Search

Mass-specific optical absorption coefficients (MACs) and the imaginary part (κ) of the refractive indices of various mineral dust components including silicate clays (illite, kaolin and bentonite), oxides (quartz, hematite and rutile), and carbonate (limestone) were determined at the wavelengths of 1064, 532, 355 and 266 nm. The MAC values were calculated from aerosol optical absorption coefficients measured by a multi-wavelength photoacoustic (PA) instrument, the mass concentration and the number size distribution of the generated aerosol samples as well as the size transfer functions of the measuring instruments. Values of κ were calculated from the measured and particle-loss-corrected data by using a Mie-theory-based retrieval algorithm. The determined values could be used for comparisons with calculated wavelength-dependent κ values typically deduced from bulk-phase measurements by using indirect measurement methods. Accordingly, the presented comparison of the measured and calculated aerosol optical absorption spectra revealed the strong need for standardized sample preparation and measurement methodology in case of bulk-phase measurements.

Humic substances (HSs) have been researched for a long time and still manage to surprise humanity today. According to the latest research, in addition to their previously well-known effects, they also have antioxidant properties. However, this previous research does not examine the difference in the antioxidant effect of the fractions extracted/produced in different processes; they do not consider the light absorption of the HSs, which falsifies analysis based on the measurement of color change over time. In the present work, HS fractions were obtained from leonardite, the extraction processes can also be implemented on an industrial scale. The fractions were characterized by elementary analysis, UV-Vis and FT-IR spectroscopies, to prove that our self-extracted samples have similar characteristics to the International Humic Substances Society (IHSS) standard samples. The different methods of HS fractionation affected the elemental composition, and the spectral characteristics. The antioxidant effect was investigated using the DPPH method to screen the antioxidant efficiency of humic, fulvic, and himatomelanic acids. In addition, we compared our results with the IHSS standard samples to obtain a more comprehensive picture of the antioxidant effect of HSs extracted in different ways according to the DPPH method. Based on our results, the extraction method affects not only the physico-chemical properties but also the free radical scavenging activity of the fractions.

Drug therapy for vascular disease has been promoted to inhibit angiogenesis in atherosclerotic plaques and prevent restenosis following surgical intervention. This paper investigates the arterial depositions and distribution of PEG-functionalized magnetic nanocomposite clusters (PEG_MNCs) following local delivery in a stented artery model in a uniform magnetic field produced by a regionally positioned external permanent magnet; also, the PEG_MNCs aggregation or chain formation in and around the implanted stent. The central concept is to employ one external permanent magnet system, which produces enough magnetic field to magnetize and guide the magnetic nanoclusters in the stented artery region. At room temperature (25 °C), optical microscopy of the suspension model's aggregation process was carried out in the external magnetic field. According to the optical microscopy pictures, the PEG_MNC particles form long linear aggregates due to dipolar magnetic interactions when there is an external magnetic field. During magnetic particle targeting, 20 mL of the model suspensions are injected (at a constant flow rate of 39.6 mL/min for the period of 30 s) by the syringe pump in the mean flow (flow velocity is Um = 0.25 m/s, corresponding to the Reynolds number of Re = 232) into the stented artery model. The PEG_MNC clusters are attracted by the magnetic forces (generated by the permanent external magnet) and captured around the stent struts and the bottom artery wall before and inside the implanted stent. The colloidal interaction among the MNC clusters was investigated by calculating the electrostatic repulsion, van der Waals and magnetic dipole-dipole energies. The current work offers essential details about PEG_MNCs aggregation and chain structure development in the presence of an external magnetic field and the process underlying this structure formation.

Understanding the physicochemical factors affecting nanoparticle transport in porous media is critical for their environmental application. Water-saturated column experiments were conducted to investigate the effects of input concentration (Co), ionic strength (IS), and sand grain size on the transport of poly(acrylic acid-co-maleic acid) coated magnetite nanoparticles (PAM@MNP). Mass recoveries in the column effluent ranged from 45.2 to 99.3%. The highest relative retention of PAM@MNP was observed for the lowest Co. Smaller Co also resulted in higher relative retention (39.8%) when IS increased to 10 mM. However, relative retention became much less sensitive to solution IS as Co increased. The high mobility is attributed to the PAM coating provoking steric stability of PAM@MNP against homoaggregation. PAM@MNP retention was about 10-fold higher for smaller grain sizes, i.e., 240 µm and 350 µm versus 607 µm. The simulated maximum retained concentration on the solid phase (Smax) and retention rate coefficient (k1) increased with decreasing Co and grain sizes, reflecting higher retention rates at these parameters. The study revealed under various IS for the first time the high mobility premise of polymer-coated magnetite nanoparticles at realistic (<10 mg L−1) environmental concentrations, thereby highlighting an untapped potential for novel environmental PAM@MNP application usage.

