A category of naked maghemite nanoparticles (γ-Fe2O3), named surface active maghemite nanoparticles (SAMNs), is characterized by biological safety, high water colloidal stability and a surface chemistry permitting the binding of ligands. In the present study, the interaction between SAMNs and an antibiotic displaying chelating properties (oxytetracycline, OxyTC) was extensively structurally and magnetically characterized. OxyTC emerged as an ideal probe for providing insights into the colloidal properties of SAMNs. At the same time, SAMNs turned out as an elective tool for water remediation from OxyTC. Therefore, a dilute colloidal suspension of SAMNs was used for the removal of OxyTC in large volume tanks where, to simulate a real in situ application, a population of zebrafish (Danio rerio) was introduced. Interestingly, SAMNs led to the complete removal of the drug without any sign of toxicity for the animal model. Moreover, OxyTC immobilized on SAMNs surface resulted safe for sensitive Escherichia coli bacteria strain. Thus, SAMNs were able to recover the drug and to suppress its antibiotic activity envisaging their feasibility as competitive option for water remediation from OxyTC in more nature related scenarios. The present contribution stimulates the use of novel smart colloidal materials to cope with complex environmental issues.
- MeSH
- antibakteriální látky chemie farmakologie MeSH
- dánio pruhované MeSH
- Escherichia coli účinky léků MeSH
- koloidy chemie MeSH
- magnetické nanočástice chemie MeSH
- mikrobiální testy citlivosti MeSH
- oxytetracyklin chemie farmakologie MeSH
- povrchové vlastnosti MeSH
- suspenze chemie MeSH
- velikost částic MeSH
- zvířata MeSH
- Check Tag
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
Arsenic compounds are carcinogenic to humans and are typically removed from contaminated water using various sorbents. The ionic composition plays a significant role in arsenate removal efficiency during the process of water remediation. Here, we quantify the effects of natural ions (chlorides, nitrates, carbonates, sulfates, and phosphates) and humic acid on the removal of arsenates by ferrate(VI) at pH = 6.6. In the experiments, the initial concentration of arsenates was 10 mg L-1 (as As) and the concentrations of ions varied in the range from 5 to 100 mg L-1 of element in ionic form and humic acid. The achieved results show that only phosphate ions had principle influence on the efficiency of arsenate removal by ferrate(VI). The effect of phosphates was elucidated by applying transmission electron microscopy, energy-dispersive X-ray spectroscopy, and low temperature in-field 57Fe Mössbauer spectroscopy to solid samples, prepared under different weight ratios of ferrate(VI), arsenates, and phosphates. These results show three crucial effects of phosphates on the arsenate removal mechanisms. At low P:As weight ratio (up to 1:1), the incorporation of arsenate ions into the crystalline structure of γ-Fe2O3/γ-FeOOH nanoparticles was found to be suppressed by the presence of phosphates. Thus, arsenates were mainly adsorbed onto the surface of γ-Fe2O3/γ-FeOOH nanoparticles. Further increase in the P:As weight ratio (more than 1:1) resulted in the competition between arsenates and phosphates sorption. With the increased concentration of phosphate ions, the number of arsenates on the surface of γ-Fe2O3/γ-FeOOH nanoparticles was reduced. Finally, the complexation of iron(III) ions with phosphate ions occurred, leading to a decrease in the arsenates removal efficiency, which resulted from a lower content of precipitated γ-Fe2O3/γ-FeOOH nanoparticles. All these aspects need to be considered prior to application of ferrate(VI) for arsenates removal in real natural waters.
