is one of the most serious worldwide environmental issues. With a focus on copper(II) ions and copper complex removal, in the present study, ultra-small primary CoFe 2 O 4 magnetic nanoparticles (MNPs) coated with octadecylamine (ODA) of adequate magnetization were solvothermally prepared. The surface modification of the initial MNPs was adapted via three different chemical approaches based on amine and/or carboxylate functional groups: (i) the deposition of polyethylimide (PEI), (ii) covalent binding with diethylenetriaminepentaacetic acid (DTPA), and (iii) conjugation with both PEI and DTPA, respectively. FT-IR, TGA, and DLS measurements confirmed that PEI or/and DTPA were successfully functionalized. The percentage of the free amine (-NH 2 ) groups was also estimated. Increased magnetization values were found in case of PEI and DTPA-modified MNPs that stemmed from the adsorbed amine or oxygen ligands. Comparative UV-Vis studies for copper(II) ion removal from aqueous solutions were conducted, and the effect of time on the adsorption capacity was analyzed. The PEI-modified particles exhibited the highest adsorption capacity (164.2 mg/g) for copper(II) ions and followed the pseudo-second-order kinetics, while the polynuclear copper(II) complex Cu x (DTPA) y was also able to be immobilized. The nanoadsorbents were quickly isolated from the solution by magnetic separation and regenerated easily by acidic treatment.

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.

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(NO 3 ) 2 ·3H 2 O and Zn(NO 3 ) 2 ·6H 2 O 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-Cu 40 Zn 25 /γ-Cu 11 Zn 24 , α-Cu 63 Zn 37 , α-Cu 47 Zn 10 /γ-Cu 19 Zn 24 , and hierarchical core/shell structures, α-Cu 59 Zn 30 @(ZnO) 11 , Cu 35 Zn 16 @(ZnO) 49 , α-Cu 37 Zn 18 @(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., (Copyright © 2019 Antonoglou, Founta, Karagkounis, Pavlidou, Litsardakis, Mourdikoudis, Thanh and Dendrinou-Samara.)

Amyloidosis, the aggregation of naturally soluble proteins into fibrils, is the main pathological hallmark of central nervous system (CNS) disorders, and new therapeutic approaches can be introduced through nanotechnology. Herein, magnetic nanoparticles (MNPs) are proposed to combat amyloidosis and act as CNS theranostic (therapy and diagnosis) candidates through magnetomechanical forces that can be induced under a low-frequency magnetic field. In that vein, a modified one-step microwave-assisted polyol process has been employed to synthesize hybrid organic/inorganic zinc ferrite (Zn x Fe 3- x O 4 ) MNPs with different levels of zinc doping (0.30 < x < 0.6) derived from the utilized polyol. The lowest doped ( x = 0.30) MNPs exhibited high magnetization (127 emu/g), high T 2 imaging ability ( r 2 = 432 mM -1 s -1 ), and relatively small hydrodynamic size (180 nm), decisive characteristics to further evaluate their CNS theranostic potential. Their effect on the fibrillation/degradation was monitored in two model proteins, insulin and albumin, in the presence/absence of variant external magnetic fields (static, rotating, or alternating) via Thioflavin T (ThT) fluorescence assay and optical fluorescence microscopy. The MNPs were injected either in oligomer solution where significant fibrillation delay was observed, boosted by zinc ionic leaching of MNPs, or in already formed amyloid plaques where up to 86% amyloid degradation was recorded in the presence of magnetic fields, unveiling magnetomechanical antifibrillation properties. The alternating magnetic field (4 Hz) allows the bouncing of the MNPs into the amyloid net driven by the magnetic forces, and thus is featured as the preferred "dancing mode", which strengthens the degrading efficacy of MNPs.

A study of the influence of polyols, with or without an additional reducing agent, on crystallites' size and magnetic features in Fe 3 O 4 nanoparticles and on their performance in magnetic particle hyperthermia is presented. Three different samples were synthesized by thermal decomposition of an iron precursor in the presence of NaBH 4 in a polyol. So far, triethylene glycol (TrEG) and polyethylene glycol (PEG 1000 and PEG 8000) that exhibit different physical and chemical properties have been used in order to investigate the influence of the polyols on the composition and the size of the NPs. Additionally, the presence of a different reducing agent such as hydrazine, has been tested for comparison reasons in case of TrEG. Three more samples were prepared solvothermally by using the same polyols, which led to different crystallite sizes. The magnetic core of the nanoparticles was characterized, while the presence of the surfactant was studied qualitatively and quantitatively. Concerning the magnetic features, all samples present magnetic hysteresis including remanence and coercivity revealing that they are thermally blocked at room temperature. Finally, a study on the influence of the MNPs heating efficiency from their size and the field amplitude was accomplished. In our polyol process the main idea was to control the specific loss power (SLP) values by the nanoparticles' size and consequently by the polyol itself., Competing Interests: The authors declare no conflict of interest. The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or in the decision to publish the results.

Young and mature leaves of Arabidopsis thaliana were exposed by foliar spray to 30 mg L - 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 (Φ PSΙΙ ) and the redox state of the plastoquinone (PQ) pool ( q p ), 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 H 2 O 2 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 Φ PSΙΙ , an increased electron transport rate (ETR), decreased singlet oxygen ( 1 O 2 ) formation, and H 2 O 2 production at the same level of control leaves.An explanation for this differential response is suggested., Competing Interests: The authors declare no conflict of interest.