When exposed to an alternating magnetic field, superparamagnetic nanoparticles can elicit the required hyperthermic effect while also being excellent magnetic resonance imaging (MRI) contrast agents. Their main drawback is that they diffuse out of the area of interest in one or two days, thus preventing a continuous application during the typical several-cycle multi-week treatment. To solve this issue, our aim was to synthesise an implantable, biodegradable membrane infused with magnetite that enabled long-term treatment while having adequate MRI contrast and hyperthermic capabilities. To immobilise the nanoparticles inside the scaffold, they were synthesised inside hydrogel fibres. First, polysuccinimide (PSI) fibres were produced by electrospinning and crosslinked, and then, magnetitc iron oxide nanoparticles (MIONs) were synthesised inside and in-between the fibres of the hydrogel membranes with the well-known co-precipitation method. The attenuated total reflectance Fourier-transform infrared spectroscopy (ATR-FTIR) investigation proved the success of the chemical synthesis and the presence of iron oxide, and the superconducting quantum interference device (SQUID) study revealed their superparamagnetic property. The magnetic hyperthermia efficiency of the samples was significant. The given alternating current (AC) magnetic field could induce a temperature rise of 5 °C (from 37 °C to 42 °C) in less than 2 min even for five quick heat-cool cycles or for five consecutive days without considerable heat generation loss in the samples. Short-term (1 day and 7 day) biocompatibility, biodegradability and MRI contrast capability were investigated in vivo on Wistar rats. The results showed excellent MRI contrast and minimal acute inflammation.

Ferrofluids investigated along for about five decades are ultrastable colloidal suspensions of magnetic nanoparticles, which manifest simultaneously fluid and magnetic properties. Their magnetically controllable and tunable feature proved to be from the beginning an extremely fertile ground for a wide range of engineering applications. More recently, biocompatible ferrofluids attracted huge interest and produced a considerable increase of the applicative potential in nanomedicine, biotechnology and environmental protection. This paper offers a brief overview of the most relevant early results and a comprehensive description of recent achievements in ferrofluid synthesis, advanced characterization, as well as the governing equations of ferrohydrodynamics, the most important interfacial phenomena and the flow properties. Finally, it provides an overview of recent advances in tunable and adaptive multifunctional materials derived from ferrofluids and a detailed presentation of the recent progress of applications in the field of sensors and actuators, ferrofluid-driven assembly and manipulation, droplet technology, including droplet generation and control, mechanical actuation, liquid computing and robotics.

The production of stable and homogeneous batches during nanoparticle fabrication is challenging. Surface charging, as a stability determinant, was estimated for 3-aminopropyltriethoxysilane (APTES) coated pre-formed magnetite nanoparticles (MNPs). An important consideration for preparing stable and homogenous MNPs colloidal systems is the dispersion stage of pre-formed samples, which makes it feasible to increase the MNP reactive binding sites, to enhance functionality. The results gave evidence that the samples that had undergone stirring had a higher loading capacity towards polyanions, in terms of filler content, compared to the sonicated ones. These later results were likely due to the harsh effects of sonication (extremely high temperature and pressure in the cavities formed at the interfaces), which induced the destruction of the MNPs.

Nowadays, numerous researches are being performed to formulate nontoxic multifunctional magnetic materials possessing both high colloidal stability and magnetization, but there is a demand in the prediction of chemical and colloidal stability in water solutions. Herein, a series of silica-coated magnetite nanoparticles (MNPs) has been synthesized via the sol-gel method with and without establishing an inert atmosphere, and then it was tested in terms of humic acids (HA) loading applied as a multifunctional coating agent. The influence of ambient conditions on the microstructure, colloidal stability and HA loading of different silica-coated MNPs has been established. The XRD patterns show that the content of stoichiometric Fe 3 O 4 decreases from 78.8% to 42.4% at inert and ambient atmosphere synthesis, respectively. The most striking observation was the shift of the MNPs isoelectric point from pH ~7 to 3, with an increasing HA reaching up to the reversal of the zeta potential sign as it was covered completely by HA molecules. The zeta potential data of MNPs can be used to predict the loading capacity for HA polyanions. The data help to understand the way for materials' development with the complexation ability of humic acids and with the insolubility of silica gel to pave the way to develop a novel, efficient and magnetically separable adsorbent for contaminant removal.