- MeSH
- adsorpce MeSH
- arsenáty chemie MeSH
- chemické látky znečišťující vodu chemie MeSH
- chloridy chemie MeSH
- čištění vody metody MeSH
- dusičnany chemie MeSH
- fosfáty chemie MeSH
- huminové látky * MeSH
- koncentrace vodíkových iontů MeSH
- sírany chemie MeSH
- spektroskopie Mossbauerova MeSH
- uhličitany chemie MeSH
- železité sloučeniny chemie MeSH
- železo chemie MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
The development of anticancer drug delivery systems which retain or enhance the cytotoxic properties of the drug to tumorous tissues, while reducing toxicity to other organs is of key importance. We investigated different poly(methacrylic acid)-g-poly(ethyleneglycol methacrylate) polymers as in situ coating agents for magnetite nanocrystallites. The obtained magnetic nano-assemblies were in turn thoroughly characterized for their structural, colloidal and physicochemical properties (drug loading capacity/release, magnetic field triggered drug release, cell uptake and localization) in order to select the best performing system. With the focus on in vivo validation of such magnetic drug delivery systems for first time, we selected cisplatin as the drug, since it is a potent anticancer agent which exhibits serious side effects due to lack of selectivity. In addition, cisplatin would offer facile determination of the metal content in the animal tissues for biodistribution studies. Alongside post-mortem Pt determination in the tissues, the biodistribution of the drug nanocarriers was also monitored in real time with PET-CT (positron emission tomography/computed tomography) with and without the presence of magnetic field gradients; using a novel chelator-free method, the nanoparticles were radiolabeled with 68Ga without having to alter their structure with chemical modifications for conjugation of radiochelators. The ability to be radiolabeled in such a straightforward but very robust way, along with their measured high MRI response, renders them attractive for dual imaging, which is an important functionality for translational investigations. Their anticancer properties were evaluated in vitro and in vivo, in a cisplatin resistant HT-29 human colon adenocarcinoma model, with and without the presence of magnetic field gradients. Enhanced anticancer efficacy and reduced toxicity was recorded for the cisplatin-loaded nanocarriers in comparison to the free cisplatin, particularly when a magnetic field gradient was applied at the tumor site. Post mortem and real-time tissue distribution studies did not reveal increased cisplatin concentration in the tumor site, suggesting that the enhanced anticancer efficacy of the cisplatin-loaded nanocarriers is driven by mechanisms other than increased cisplatin accumulation in the tumors.
- MeSH
- adenokarcinom farmakoterapie patologie MeSH
- antitumorózní látky aplikace a dávkování farmakokinetika farmakologie MeSH
- buňky HT-29 MeSH
- chemorezistence MeSH
- cisplatina aplikace a dávkování farmakokinetika farmakologie MeSH
- kyseliny polymethakrylové chemie MeSH
- lidé MeSH
- magnetické nanočástice * MeSH
- methakryláty chemie MeSH
- myši nahé MeSH
- myši SCID MeSH
- nádory tračníku farmakoterapie patologie MeSH
- PET/CT MeSH
- polyethylenglykoly chemie MeSH
- systémy cílené aplikace léků * MeSH
- tkáňová distribuce MeSH
- xenogenní modely - testy antitumorózní aktivity MeSH
- zvířata MeSH
- Check Tag
- lidé MeSH
- ženské pohlaví MeSH
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
Despite the importance of phosphorus as a nutrient for humans and its role in ecological sustainability, its high abundance, resulting in large part from human activities, causes eutrophication that negatively affects the environment and public health. Here, we present the use of ferrate(VI) as an alternative agent for removing phosphorus from aqueous media. We address the mechanism of phosphate removal as a function of the Fe/P mass ratio and the pH value of the solution. The isoelectric point of γ-Fe2O3 nanoparticles, formed as dominant Fe(VI) decomposition products, was identified to play a crucial role in predicting their efficiency in removing of phosphates. Importantly, it was found that the removal efficiency dramatically changes if Fe(VI) is added before (ex-situ conditions) or after (in-situ conditions) the introduction of phosphates into water. Removal under in-situ conditions showed remarkable sorption capacity of 143.4 mg P per gram of ferric precipitates due to better accessibility of active surface sites on in-situ formed ferric oxides/oxyhydroxides. At pH = 6.0-7.0, complete removal of phosphates was observed at a relatively low Fe/P mass ratio (5:1). The results show that phosphates are removed from water solely by sorption on the surface of γ-Fe2O3/γ-FeOOH core/shell nanoparticles. The advantages of Fe(VI) utilization include its environmentally friendly nature, the possibility of easy separation of the final product from water by a magnetic field or by natural settling, and the capacity for successful phosphate elimination at pH values near the neutral range and at low Fe/P mass ratios.