Magnetic hybrid inorganic/organic nanocarriers are promising alternatives for targeted cancer treatment. The present study evaluates the preparation of manganese ferrite magnetic nanoparticles (MnFe 2 O 4 MNPs) encapsulated within Paclitaxel (PTX) loaded thioether-containing ω-hydroxyacid-co-poly(d,l-lactic acid) (TEHA-co-PDLLA) polymeric nanoparticles, for the combined hyperthermia and chemotherapy treatment of cancer. Initially, TEHA-co-PDLLA semitelechelic block copolymers were synthesized and characterized by 1 H-NMR, FTIR, DSC, and XRD. FTIR analysis showed the formation of an ester bond between the two compounds, while DSC and XRD analysis showed that the prepared copolymers were amorphous. MnFe 2 O 4 MNPs of relatively small crystallite size (12 nm) and moderate saturation magnetization (64 emu·g -1 ) were solvothermally synthesized in the sole presence of octadecylamine (ODA). PTX was amorphously dispersed within the polymeric matrix using emulsification/solvent evaporation method. Scanning electron microscopy along with energy-dispersive X-ray spectroscopy and transmission electron microscopy showed that the MnFe 2 O 4 nanoparticles were effectively encapsulated within the drug-loaded polymeric nanoparticles. Dynamic light scattering measurements showed that the prepared nanoparticles had an average particle size of less than 160 nm with satisfactory yield and encapsulation efficiency. Diphasic PTX in vitro release over 18 days was observed while PTX dissolution rate was mainly controlled by the TEHA content. Finally, hyperthermia measurements and cytotoxicity studies were performed to evaluate the magnetic response, as well as the anticancer activity and the biocompatibility of the prepared nanocarriers.

Inorganic nanoparticles (NPs) have been proposed as alternative fertilizers to suppress plant disease and increase crop yield. However, phytotoxicity of NPs remains a key factor for their massive employment in agricultural applications. In order to investigate new effective, nonphytotoxic, and inexpensive fungicides, in the present study CuZn bimetallic nanoparticles (BNPs) have been synthesized as antifungals, while assessment of photosystem II (PSII) efficiency by chlorophyll fluorescence imaging analysis is utilized as an effective and noninvasive phytotoxicity evaluation method. Thus, biocompatible coated, nonoxide contaminated CuZn BNPs of 20 nm crystallite size and 250 nm hydrodynamic diameter have been prepared by a microwave-assisted synthesis. BNPs' antifungal activity against Saccharomyces cerevisiae was found to be enhanced compared to monometallic Cu NPs. Reactive oxygen species (ROS) formation and photosystem II (PSII) functionality at low light (LL) and high light (HL) intensity were determined on tomato plants sprayed with 15 and 30 mg L -1 of BNPs for the evaluation of their phytotoxicity. Tomato leaves sprayed with 15 mg L -1 of BNPs displayed no significant difference in PSII functionality at LL, while exposure to 30 mg L -1 of BNPs for up to 90 min resulted in a reduced plastoquinone (PQ) pool that gave rise to H 2 O 2 accumulation, initiating signaling networks and regulating acclimation responses. After 3 h of exposure to 30 mg L -1 of BNPs, PSII functionality at LL was similar to control, indicating nonphytotoxic effects. Meanwhile, exposure of tomato leaves either enhanced (15 mg L -1 ) or did not have any significant effect (30 mg L -1 ) on PSII functionality at HL, attributed to the absence of semiconducting oxide phases and photochemical toxicity-reducing modifications. The use of chlorophyll fluorescence imaging analysis is recommended as a tool to monitor NPs behavior on plants.

The use of magnetic nanostructures as theranostic agents is a multiplex task as physiochemical and biochemical properties including excellent magneto-responsive properties, low toxicity, colloidal stability and facile surface engineering capability are all required. Nonetheless, much progress has been made in recent years synthesis of "all-in-one" MNPs remain unambiguously challenging. Towards this direction, in this study is presented a facile incorporation of a soft magnetic phase (MnFe 2 O 4 NPs) with a hard phase (CoFe 2 O 4 NPs) in the presence of the biocompatible polymer sodium dodecyl sulfate (SDS), into spherical and compact bi-magnetic nanoclusters (NCs) with modulated magnetic properties that critically enhance hyperthermic efficiency and MRI contrast effect. Hydrophobic MnFe 2 O 4 and CoFe 2 O 4 NPs coated with oleylamine of the same size (9 nm) were used as primary building units for the formation of the bi-magnetic NCs through a microemulsion approach where a set of experiments were conducted to identify the optimal concentration of SDS (19.5 mM) for the cluster formation. Additionally, homo-magnetic NCs of MnFe 2 O 4 NPs and CoFe 2 O 4 NPs, respectively were synthesized for comparative studies. The presence of distinct magnetic phases within the bi-magnetic NCs resulting in synergistic behavior, where the soft phase offers moderate coercivity H c and the hard one high magnetization M s . Increased specific loss power (SLP) value was obtained for the bi-magnetic system (525 W/g) when compared with the homo-magnetic NCs (104 W/g for MnNCs and 223 W/g for CoNCs) under field conditions of 25 kA/m and 765 kHz. Relaxivities (r 2 ) of the bi-magnetic NCs were also higher (81.8 mM -1  s -1 ) than those of the homo-magnetic NCs (47.4 mM -1  s -1 for MnNCs and 3.1 mM -1  s -1 for CoNCs), while the high r 2 /r 1 value renders the system suitable for T 2 -weighted MRI imaging., (Copyright © 2017 Elsevier Inc. All rights reserved.)

Adequately designed multiresponsive water-soluble graft copolymers were used to serve as a multifunctional polymeric platform for the encapsulation and transfer in aqueous media of hydrophobic magnetic nanoparticles (MNPs). The backbone of the graft copolymers was composed of hydrophilic sodium methacrylate units, hydrophobic dodecyl methacrylate units, and luminescent quinoline-based units, while either the homopolymer poly(N-isopropylacrylamide) or a poly(N,N-dimethylacrylamide-co-N-isopropylacrylamide) copolymer was used as thermosensitive pendent side chains. The polymeric platform forms micellar-type assemblies in aqueous solution, and exhibits pH-responsive luminescent properties and a lower critical solution temperature behavior in water. Depending on the design of the side chains, the cloud point temperatures were determined at 38 and 42 °C, close or slightly above body temperature (37 °C). Above the critical micelle concentration (CMC), both graft copolymers can effectively stabilize in aqueous media as magnetic colloidal superparticles (MSPs), oleylamine-coated MnFe 2 O 4 MNPs, as well as 1:1 mixture of oleylamine-coated MnFe 2 O 4 and CoFe 2 O 4 MNPs. When CoFe 2 O 4 particles were mixed with MnFeO 4 in equal amounts, the specific loss power increased significantly, while an opposite trend was observed in the magnetic resonance imaging (MRI) studies, probably due to the anisotropy of cobalt. As a consequence, fine-tuning of the chemical structure of the copolymers and the composition of the MSPs can lead to materials that are able to act simultaneously as luminescent, hyperthermia, and contrast MRI agents.