The scientific community has made great efforts in advancing magnetic hyperthermia for the last two decades after going through a sizeable research lapse from its establishment. All the progress made in various topics ranging from nanoparticle synthesis to biocompatibilization and in vivo testing have been seeking to push the forefront towards some new clinical trials. As many, they did not go at the expected pace. Today, fruitful international cooperation and the wisdom gain after a careful analysis of the lessons learned from seminal clinical trials allow us to have a future with better guarantees for a more definitive takeoff of this genuine nanotherapy against cancer. Deliberately giving prominence to a number of critical aspects, this opinion review offers a blend of state-of-the-art hints and glimpses into the future of the therapy, considering the expected evolution of science and technology behind magnetic hyperthermia.

We present a study on the magnetic hyperthermia properties of graphene oxide/magnetite (GO/MNP) nanocomposites to investigate their heat production behavior upon the modification of the oxidation degree of the carbonaceous host. Avoiding the harsh chemical conditions of the regular in situ co-precipitation-based routes, the oppositely charged MNPs and GO nanosheets were combined by the heterocoagulation process at pH ~ 5.5, which is a mild way to synthesize composite nanostructures at room temperature. Nanocomposites prepared at 1/5 and 1/10 GO/MNP mass ratios were reduced by NaBH 4 and L-ascorbic acid (LAA) under acidic (pH ~ 3.5) and alkaline conditions (pH ~ 9.3). We demonstrate that the pH has a crucial effect on the LAA-assisted conversion of graphene oxide to reduced GO (rGO): alkaline reduction at higher GO loadings leads to doubled heat production of the composite. Spectrophotometry proved that neither the moderately acidic nor alkaline conditions promote the iron dissolution of the magnetic core. Although the treatment with NaBH 4 also increased the hyperthermic efficiency of aqueous GO/MNP nanocomposite suspensions, it caused a drastic decline in their colloidal stability. However, considering the enhanced heat production and the slightly improved stability of the rGO/MNP samples, the reduction with LAA under alkaline condition is a more feasible way to improve the hyperthermic efficiency of magnetically modified graphene oxides.

Iron oxide nanoparticles are the basic components of the most promising magnetoresponsive nanoparticle systems for medical (diagnosis and therapy) and bio-related applications. Multi-core iron oxide nanoparticles with a high magnetic moment and well-defined size, shape, and functional coating are designed to fulfill the specific requirements of various biomedical applications, such as contrast agents, heating mediators, drug targeting, or magnetic bioseparation. This review article summarizes recent results in manufacturing multi-core magnetic nanoparticle (MNP) systems emphasizing the synthesis procedures, starting from ferrofluids (with single-core MNPs) as primary materials in various assembly methods to obtain multi-core magnetic particles. The synthesis and functionalization will be followed by the results of advanced physicochemical, structural, and magnetic characterization of multi-core particles, as well as single- and multi-core particle size distribution, morphology, internal structure, agglomerate formation processes, and constant and variable field magnetic properties. The review provides a comprehensive insight into the controlled synthesis and advanced structural and magnetic characterization of multi-core magnetic composites envisaged for nanomedicine and biotechnology., Competing Interests: The authors declare no conflict of interest.

Current paper presents biological effects of magnetite nanoparticles (MNPs). "Relations of MNP' characteristics (zeta-potential and hydrodynamic diameters) with effects on bacteria and their enzymatic reactions were the main focus.". Photobacterium phosphoreum and bacterial enzymatic reactions were chosen as bioassays. Three types of MNPs were under study: bare Fe 3 O 4 , Fe 3 O 4 modified with 3-aminopropyltriethoxysilane (Fe 3 O 4 /APTES), and humic acids (Fe 3 O 4 /HA). Effects of the MNPs were studied at a low concentration range (< 2 mg/L) and attributed to availability and oxidative activity of Fe 3+ , high negative surface charge, and low hydrodynamic diameter of Fe 3 O 4 /HA, as well as higher Fe 3+ content in suspensions of Fe 3 O 4 /HA. Low-concentration suspensions of bare Fe 3 O 4 provided inhibitory effects in both bacterial and enzymatic bioassays, whereas the MNPs with modified surface (Fe 3 O 4 /APTES and Fe 3 O 4 /HA) did not affect the enzymatic activity. Under oxidative stress (i.e., in the solutions of model oxidizer, 1,4-benzoquinone), MNPs did not reveal antioxidant activity, moreover, Fe 3 O 4 /HA demonstrated additional inhibitory activity. The study contributes to the deeper understanding of a role of humic substances and silica in biogeochemical cycling of iron. Bioluminescence assays, cellular and enzymatic, can serve as convenient tools to evaluate bioavailability of Fe 3+ in natural dispersions of iron-containing nanoparticles, e.g., magnetite, ferrihydrite, etc.