Targeted delivery combined with controlled drug release has a pivotal role in the future of personalized medicine. This review covers the principles, advantages, and drawbacks of passive and active targeting based on various polymer and magnetic iron oxide nanoparticle carriers with drug attached by both covalent and noncovalent pathways. Attention is devoted to the tailored conjugation of targeting ligands (e.g., enzymes, antibodies, peptides) to drug carrier systems. Similarly, the approaches toward controlled drug release are discussed. Various polymer-drug conjugates based, for example, on polyethylene glycol (PEG), N-(2-hydroxypropyl)methacrylamide (HPMA), polymeric micelles, and nanoparticle carriers are explored with respect to absorption, distribution, metabolism, and excretion (ADME scheme) of administrated drug. Design and structure of superparamagnetic iron oxide nanoparticles (SPION) and condensed magnetic clusters are classified according to the mechanism of noncovalent drug loading involving hydrophobic and electrostatic interactions, coordination chemistry, and encapsulation in porous materials. Principles of covalent conjugation of drugs with SPIONs including thermo- and pH-degradable bonds, amide linkage, redox-cleavable bonds, and enzymatically-cleavable bonds are also thoroughly described. Finally, results of clinical trials obtained with polymeric and magnetic carriers are analyzed highlighting the potential advantages and future directions in targeted anticancer therapy.
- MeSH
- koncentrace vodíkových iontů MeSH
- ligandy MeSH
- magnetické nanočástice chemie MeSH
- nosiče léků chemie MeSH
- polymery chemie MeSH
- poréznost MeSH
- povrchové vlastnosti MeSH
- systémy cílené aplikace léků * MeSH
- uvolňování léčiv * MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- přehledy MeSH
In this critical review, we outline various covalent and non-covalent approaches for the functionalization of iron oxide nanoparticles (IONPs). Tuning the surface chemistry and design of magnetic nanoparticles are described in relation to their applicability in advanced medical technologies and biotechnologies including magnetic resonance imaging (MRI) contrast agents, targeted drug delivery, magnetic separations and immobilizations of proteins, enzymes, antibodies, targeting agents and other biosubstances. We review synthetic strategies for the controlled preparation of IONPs modified with frequently used functional groups including amine, carboxyl and hydroxyl groups as well as the preparation of IONPs functionalized with other species, e.g., epoxy, thiol, alkane, azide, and alkyne groups. Three main coupling strategies for linking IONPs with active agents are presented: (i) chemical modification of amine groups on the surface of IONPs, (ii) chemical modification of bioactive substances (e.g. with fluorescent dyes), and (iii) the activation of carboxyl groups mainly for enzyme immobilization. Applications for drug delivery using click chemistry linking or biodegradable bonds are compared to non-covalent methods based on polymer modified condensed magnetic nanoclusters. Among many challenges, we highlight the specific surface engineering allowing both therapeutic and diagnostic applications (theranostics) of IONPs and magnetic/metallic hybrid nanostructures possessing a huge potential in biocatalysis, green chemistry, magnetic bioseparations and bioimaging.
The removal efficiency of heavy metal ions (cadmium(II), Cd(II); cobalt(II), Co(II); nickel(II), Ni(II); copper(II), Cu(II)) by potassium ferrate(VI) (K2FeO4, Fe(VI)) was studied as a function of added amount of Fe(VI) (or Fe) and varying pH. At pH = 6.6, the effective removal of Co(II), Ni(II), and Cu(II) from water was observed at a low Fe-to-heavy metal ion ratio (Fe/M(II) = 2:1) while a removal efficiency of 70% was seen for Cd(II) ions at a high Fe/Cd(II) weight ratio of 15:1. The role of ionic radius and metal valence state was explored by conducting similar removal experiments using Al(III) ions. The unique combination of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), in-field Mössbauer spectroscopy, and magnetization measurements enabled the delineation of several distinct mechanisms for the Fe(VI)-prompted removal of metal ions. Under a Fe/M weight ratio of 5:1, Co(II), Ni(II), and Cu(II) were removed by the formation of MFe2O4 spinel phase and partially through their structural incorporation into octahedral positions of γ-Fe2O3 (maghemite) nanoparticles. In comparison, smaller sized Al(III) ions got incorporated easily into the tetrahedral positions of γ-Fe2O3 nanoparticles. In contrast, Cd(II) ions either did not form the spinel ferrite structure or were not incorporated into the lattic of iron(III) oxide phase due to the distinct electronic structure and ionic radius. Environmentally friendly removal of heavy metal ions at a much smaller dosage of Fe than those of commonly applied iron-containing coagulants and the formation of ferrimagnetic species preventing metal ions leaching back into the environment and allowing their magnetic separation are highlighted.