Magnetic nanoparticles (MNPs) can play a distinct role in magnetic drug delivery via their distribution to the targeted area. The preparation of such MNPs is a challenging multiplex task that requires the optimization of size, magnetic, and surface properties for the achievement of desirable target selectivity, along with the sustained drug release as a prerequisite. In that context, CoFe2O4 MNPs with a small size of ∼7 nm and moderate saturation magnetization of ∼60 emu g(-1) were solvothermally synthesized in the presence of octadecylamine (ODA) with a view to investigate the functionalization route effect on the drug release. Synthetic regulations allowed us to prepare MNPs with aminated (AmMNPs) and amine-free (FAmMNPs) surface. The addition of the nonsteroidal anti-inflammatory drug with a carboxylate donor, Naproxen (NAP), was achieved by direct coupling with the NH2 groups, rendered by ODA, through the formation of an amide bond in the case of AmMNPs. In the case of FAmMNPs, indirect coupling of NAP was performed through an intermediate linker (polyethylenimine) and on PEG-ylated MNPs. FT-IR, (1)H NMR, (13)C NMR, and UV-vis data confirmed the addition of NAP, whereas diverse drug-release behavior was observed for the different functionalization approaches. The biological behavior of the MNPs@NAP was evaluated in vitro in rat serum and in vivo in mice, after radiolabeling with a γ-emitting radionuclide, (99m)Tc. The in vivo fate of MNPs@NAP carriers was in straightforward relation with the direct or indirect coupling of NAP. Furthermore, an inflammation was induced intramuscularly, where the directly coupled (99m)Tc-MNPs@NAP carriers showed increased accumulation at the inflammation site.

The ability to encapsulate hydrophobic ferrites in colloidal superparticle structures of an a-telechelic hexadecyl-functionalized poly(methacrylic acid) (C16H33-PMAA) polymer with a linear architecture was investigated and compared with that of two amphiphilic comb-type water-soluble copolymers, namely, P(ANa-co-DAAm) and P(MANa-co-DMA), which are comprised of a poly(sodium acrylate) or poly(sodium methacrylate) backbone and pendent dodecyl acrylamide or dodecyl methacrylate chains, respectively. In the case of C16H33-PMAA, the pH-sensitive self-assembly behavior, which was studied through Nile Red probing and TEM, was related to its encapsulation properties. Hydrophobic MFe2O4 nanoparticles coated with oleylamine (MFe2O4@OAm MNPs, where M = Co, Mn, Ni) with a similar shape and size (∼9 nm) and magnetization values of 87.4, 63.1 and 55.0 emu g(-1) for CoFe2O4@OAm, MnFe2O4@OAm and NiFe2O4@OAm, respectively, were successfully encapsulated into the hydrophobic cores of spherical micellar structures formed by the copolymers in an aqueous solution through a solvent mixing procedure. The synthesized magnetic colloidal superparticles fell in the static dephasing regime (SDR). NMR relaxivity measurements of MFe2O4@P(ANa-co-DAAm), MFe2O4@P(MANa-co-DMA) and MFe2O4@C16H33-PMAA at pH = 4.5 and pH = 7 (where M = Co, Mn, Ni) at 11.7 T were recorded and the transverse relaxivity (r2) (mM(-1) s(-1)) was determined. Among all, the CoFe2O4@polymers demonstrated the highest r2 relaxivity values, ranging from 61.6 for CoFe2O4@C16H33-PMAA (pH = 7) to 316.0 mM(-1) s(-1) for CoFe2O4@P(ANa-co-DAAm). The relaxation efficiency (r1 and r2) of CoFe2O4@P(ANa-co-DAAm) was investigated further by magnetic resonance imaging (MRI) at 1.5 T and 3 T and the r2/r1 ratios were found to be 16.5 and 18.2, respectively, indicating its potential use as a T2 contrast agent.

Manganese doped ferrite (MnxFe3-xO4) nanoparticles with x = 0.29-0.77 were prepared under solvothermal conditions in the presence solely of a polyol using the trivalent manganese and iron acetylacetonates as precursors. In this facile approach, a variety of polyols such as polyethylene glycol (PEG 8000), tetraethylene glycol (TEG), propylene glycol (PG) and a mixture of TEG and PG (1 : 1) were utilized in a triple role as a solvent, a reducing agent and a surface-functionalizing agent. The composition of the fine cubic-spinel structures was found to be related to the reductive ability of each polyol, while determination of structural characteristics plus the inversion parameter (i = 0.18-0.38) were provided by X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy at both the Fe and Mn K-edges. The saturation magnetization increased up to 80 emu g(-1) when x = 0.35 and i = 0.22. In addition, the as-prepared nanocrystals coated with PEG, PG and PG&TEG showed excellent colloidal stability in water, while the TEG-coated particles were not water dispersible and converted to hydrophilic when were extra PEGylated. Measurements of the (1)H NMR relaxation in water were carried out and the nanoprobes were evaluated as potential contrast agents.