Biopolymer coated magnetite nanoparticles (MNPs) are suitable to fabricate biocompatible magnetic fluid (MF). Their comprehensive characterization, however, is a necessary step to assess whether bioapplications are feasible before expensive in vitro and in vivo tests. The MNPs were prepared by co-precipitation, and after careful purification, they were coated by chondroitin-sulfate-A (CSA). CSA exhibits high affinity adsorption to MNPs (H-type isotherm). We could only make stable MF of CSA coated MNPs (CSA@MNPs) under accurate conditions. The CSA@MNP was characterized by TEM (size ~10 nm) and VSM (saturation magnetization ~57 emu/g). Inner-sphere metal-carboxylate complex formation between CSA and MNP was proved by FTIR-ATR and XPS. Electrophoresis and DLS measurements show that the CSA@MNPs at CSA-loading > 0.2 mmol/g were stable at pH > 4. The salt tolerance of the product improved up to ~0.5 M NaCl at pH~6.3. Under favorable redox conditions, no iron leaching from the magnetic core was detected by ICP measurements. Thus, the characterization predicts both chemical and colloidal stability of CSA@MNPs in biological milieu regarding its pH and salt concentration. MTT assays showed no significant impact of CSA@MNP on the proliferation of A431 cells. According to these facts, the CSA@MNPs have a great potential in biocompatible MF preparation for medical applications.

For biomedical applications, superparamagnetic nanoparticles (MNPs) have to be coated with a stealth layer that provides colloidal stability in biological media, long enough persistence and circulation times for reaching the expected medical aims, and anchor sites for further attachment of bioactive agents. One of such stealth molecules designed and synthesized by us, poly(polyethylene glycol methacrylate- co -acrylic acid) referred to as P(PEGMA-AA), was demonstrated to make MNPs reasonably resistant to cell internalization, and be an excellent candidate for magnetic hyperthermia treatments in addition to possessing the necessary colloidal stability under physiological conditions (Illés et al. J. Magn. Magn. Mater. 2018, 451, 710⁻720). In the present work, we elaborated on the molecular background of the formation of the P(PEGMA-AA)-coated MNPs, and of their remarkable colloidal stability and salt tolerance by using potentiometric acid⁻base titration, adsorption isotherm determination, infrared spectroscopy (FT-IR ATR), dynamic light scattering, and electrokinetic potential determination methods. The P(PEGMA-AA)@MNPs have excellent blood compatibility as demonstrated in blood sedimentation, smears, and white blood cell viability experiments. In addition, blood serum proteins formed a protein corona, protecting the particles against aggregation (found in dynamic light scattering and electrokinetic potential measurements). Our novel particles also proved to be promising candidates for MRI diagnosis, exhibiting one of the highest values of r 2 relaxivity (451 mM -1 s -1 ) found in literature.

This paper is an in-depth analysis devoted to two basic types of water based magnetic fluids (MFs), containing magnetite nanoparticles with electrostatic and with electro-steric stabilization, both obtained by chemical coprecipitation synthesis under atmospheric conditions. The two sets of magnetic fluid samples, one with citric acid (MF/CA) and the other with oleic acid (MF/OA) coated magnetic nanoparticles, respectively, achieved saturation magnetization values of 78.20 kA m-1 for the electrostatically and 48.73 kA m-1 for the electro-sterically stabilized aqueous ferrofluids which are among the highest reported to date. A comprehensive comparative analysis combining electron microscopy, X-ray photoelectron spectroscopy, attenuated total reflectance Fourier transform infrared spectroscopy, vibrating sample magnetometry, small-angle X-ray and neutron scattering, dynamic light scattering and magneto-rheometry revealed similarities and essential differences on the microscopic and macroscopic level between the two kinds of water-based ferrofluids. While the saturation magnetization values are quite different, the hydrodynamic volume fractions of the highest concentration MF/CA and MF/OA samples are practically the same, due to the significantly different thicknesses of the particles' coating layers. The results of volume fraction dependent structure analyses over a large concentration range by small-angle X-ray and neutron scattering, correlated with magneto-rheological investigations for the electrostatically stabilized MFs, demonstrate formation of short chains of magnetic nanoparticles which are relatively stable against coagulation with increasing concentration, while for MFs with electro-steric stabilization, magnetic field and shear rate dependent loosely bound structures are observed. These particle structures in MF/OA samples manifest themselves already at low volume fraction values, which can be attributed mainly to magnetic interactions of larger size particles, besides non-magnetic interactions mediated by excess surfactant.