- MeSH
- chemické látky znečišťující vodu chemie izolace a purifikace MeSH
- čištění vody metody MeSH
- difrakce rentgenového záření MeSH
- fotoelektronová spektroskopie MeSH
- kationty chemie MeSH
- koncentrace vodíkových iontů MeSH
- magnetické nanočástice chemie MeSH
- sloučeniny draslíku chemie MeSH
- sloučeniny železa chemie MeSH
- spektroskopie Mossbauerova MeSH
- těžké kovy chemie izolace a purifikace MeSH
- voda MeSH
- železité sloučeniny chemie MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
The preparation and thorough characterization of a hybrid magnetic carrier system for the possible transport of activated platinum-based anticancer drugs, as demonstrated for cisplatin (cis-[Pt(NH3)2Cl2], CDDP), are described. The final functionalized mag/Au-LA-CDDP* system consists of maghemite/gold nanoparticles (mag/Au) coated by lipoic acid (HLA; LA stands for deprotonated form of lipoic acid) and functionalized by activated cisplatin in the form of cis-[Pt(NH3)2(H2O)2]2+ (CDDP*). The relevant techniques (XPS, EDS, ICP-MS) proved the incorporation of the platinum-containing species on the surface of the studied hybrid system. HRTEM, TEM and SEM images showed the nanoparticles as spherical with an average size of 12 nm, while their superparamagnetic feature was proven by 57Fe Mössbauer spectroscopy. In the case of mag/Au, mag/Au-HLA and mag/Au-LA-CDDP*, weaker magnetic interactions among the Fe3+ centers of maghemite, as compared to maghemite nanoparticles (mag), were detected, which can be associated with the non-covalent coating of the maghemite surface by gold. The pH and time-dependent stability of the mag/Au-LA-CDDP* system in different media, represented by acetate (pH 5.0), phosphate (pH 7.0) and carbonate (pH 9.0) buffers and connected with the release of the platinum-containing species, showed the ability of CDDP* to be released from the functionalized nanosystem.
- MeSH
- biologický transport MeSH
- diferenční termická analýza MeSH
- fotoelektronová spektroskopie MeSH
- koncentrace vodíkových iontů MeSH
- kovové nanočástice chemie ultrastruktura MeSH
- magnetické jevy * MeSH
- nanotechnologie metody MeSH
- nosiče léků chemie MeSH
- platina terapeutické užití MeSH
- spektrofotometrie atomová MeSH
- spektrofotometrie infračervená MeSH
- spektrometrie rentgenová emisní MeSH
- spektroskopie Mossbauerova MeSH
- termogravimetrie MeSH
- železité sloučeniny chemie MeSH
- zlato chemie MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
Steroidal estrogens are one of the most challenging classes of hazardous contaminants as they can cause adverse effects to biota in extremely low concentrations. They emerge in both waste waters and surface waters serving as a source of drinking water. Environmental Quality Standards for 17β-estradiol (E2) and 17α-ethinylestradiol (EE2), promulgated within the EU Water Framework Directive, are 0.4 and 0.035 ng L(-1), respectively. Because nanoscale zero-valent iron (nZVI) particles have been previously used in numerous remediation technologies and have the advantage of possible magnetic separation, interaction of nZVI with E2 and EE2 in water was investigated to assess the potential role of nZVI in removing steroidal estrogens. A mixture of E2 and EE2 dissolved in water was shaken with varying doses of nZVI for 1-5 h. Concentration-dependent removal of the estrogens was observed but removal did not increase significantly with time. Concentrations of the estrogens were determined by HPLC/MS/MS and a biodetection reporter gene assay. Sorption and nonspecific oxygen-mediated oxidation of estrogens were identified as the most probable removal mechanisms. Two independent experiments confirmed that significant decrease of estrogens concentration is achieved when at least 2 g L(-1) of nZVI is applied. The presented study provides insights into the mechanisms of nZVI interaction with steroidal estrogens under aerobic conditions prevailing in currently applied water treatment technologies.