Hydrophobically modified water-soluble polymers (HMWSPs), comprised of a poly(sodium methacrylate) (PMANa) or poly(sodium acrylate) (PANa) backbone and pendent dodecyl methacrylate (DMA) or dodecyl acrylamide (DAAm) chains, respectively, were synthesized. The hydrophobic content of the copolymers, P(MANa-co-DMA) and P(ANa-co-DAAm), is in the range of 0 to 25 mol%, while their weight-average molar mass varies from ~10 000 up to ~75 000. Their self-assembly behavior in dilute aqueous solution was followed through Nile Red probing, DLS and TEM measurements. The critical micelle concentration (CMC) is mainly controlled by the hydrophobic content and not the molar mass of the copolymers. Above CMC, spherical and large-compound micelles are identified by DLS and TEM. Moreover, oleylamine coated CoFe2O4 nanoparticles (CoFe2O4@OAm MNPs) of 9.4 nm with a saturation magnetization Ms = 85 emu g(-1) were solvothermally prepared. The hydrophobic CoFe2O4@OAm MNPs were successfully encapsulated into the hydrophobic cores of the structures formed by the copolymers above CMC through a solvent mixing procedure, and in that way hydrophilic CoFe2O4@HMWSP nanohybrids resulted. For comparison purposes, two alternate phase transfer approaches were also used to convert CoFe2O4@OAm MNPs to hydrophilic ones: (a) addition of a coating layer by cetyltrimethyl ammonium bromide (CTAB) and (b) by the ligand exchange procedure with 2,3-dimercaptosuccinic acid (DMSA). NMR transverse relaxivity measurements of the aqueous suspensions of CoFe2O4@P(ANa-co-DAAm), CoFe2O4@CTAB and CoFe2O4@DMSA were recorded and the r2 relaxivity was determined. CoFe2O4@CTAB demonstrated the highest r2 relaxivity of 554.0 mM(-1) s(-1), while CoFe2O4@P(ANa-co-DAAm) and CoFe2O4@DMSA showed lower values of 313.6 mM(-1) s(-1) and 76.3 mM(-1) s(-1), respectively.

The multifunctional role of oleylamine (OAm) as a versatile and flexible reagent in synthesis as well as a desired surface ligand for the synthesis of CoFe2O4 nanoparticles (NPs) is described. CoFe2O4 NPs were prepared by a facile, reproducible and scalable solvothermal approach in the presence of pure OAm. By monitoring the volume of OAm, different shapes of NPs, spherical and truncated, were formed. The syntheses led to high yields of monodispersed and considerably small (9-11 nm) CoFe2O4 NPs with enhanced magnetization (M(s) = 84.7-87.5 emu g(-1)). The resulting hydrophobic CoFe2O4 NPs were easily transferred to an aqueous phase through the formation of reverse micelles between the hydrophobic chains of OAm and cetyltrimethylammonium bromide (CTAB) and transverse relaxivities (r2) were measured. The spherical NPs had a greater effect on water proton relaxivity (r2 = 553 mM(-1) s(-1)) at an applied magnetic field of 11.7 T. The NPs became fluorescent probes by exploiting the presence of the double bond of OAm in the middle of the molecule; a thiol-ene "click" reaction with the fluorophore bovine serum albumin (FITC-BSA) was achieved. The labeled/biofunctionalized CoFe2O4 NPs interacted with cancer (HeLa and A549) and non-cancer cell lines (MRC5 and dental MSCS) and cell viability was estimated. A clear difference of toxicity between the cancer and non-cancer cells was observed while low cytotoxicity in living cells was supported. Confocal laser microscopy showed that NPs entered the cell membranes and were firstly localized close to them provoking a membrane expansion and were further accumulated perinuclearly without entering the nuclei.

The mononuclear complex [Mn(thiophenyl-2-carboxylate)(2)(H(3)tea)] (1), where H(3)tea=triethanolamine has been synthesized, characterized, while the DNA binding properties and the antioxidant activity were studied. The crystal structure of 1 is also reported. The interaction between 1 and calf thymus double stranded (ds) DNA was electrochemically at a calf thymus DNA (CT-DNA) modified carbon paste electrode (CPE) and spectrophotometrically investigated, respectively. Adsorptive transfer stripping voltammetry showed that the interaction mode between 1 and CT-DNA depends on manganese(II) complex concentration. UV studies between 1 and CT-DNA revealed that 1 can bind to CT-DNA by the intercalative binding mode and the binding constant has been calculated. A competitive study with acridine orange (AO) showed that 1 exhibits the ability to displace the DNA-bound AO, since 1 binds to the DNA in competition with AO. In vitro antioxidant activity of free ligands and 1 was evaluated using five different antioxidant assays: a) interaction with 1, 1-diphenyl-2-picryl-hydrazyl (DPPH) stable free radical, b) the ΗΟ mediated oxidation of DMSO, c) scavenging of superoxide anion radicals, d) inhibition of lipid peroxidation and e) soybean lipoxygenase (LOX) inhibition. The results revealed the selectivity of the manganese complex to different free radicals as a consequence of its physicochemical feature. In particular, 1 presents significant inhibitory activity on LOX, with IC(50)=30 μM and selectivity to the inhibition of superoxide anion radicals and thus a promising candidate as a superoxide dismutase (SOD) biomimetic., (Copyright © 2012 Elsevier Inc. All rights reserved.)

Interaction of phenyl 2-pyridyl ketoxime (PhPyCNO)/X(-)"blends" (X(-) = OH(-), Cl(-), ClO(4)(-), 2,4-D) (2,4-DH = 2,4-dichlorophenoxyacetic acid) with copper perchlorate has yielded trinuclear clusters that have been characterized as inverse-9-metallacrown-3, accommodating one or two anions. The structure of the complex [Cu(3)(PhPyCNO)(3)(mu(3)-OH)(2,4-D)(2)] x 1.25CH(3)OH.0.25CH(3)CN (1) has been determined by single-crystal X-ray crystallography. Spectroscopic studies of the interaction of copper inverse {(OH)[9-MC(CuN(PhPyCNO))-3]} metallacrowns with DNA showed that these compounds bind to dsDNA by intercalative mode with an additional covalent {(OH)[9-MC(Cu(PhPyCNO))-3]}-DNA interaction leading to hydrolytic cleavage of DNA that may be assigned to the presence of the hydroxyl group in the inverse metallacrown ring. The binding strength of [Cu(3)(PhPyCNO)(3)(mu(3)-OH)(2,4-D)(2)] (1) complex for CT-DNA was determined to be 0.56 x 10(5) M(-1). All the complexes exhibited the ability to displace the DNA-bound EthBr. DNA electrophoretic mobility experiments showed that all complexes, at low cluster concentration, are capable of binding to pDNA and linear DNA. At higher cluster concentration and in the absence of any reducing agent they showed marked chemical nuclease activity.