Manganese (Mn) is a toxic heavy metal exposing workers in various occupational settings and causing, among others, nervous system damage. Metal fumes of welding, a typical source of Mn exposure, contain a complex mixture of metal oxides partly in nanoparticle form. As toxic effects of complex substances cannot be sufficiently understood by examining its components separately, general toxicity and functional neurotoxicity of a main pathogenic welding fume metal, Mn, was examined alone and combined with iron (Fe) and chromium (Cr), also frequently found in fumes. Oxide nanoparticles of Mn, Mn + Fe, Mn + Cr and the triple combination were applied, in aqueous suspension, to the trachea of young adult Wistar rats for 4 weeks. The decrease of body weight gain during treatment, caused by Mn, was counteracted by Fe, but not Cr. At the end of treatment, spontaneous and evoked cortical electrical activity was recorded. Mn caused a shift to higher frequencies, and lengthened evoked potential latency, which were also strongly diminished by co-application of Fe only. The interaction of the metals seen in body weight gain and cortical activity were not related to the measured blood and brain metal levels. Fe might have initiated protective, e.g. antioxidant, mechanisms with a more general effect.

Nanoparticles do not exist in thermodynamical equilibrium because of high surface free energy, thus they have only kinetic stability. Spontaneous changes can be delayed by designed surface coating. In biomedical applications, superparamagnetic iron oxide nanoparticles (SPIONs) require an optimized coating in order to fulfil the expectation of medicine regulatory agencies and ultimately that of biocompatibility. In this work, we show the high surface reactivity of naked SPIONs due to ≡Fe-OH sites, which can react with H + /OH - to form pH- and ionic strength-dependent charges. We explain the post-coating of naked SPIONs with organic polyacids via multi-site complex bonds formed spontaneously. The excess polyacids can be removed from the medium. The free COOH groups in coating are prone to react with active biomolecules like proteins. Charging and pH- and salt-dependent behaviour of carboxylated SPIONs were characterized quantitatively. The interrelation between the coating quality and colloidal stability measured under biorelevant conditions is discussed. Our coagulation kinetics results allow us to predict colloidal stability both on storage and in use; however, a simpler method would be required to test SPION preparations. Haemocompatibility tests (smears) support our qualification for good and bad SPION manufacturing; the latter 'promises' fatal outcome in vivo .

Functionalized superparamagnetic iron oxide nanoparticles are frequently used to develop vehicles for drug delivery, hyperthermia, and photodynamic therapy and as tools used for magnetic separation and purification of proteins or for biomolecular imaging. Depending on the application, there are various possible covalent and non-covalent approaches for the functionalization of particles, each of them shows different advantages and disadvantages for drug release and activity at the desired location.Particularly important for the production of adsorptive and covalent bound drugs to nanoparticles is the pureness of the involved formulation. Especially the covalent binding strategy demands defined chemistry of the drug, which is stabilized by excess free amino acids which could reduce reaction efficiency. In this study, we therefore used tangential flow filtration (TFF) method to purify the drugs before the reaction and used the frequently applied and clinically available recombinant tissue plasminogen activator (tPA; Actilyse(®)) as a proof of concept. We then coupled the tPA preparation to polyacrylic acid-co-maleic acid (PAM)-coated superparamagnetic iron oxide nanoparticles (SPIONs) using an amino-reactive activated ester reaction and compared these particles to PAM-coated SPIONs with electrostatically adsorbed tPA.Using dynamic light scattering (DLS) and pH-dependent electrokinetic mobility measurements, we showed that surface properties of the SPIONs were significantly greater affected after activation of the particles compared to the adsorption controls. Different in vitro assays were used to investigate the activity of tPA after coupling to the particles and purification of the ferrofluid. Covalent linkage significantly improves the reactivity and long-term stability of the conjugated SPION-tPA system compared to simple adsorption. In conclusion, we have shown an effective way to produce SPIONs with covalent and non-covalent ultra-filtrated drugs. We showed that using activated ester reaction, immobilization of the protein was significantly better than in adsorptive approaches. Investigation of those functionalized SPIONs revealed diverging attributes, which should be taken into account when developing nanoparticles for different applications.

Recent developments in nanotechnology and application of magnetic nanoparticles, in particular in magnetic iron oxide nanosystems, offer exciting possibilities for nanomedicine. Facile and precise synthesis procedures, high magnetic response, tunable morphologies and multiple bio-functionalities of single- and multi-core magnetic particles designed for nanomedicine applications are thoroughly appraised. This review focuses on the structural and magnetic characterization of the cores, the synthesis of single- and multicore iron oxide NPs, especially the design of the latter, as well as their protection, stabilization and functionalization by desired coating in order to protect against the corrosion of core, to prevent non-specific protein adsorption and particle aggregation in biological media, and to provide binding sites for targeting and therapeutic agents., (Copyright © 2015 Elsevier Inc. All rights reserved.)

Understanding of water-related electrical conduction is of utmost importance in applications that utilize solid-state proton conductors. However, in spite of the vast amount of theoretical and experimental work published in the literature, thus far its mechanism remained unsolved. In this study, the structure-related ambient temperature electrical conduction of one-dimensional hydrophilic nanostructures was investigated. Cerium phosphate nanowires with monoclinic and hexagonal crystal structures were synthesized via the hydrothermal and ambient temperature precipitation routes, and their structural and surface properties were examined by using high-resolution transmission electron microscopy, X-ray diffractometry, nitrogen and water sorption, temperature-programmed ammonia desorption, and potentiometric titration techniques. The relative humidity (RH)-dependent charge-transport processes of hexagonal and monoclinic nanowires were investigated by means of impedance spectroscopy and transient ionic current measurement techniques to gain insight into their atomistic level mechanism. Although considerable differences in RH-dependent conductivity were first found, the distinct characteristics collapsed into a master curve when specific surface area and acidity were taken into account, implying structure-independent proton conduction mechanism in both types of nanowires.

The catalytic performance of multi-walled carbon nanotubes (MWCNTs) with different surface chemistry was studied in the decomposition reaction of H2O2 at various values of pH and temperature. A comparative analysis of experimental and quantum chemical calculation results is given. It has been shown that both the lowest calculated activation energy (∼18.9 kJ/mol) and the highest rate constant correspond to the N-containing CNT. The calculated chemisorption energy values correlate with the operation stability of MWCNTs. Based on the proposed quantum chemical model it was found that the catalytic activity of carbon materials in electron transfer reactions is controlled by their electron donor capability., (Copyright © 2014 Elsevier Inc. All rights reserved.)

Magnetite nanoparticles (MNPs) with biocompatible coatings are good candidates for MRI (magnetic resonance imaging) contrasting, magnetic hyperthermia treatments, and drug delivery systems. The spontaneous surface induced polymerization of dissolved organic matter on environmental mineral particles inspired us to prepare carboxylated core-shell MNPs by using a ubiquitous polyphenolic precursor. Through the adsorption and in situ surface polymerization of gallic acid (GA), a polygallate (PGA) coating is formed on the nanoparticles (PGA@MNP) with possible antioxidant capacity. The present work explores the mechanism of polymerization with the help of potentiometric acid-base titration, dynamic light scattering (for particle size and zeta potential determination), UV-vis (UV-visible light spectroscopy), FTIR-ATR (Fourier-transformed infrared spectroscopy by attenuated total reflection), and XPS (X-ray photoelectron spectroscopy) techniques. We observed the formation of ester and ether linkages between gallate monomers both in solution and in the adsorbed state. Higher polymers were formed in the course of several weeks both on the surface of nanoparticles and in the dispersion medium. The ratio of the absorbances of PGA supernatants at 400 and 600 nm (i.e., the E4/E6 ratio commonly used to characterize the degree of polymerization of humic materials) was determined to be 4.3, similar to that of humic acids. Combined XPS, dynamic light scattering, and FTIR-ATR results revealed that, prior to polymerization, the GA monomers became oxidized to poly(carboxylic acid)s due to ring opening while Fe(3+) ions reduced to Fe(2+). Our published results on the colloidal and chemical stability of PGA@MNPs are referenced thoroughly in the present work. Detailed studies on biocompatibility, antioxidant property, and biomedical applicability of the particles will be published.