Use of PhPyCNO (-)/X (-) "blends" (PhPyCNOH = phenyl 2-pyridyl ketoxime; X (-) = OH (-), alkanoato, ClO 4 (-)) in copper chemistry yielded trinuclear clusters that have been characterized as inverse-9-metallacrown-3 compounds and accommodate one or two guest ligands. The magnetic behavior showed a large antiferromagnetic interaction and a discrepancy between the low-temperature magnetic behavior observed experimentally and that predicted from a magnetic model. The discrepancy between the Brillouin curve and the experimental result provides clear evidence of the influence of the antisymmetric interaction. Introducing the antisymmetric terms derived from the fit of the susceptibility data into the magnetization formula caused the simulated curve to become nearly superimposable on the experimental one. The EPR data indicated that the compound [Cu 3(PhPyCNO) 3(mu 3-OH)(2,4,5-T) 2] ( 1), where 2,4,5-T is 2,4,5-trichlorophenoxyacetate, has isosceles or lower magnetic symmetry (delta not equal 0), that antisymmetric exchange is important ( G not equal 0), and that Delta E > hnu. The structures of the complexes 1 and [Cu 3(PhPyCNO) 3(mu 3-OH)(H 2O)(ClO 4) 2] ( 2) were determined using single-crystal X-ray crystallography. Theoretical calculations based on density functional theory were performed using the full crystal structures of 1, 2, [Cu 3(PhPyCNO) 3(OH)(CH 3OH) 2(ClO 4) 2] ( 3), and [Cu 3(PhPyCNO) 3(mu 3-OMe)(Cl)(ClO 4)] ( 4). The geometries of the model compounds [Cu 3(kappa (3) N, N, O-HNCHCHNO) 3(mu 3-OH)(mu 2-HCOO)(HCOO)] ( 5), [Cu 3(kappa (3) N, N, O-HNCHCHNO) 3(mu 2-HCOO)(HCOO)] (+) ( 6), [Cu 3(kappa (3) N, N, O-HNCHCHNO) 3(mu 3-O)] (+) ( 7), and [Cu 3(kappa (3) N, N, O-HNCHCHNO) 3] (3+) ( 8) were optimized at the same level of theory for both the doublet and quartet states, and vibrational analysis indicated that the resulting equilibrium geometries corresponded to minima on the potential energy surfaces. Both e g and t 2g magnetic orbitals seem to contribute to the magnetic exchange coupling. The latter contribution, although less important, might be due to overlap of the t 2g orbitals with the p-type orbitals of the central triply bridging oxide ligand, thereby affecting its displacement from the Cu 3 plane and contributing to the antiferromagnetic coupling. The crucial role of the triply bridging oxide (mu 3-O) ligand on the antiferromagnetic exchange coupling between the three Cu(II) magnetic centers is further evidenced by the excellent linear correlation of the coupling constant J with the distance of the mu 3-O ligand from the centroid of the Cu 3 triangle.

Two tetranuclear Mn complexes with an average Mn oxidation state of +2.5 have been prepared. These valence isomers have been characterized by a combination of X-ray crystallography, X-ray absorption spectroscopy, and magnetic susceptibility. The Mn(II)3Mn(IV) tetramer has the Mn ions arranged in a distorted tetrahedron, with an S = 6 ground spin state, dominated by ferromagnetic exchange among the manganese ions. The Mn(II)2Mn(III)2 tetramer also has a distorted tetrahedral arrangement of Mn ions but shows magnetic behavior, suggesting that it is a single-molecule magnet. The X-ray absorption near-edge structure (XANES) spectra for the two complexes are similar, suggesting that, while Mn XANES has sufficient sensitivity to distinguish between trinuclear valence isomers (Alexiou et al. Inorg. Chem. 2003, 42, 2185), similar distinctions are difficult for tetranuclear complexes such as that found in the photosynthetic oxygen-evolving complex.

Reaction of Mn(II) with phenoxyalkanoic acids and di-2-pyridyl ketone oxime (Hpko) leads to neutral tetranuclear complexes of the general formula Mn(4)(O)(pko)(4)(phenoxyalkanoato)(4) (phenoxyalkanoic acids: H-mcpa=2-methyl-4-chloro-phenoxy-acetic acid, H-2,4,5-T=2,4,5-trichloro-phenoxy-acetic acid or H3,4-D=3,4-dichloro-phenoxy-acetic acid). The compounds were synthesized by adding di-2-pyridyl ketone oxime to MnCl(2) in the presence of the sodium salts of the alkanoic acids in methanol. The crystal structure of Mn(4)(II/II/II/IV)(O)(pko)(4)(2,4,5-T)(4).2.5CH(3)OH.0.25H(2)O 1 shows that the complex consists of a [Mn(4)(mu(4)-O)](8+) core with a Mn(IV) and 3 Mn(II) ions in octahedral environment and a mu(4)-O atom bridging the four manganese ions. Spectroscopic studies of the interaction of these tetranuclear clusters with DNA showed that these compounds bind to dsDNA. The binding strength of the Mn(4)(II/II/II/IV)(O)(pko)(4)(2,4,5-T)(4) complex for calf thymus DNA is equal to 1.1x10(4)M(-1). Among the deoxyribonucleotides they bind preferentially to deoxyguanylic acid (dGMP). Competitive studies with ethidium bromide (EthBr) showed that the Mn(4)(II/II/II/IV)(O)(pko)(4)(2,4,5-T)(4) complex exhibited the ability to displace the DNA-bound EthBr indicating that the complex binds to DNA via intercalation in strong competition with EthBr for the intercalative binding site. Additionally, DNA electrophoretic mobility experiments showed that all three complexes, at low cluster concentration, are obviously capable of binding to pDNA causing its cleavage (relaxation) at physiological pH and temperature. At higher cluster concentration, catenated dimer forms of pDNA was formed.