Bile salt aggregates are promising candidates for drug delivery vehicles due to their unique fat-solubilizing ability. However, the toxicity of bile salts increases with improving fat-solubilizing capability and so an optimal combination of efficient solubilization and low toxicity is necessary. To improve hydrophilicity (and decrease toxicity), we substituted hydroxyl groups of several natural bile acid (BA) molecules for oxogroups and studied their intrinsic molecular association behavior. Here we present the comparative Langmuir trough study of the two-dimensional (2D) association behavior of eight natural BAs and four oxoderivatives (traditionally called keto-derivatives) floated on an aqueous subphase. The series of BAs and derivatives showed systematic changes in the shape of the compression isotherms. Two types of association could be distinguished: the first transition was assigned to the formation of dimers through H-bonding and the second to the hydrophobic aggregation of BA dimers. Hydrophobic association of BA molecules in the films is linked to the ability of forming H-bonded dimers. Both H-bond formation and hydrophobic association weakened with increasing number of hydroxyl groups, decreasing distance between hydroxyl groups, and increasing oxosubstitution. The results also show that the Langmuir trough method is extremely useful in selecting appropriate BA molecules to design drug delivery systems.

Despite the large efforts to prepare super paramagnetic iron oxide nanoparticles (MNPs) for biomedical applications, the number of FDA or EMA approved formulations is few. It is not known commonly that the approved formulations in many instances have already been withdrawn or discontinued by the producers; at present, hardly any approved formulations are produced and marketed. Literature survey reveals that there is a lack for a commonly accepted physicochemical practice in designing and qualifying formulations before they enter in vitro and in vivo biological testing. Such a standard procedure would exclude inadequate formulations from clinical trials thus improving their outcome. Here we present a straightforward route to assess eligibility of carboxylated MNPs for biomedical tests applied for a series of our core-shell products, i.e., citric acid, gallic acid, poly(acrylic acid) and poly(acrylic acid-co-maleic acid) coated MNPs. The discussion is based on physicochemical studies (carboxylate adsorption/desorption, FTIR-ATR, iron dissolution, zeta potential, particle size, coagulation kinetics and magnetization measurements) and involves in vitro and in vivo tests. Our procedure can serve as an example to construct adequate physico-chemical selection strategies for preparation of other types of core-shell nanoparticles as well.

Magnetite nanoparticles (MNPs) coated with poly(acrylic acid-co-maleic acid) polyelectrolyte (PAM) have been prepared with the aim of improving colloidal stability of core-shell nanoparticles for biomedical applications and enhancing the durability of the coating shells. FTIR-ATR measurements reveal two types of interaction of PAM with MNPs: hydrogen bonding and inner-sphere metal-carboxylate complex formation. The mechanism of the latter is ligand exchange between uncharged -OH groups of the surface and -COO(-) anionic moieties of the polyelectrolyte as revealed by adsorption and electrokinetic experiments. The aqueous dispersion of PAM@MNP particles (magnetic fluids - MFs) tolerates physiological salt concentration at composition corresponding to the plateau of the high-affinity adsorption isotherm. The plateau is reached at small amount of added PAM and at low concentration of nonadsorbed PAM, making PAM highly efficient for coating MNPs. The adsorbed PAM layer is not desorbed during dilution. The performance of the PAM shell is superior to that of poly(acrylic acid) (PAA), often used in biocompatible MFs. This is explained by the different adsorption mechanisms; metal-carboxylate cannot form in the case of PAA. Molecular-level understanding of the protective shell formation on MNPs presented here improves fundamentally the colloidal techniques used in core-shell nanoparticle production for nanotechnology applications.

A commercial multiwall carbon nanotube and its carboxylated derivate (CNTC and COOHC, respectively) was used after purification to study the competitive adsorption of phenol (P) and m-chlorophenol (CP) from 0.1 M aqueous NaCl solutions without external pH control. The adsorption takes place practically exclusively on the external surface of the nanotubes. The uptake of P is suppressed in comparison to its single solute behaviour on both nanotubes, independently of the initial pollutant concentration. The uptake of CP however is more sensitive to the concentration and the surface chemistry of the nanotube. The measured co-adsorption isotherms were compared to the isotherms calculated from the competitive Langmuir model (CLM). Preferential adsorption of CP was observed in about 95% of the relative concentration range. The total adsorption may exceed the corresponding single component sorption capacity., (Copyright © 2012 Elsevier Inc. All rights reserved.)