The use of phenyl 2-pyridyl ketoxime (PhPyCNO)/X(-)"blends" (X(-) = OH(-), Cl(-), ClO(4)(-)) in copper chemistry has yielded trinuclear clusters that have been characterized as inverse-9-metallacrown-3 accommodating one or two anions. The magnetic behaviour has shown a large antiferromagnetic interaction. The discrepancy between the Brillouin curve and the experiment has been assigned to the influence of the antisymmetric interaction. By introducing in the magnetization formula the antisymmetric terms derived from the fitting of the susceptibility data the simulated curve become almost superimposable to the experimental one. From the EPR findings it has been shown that the compound [Cu(3)(PhPyCNO)(3)(OCH(3))(Cl)(ClO(4))] () having isosceles magnetic symmetry or lower (delta not equal 0), the antisymmetric exchange is important (G not equal 0) and DeltaE > hv. The structures of the two complexes have been determined by single-crystal X-ray crystallography.

The use of di-2-pyridyl ketone oxime (Hpko)/X- "blends" (X- = OH-, Cl-, ClO4-) in copper chemistry has yielded neutral binuclear and cationic trinuclear, pentanuclear or hexanuclear complexes. Various synthetic procedures have led to the synthesis of compounds [Cu5(pko)7].[ClO4]3.2CH3OH.2H2O (1), [Cu3(pko)3(OH)(Cl)]2[Ph4B]2.4DMF.2H2O (2), [Cu2(pko)4] (3), {[Cu6(pko)6ClO4(CH3CN)6][Cu6(pko)6(ClO4)3(CH3CN)4]}.8ClO4.14CH3CN.H2O (4). The structures of the complexes have been determined by single-crystal X-ray crystallography.

The structural characterization of complexes [Mn(II)4Mn(III)22(pdol)12(OCH3)12(O)16(N3)6] (1) and [Mn(II)4Mn(III)22(pdol)12(OCH3)12(O)16(OH)2(H3O)(OCH3)3].ClO4.5CH3OH (2), where pdol(2-) is di-2-pyridyl methanediol, reveals that each has a metallacryptand shell that encapsulates a manganese oxide core. Variable-temperature direct current magnetic susceptibility measurements on 2 indicate a paramagnetic ground state that results from an overall antiferromagnetic interaction in the cluster, with chiT values decreasing from 300 K (51.2 cm3 K mol(-1)) to 2 K (19.8 cm3 K mol(-1)). Variable-temperature alternating current magnetic susceptibility measurements imply that both 1 and 2 behave as single-molecule magnets. Fitting the frequency-dependent out-of-phase magnetic susceptibility to the Arrhenius equation yields an effective energy barrier, Ueff, to magnetization relaxation of 16.5 +/- 0.7 K (11.5 +/- 0.5 cm(-1)) for 1 and 36.2 +/- 2.0 K (25.1 +/- 1.4 cm(-1)) for 2. The larger value for 2 is in agreement with the lower molecular symmetry, larger magnetoanisotropy, and higher ground spin state of 2 compared to those of 1. This observation suggests a new strategy for increasing the blocking temperatures in high-nuclearity manganese clusters.

Interaction of manganese with salicylhydroxamic ligands (shi) in methanol, in the presence of pyridine, leads to the formation of a series of 15-membered metallacrown (MC) Mn(II)(L)2[15-MCMn(III)N(shi)-5](py)6 or 7, (L=formato, benzoate or alkanoato ligand, py=pyridine). In the absence of pyridine, the Mn(II)(L)2[12-MCMn(III)N(shi)-4](MeOH)6 metallacrown was isolated and structurally characterized. The crystal structure of {[Mn(II)(HCOO)2][(15-MCMn(III)N(shi)-5)(py)7]}.py.1.9CH3OH.H2O (1) contains a neutral 15-membered metallacrown ring consisting of five Mn(III) and five shi(-3) ligands. The 15-membered metallacrown ring is formed by the succession of five structural moieties of the type [Mn(III)-N-O]. The diverse in the configuration (planar or propeller) for the ring Mn(III) ions gives the metallacrown core a bending structure. The crystal structure of {[Mn(II)(C6H5COO)2][(12-MCMn(III)N(shi)-4)(CH3OH)6]}.2CH3OH (2) contains a neutral 12-membered metallacrown ring consisting of four Mn(III) and four shi(-3) ligands. The 12-membered metallacrown ring is formed by the same way of succession of four structural moieties of the type [Mn(III)-N-O], while the presence of a planar only configuration of shi ligands around ring Mn(III) ions gives to the metallacrown core a planar structure. The encapsulated Mn(II) is six and seven-coordinate for (1) and (2), respectively, and is bound to the hydroximate oxygen of the metallacrown core and two oxygen atoms from the carboxylate ligands. Antibacterial screening data showed that, among all the compounds tested, manganese metallacrowns are more active compared to the simple manganese herbicide or carboxylate complexes, with increased efficiency for [15-MCMn(III)N(shi)-5] compared to the analogous [12-MCMn(III)N(shi)-4].

Reaction of Mn(ClO4)2 with di-pyridyl ketone oxime, (2-py)2C=NOH, gives the novel cluster [Mn(II)4Mn(III)6Mn(IV)2(mu4-O)2(mu3-O)4(mu3-OH)4(mu3-OCH3)2(pko)12](OH)(ClO4)3 1. It is the only example of a 24-MC-8, and the first metallacrown with ring metal ions in three different oxidation states. Magnetic measurements show antiferromagnetic behavior.

The trinuclear complex Mn(3)(pko)(4)(CH(3)O)(2)(SCN)(2).CH(3)OH, 1, where Hpko is 2,2'-dipyridylketonoxime, is a rare example of a complex simultaneously containing Mn(II) and Mn(IV). X-ray crystallography and XANES spectroscopy clearly distinguish the Mn(II)(2)Mn(IV) valence isomer from the more commonly observed Mn(III)(2)Mn(II) formulation. Fits to variable-temperature magnetic susceptibility data indicate that the Mn(II) and Mn(IV) are ferromagnetically coupled (J = +6.13 cm(-1)) and that 1 has an S = (13)/(2) ground state.

The effect on DNA and the antibacterial activity of a series of high nuclearity nickel compounds with three, four and five metal atoms were examined. The compounds have a mixed ligand composition with salicylhydroxamic acid and di-2-pyridyl-ketonoxime as chelate agents. In the trinuclear compound Ni(3)(shi)(2)(Hpko)(2)(py)(2)(1), two metal ions show a square planar geometry while the third one is in an octahedral environment. The compounds with four and five nickel atoms construct metallacrown cores with two distinct connectivities. The tetranuclear vacant metallacrown [12-MC(Ni(II)N(Hshi)2(pko)2)-4](2+) shows the connectivity pattern [-O-Ni-O-N-Ni-N-](2), while the pentanuclear ([Ni(II)][12-MC(Ni(II)N(shi)2(pko)2)-4])(2+) follows the pattern [-Ni-O-N-](4). Two distinct arrangements of the chelates around the ring metal ions were observed; a 6-5-6-5-6-5-6-5 arrangement for the [12-MC(Ni(II)N(Hshi)2(pko)2)-4] core and a 6-6-5-5-6-6-5-5 arrangement for the [12-MC(Ni(II)N(shi)2(pko)2)-4] core. Magnetic variable temperature susceptibility study of the trinuclear compound revealed the presence of one paramagnetic nickel(II) ion with strong crystal field dependence, with D=5.0(4) cm(-1), g(xy)=2.7(3) and g(z)=2.3(3). The effect of the synthesized Ni(II) complexes on the integrity and electrophoretic mobility of nucleic acids was examined. Only compounds 2, 3 and 4 altered the mobility of pDNA, forming high molecular weight concatamers at low concentrations or precipitates at higher concentrations. Antibacterial activity screening of the above compounds suggests that nickel compounds 2, 3 and 4 were the most active and can act as potent antibacterial agents.

In this paper we report the synthesis and characterization of Ca(II), Gd(III) and Ce(III) complexes with chlorophenoxyalkanoic acids, which are commonly used as herbicides. The Gd(III) and Ca(II) complexes were characterized by the typical formulas [Gd(III)(L)(3)(H(2)O)(2).2dmf](n) and [Ca(L)(2)(MeOH)(2)](n) [L=[2,4-D=2,4-dichlorophenoxyacetic acid, 2,4,5-T=2,4,5-trichlorophenoxyacetic acid, MCPA=2-methyl-4-chlorophenoxy acetic acid and 2,4-DP=2-(2,4-dichlorophenoxy)propanoic acid]]. The crystal structure of the Gd(III) complex with 2,4-D shows that the compound is a one-dimensional polymer with a [Gd(III)(2)(2,4-D)(6)(H(2)O)(4)] dimeric repeat unit and the gadolinium atoms are in a nine-coordination environment, while the crystal structure of the Ca analog shows that it also has a polymeric structure with a [Ca(2)(2,4-D)(4)(CH(3)OH)(4)] dimeric repeat unit and the calcium atoms are in an eight-coordination environment. The gadolinium compound displays three different coordination modes for the carboxylato moiety, bidentate chelate, bidentate double bound and bidentate triple bound, while the calcium compound displays only one, bidentate triple bound. Coordination spheres are completed with oxygens of H(2)O or MeOH molecules, respectively. The complexes were tested against a few common bacteria by minimum inhibitory concentration (MIC) experiments and did not exhibit any antimicrobial action at concentrations up to 1600 microg/ml.

Interaction of ZnCl(2) with Hpko (Hpko, di-2-pyridyl-ketonoxime) results in the formation of a uninuclear Zn(Hpko)Cl(2) (1) compound or in a 12-membered tetranuclear metallacrown (OH)(2)[inv12-MC(Zn(II)N(pko))-4]Cl(2) (2) depending on the pH of the mother solution. The addition of H(3)shi (H(3)shi, salicylhydroxamic acid) leads to the formation of the octanuclear 12-membered tetranuclear metallacrown [Zn(2)]([Zn(2)(pko)(4)][12-MC(Zn(II)N(shi))-4](CH(3)OH)(2)) (3). The metallacrown core of 2 is characterized as "inverse" because the zinc atoms, rather than oxygen atoms, are oriented toward the central cavity. Two triply bridging hydroxides are accommodated in the center of the metallacrown ring. The pko(-) ligands form a propeller configuration that imposes absolute stereoisomerism with Lambda and Delta chirality. Each hydroxo oxygen bridges two octahedral zinc atoms and a tetrahedral one. The octanuclear cluster Zn(8)(shi)(4)(pko)(4)(CH(3)OH)(2) contains a 12-membered tetranuclear metallacrown core constructed by four Zn metal atoms and four shi(3-) ligands. So, a part of the cluster can be described as having the formally anionic [12-MC(Zn(II)N(shi))-4](4-) core. Two of the zinc atoms are in octahedral coordination environment while for the other two the geometry is best described as distorted trigonal bipyramidal. The metallacrown core accommodates a binuclear compound with the formula [Zn(2)(pko)(4)]. Two of the ring metal ions create binuclear units with two zinc ions, respectively, with two oxamato oxygens, and two phenolato oxygens, of the four interlinked shi(3-) ligands acting as bridging atoms.

Interaction of manganese with salicylhydroxamic ligands leads to the formation of a series of 15-membered metallacrown Mn(II)(L)(2)[15-MC(Mn(III)N(shi))-5](py)(6) (L=alkanoato ligand). The crystal structure contains a neutral 15-membered metallacrown ring of the type [15-MC(Mn(III)N(shi))-5]. The metallacrown core consists of five Mn(III) and five shi(-3) ligands. The 15-membered metallacrown ring is formed by the succession of five structural moieties of the type [Mn(III)-N-O]. The diversity in the configuration (planar or propeller) for the ring Mn(III) ions gives to the metallacrown core flexibility and simultaneously allows the encapsulation of the sixth Mn(II). The encapsulated Mn(II) is seven-coordinate and is bound to the five hydroximate oxygen donors provided by the metallacrown core, and two oxygen atoms from the carboxylate herbicide ligands. Antibacterial screening data showed that among all the compounds tested, manganese metallacrowns are more active than the simple manganese herbicide or carboxylate complexes while an increase in the efficiency of [15-MC(Mn(III)N(shi))-5] towards the analogous [12-MC(Mn(III)N(shi))-4] can be observed.

Interaction of manganese with salicylhydroxamic ligands leads to the formation of the 12-membered metallacrown [Mn(II)(2(2,4-DP)2(HCOO)2]-[12-MC(Mn(III)N(shi)-4](py)6 (2) (H-2,4-DP =2-(2,4-dichlorophenoxy)propionic acid) and the 15-membered metallacrown [Mn(II)(2,4-D)2][15-MC(Mn(III)N(shi)-5](py)6 (1) (H-2,4-D = 2,4-dichlorophenoxyacetic acid). The crystal structure analysis shows that mononuclear and dinuclear alkanoato complexes are accommodated in the cavity of the metallacrown ring. The magnetic behaviour of 1 and 2 and the magnetic behaviour of the fused 12-membered metallacrown [Ni(II)(mcpa)]2-[12-MC(Ni(II)N(shi)2(pko)2-4][12-MC(Ni(II)N(shi)3(pko)-4]-(CH3OH)3(H2O) (3) (Hmcpa = 2-methyl-4-chlorophenoxyacetic acid) have shown that the zero field and/or the population of many energy levels at low temperatures is the reason for the divergence of the susceptibility data at high fields. For compound 3, the ground state is S = 0, with S = 1 and S = 2 low-lying excited states. This leads to a non-Brillouin behaviour of the magnetisation, since the ground state is very close to the excited states.

Assembly reactions that can prepare reliably regioselective metallamacrocyclic complexes have been a target in the development of metallacrowns. To this end, a series of mixed ligand and mixed ligand/mixed metal metallacrowns have been synthesized in high yield and structurally characterized. Two distinct connectivities have been observed in these types of metallacrowns. The monomeric, vacant metallacrown with mixed ligand composition [12-MC(Ni(II)N(Hshi)2(pko)2-4)] (1a) shows the connectivity pattern [-O-Ni-O-N-Ni-N-]2 while the other Ni metallacrowns, [12-MC(Ni(II)N(shi)2(pko)2-4)] (2a) and the coupled [12-MC(Ni(II)N(shi))2(pko)2-4)][12-MC(Ni(II)N(shi))3(pko)-4)] (3a) fused metallacrowns as well as the mixed metal Mn-Ni metallacrown [12-MC(Ni(II)Mn(III)N(shi)2(pko)2-4)] (4a), follow the pattern [-Ni-O-N-]4. Also, three distinct arrangements of the chelate rings around the metal ions have been observed. The syntheses are completely general, allowing for the substitution of different ligands into the metallacrown core. Compounds 1 and 4 show the 6-5-6-5-6-5-6-5 arrangement, compounds 2 and 3(1) the 6-6-5-5-6-6-5-5, and the 3(2) component the 6-6-5-5-6-5-6-5. The obtained structures can be rationalized by balancing the charge at each metal site in the metallacrown. Variable temperature magnetic susceptibility measurements show that exchange interactions for all the compounds are weak and dominantly antiferromagnetic (e.g., 2a gives an exchange coupling of J = -1.2 cm(-1) with g = 2.2). In solution, the metallacrowns are shown to be stable both to decomposition and ligand exchange.

The copper complexes with the commercial auxin herbicides MCPA, 2,4-D, and 2,4,5-T in the presence of a nitrogen donor heterocyclic ligand, phen or bipyam, were prepared and characterized. The available evidence supports a dimeric structure for the 2,4-D complex in the presence of bipyam while phen leads to monomeric forms. The EPR spectrum of Cu2(2,4-D)4(bipyam)2 at 4 K in the solid state exhibits an axial signal which corresponds to almost isolated S = 1/2 magnetic ions. Magnetic data for the dimer show a weak antiferromagnetic interaction between the two metal ions with J = -08 cm-1. The crystal structures of tetrakis[(2,4-dichlorophenoxy)acetato]bis(2,2'-bipyridylamine)dicopper(II), 1, bis(1,10-phenanthroline)[(2,4,5-trichlorophenoxy)acetato]copper(II) chloride, 2, and aqua(1,10-phenanthroline)bis[((2-methyl-4-chlorophenoxyacetato]copper(II), 3, were determined and refined by least-squares methods using three-dimensional MoK alpha data. 1 crystallizes in space group P1, in a cell of dimensions a = 10813(1) A, b = 12138(1) A, c = 11909(1) A, alpha = 86448(3) degrees, beta = 80127(3) degrees, and gamma = 63982(3) degrees, and V = 13837(2) A3, with Z = 1 2 crystallizes in space group I2/a, in a cell of dimensions a = 29958(9) A, b = 11342(3) A, c = 21196(7) A, beta = 10794(1) degrees, and V = 68522(4) A3, with Z = 8 3 crystallizes in space group P1, in a cell of dimensions a = 87419(8) A, b = 12512(1) A, c = 14598(1) A, alpha = 110737(1) degrees, beta = 95742(2) degrees, gamma = 103286(2) degrees, V = 14241(2) A3, with Z = 2.