Superparamagnetic iron oxide nanoparticles (SPIONs) have proved their use in many biomedical applications, such as drug delivery, hyperthermia, and MRI (magnetic resonance imaging) contrast agents. Due to their instability in fluids, several surface coatings have been used to both stabilize and tune the properties of these nanoparticles (NPs) according to their applications. These coatings will strongly modify their surface properties and influence their interaction with the environment proteins in a relevant biological medium with a clear impact on their function. It is well-accepted that a protein corona is immediately formed when nanoparticles come in contact with a biological milieu, and the emergent bionano interface represents the biological identity of the particles. Here, we investigate how a different coating on the same magnetic core can influence the protein corona composition and structure with clear relevance to application of these NPs in medicine. In particular, we have studied the structure and composition of the protein corona-SPION complexes of magnetite nanoparticles stabilized with citric acid, poly(acrylic acid), or double layer oleic acid by a range of approaches, including dynamic light scattering, nanoparticle tracking analysis, differential centrifugal sedimentation, infrared spectroscopy, 1-D SDS gel electrophoresis, and mass spectroscopy.

The perfluorooctanoic acid (PFOA) sorption behavior of two commercial multi-walled carbon nanotubes (MWCNTs) (C 150 P from Bayer MaterialScience: BA and C-MWNTs from NanoTechLabs Inc.: CP) was investigated from aqueous solution. The BA nanotubes contained Co/Mn/Mg/Al catalysts both on their outer surface and in the inner bore while CP contained Fe-based catalyst typically within the tubes. The adsorption isotherms of (14)C-radiolabeled PFOA were measured by batch experiments and fitted to the Freundlich model (r(2)>0.92). The adsorption affinity and capacity on BA were significantly higher than on CP. Increasing the pH reduced the adsorption of PFOA due to the electrostatic interaction between the pH-sensitive surface and the adsorbate. Increasing the NaCl concentration led to the aggregation of the MWCNTs reducing the available surface and thus the adsorption capacity. Removal of the catalyst from the outer surface of BA changed the electrophoretic mobility from a positive to a negative value and also decreased the adsorbed amount of PFOA. The surface charge of the surface-associated metal catalyst favors the electrostatic sorption of PFOA. Such surface modifications may be a promising way to improve the sorption capacity of MWCNTs for pollutants such as PFOA and to broaden their potential application in water purification., (Copyright © 2012 Elsevier Inc. All rights reserved.)

Magnetite nanoparticles (MNPs) were prepared by alkaline hydrolysis of Fe(II) and Fe(III) chlorides. Adsorption of polyacrylic acid (PAA) on MNPs was measured at pH=6.5±0.3 and I=0.01 M (NaCl) to find the optimal PAA amount for MNP stabilization under physiological conditions. We detected an H-bond formation between magnetite surface groups and PAA by ATR-FTIR measurements, but bonds of metal ion-carboxylate complexes, generally cited in literature, were not identified at the given pH and ionic strength. The dependence of the electrokinetic potential and the aggregation state on the amount of added PAA at various pHs was measured by electrophoretic mobility and dynamic light-scattering methods. The electrokinetic potential of the naked MNPs was low at near physiological pH, but PAA adsorption overcharged the particles. Highly negatively charged, well-stabilized carboxylated MNPs formed via adsorption of PAA in an amount of approximately ten times of that necessary to compensate the original positive charge of the magnetite. Coagulation kinetics experiments revealed gradual enhancement of salt tolerance at physiological pH from ~0.001 M at no added PAA up to ~0.5 M at 1.12 mmol/g PAA. The PAA-coated MNPs exert no substantial effect on the proliferation of malignant (HeLa) or non-cancerous fibroblast cells (MRC-5) as determined by means of MTT assays., (Copyright © 2012 Elsevier B.V. All rights reserved.)

The extensive oxygen-group functionality of single-layer graphene oxide proffers useful anchor sites for chemical functionalization in the controlled formation of graphene architecture and composites. However, the physicochemical environment of graphene oxide and its single-atom thickness facilitate its ability to undergo conformational changes due to responses to its environment, whether pH, salinity, or temperature. Here, we report experimental and molecular simulations confirming the conformational changes of single-layer graphene oxide sheets from the wet or dry state. MD, PM6, and ab initio simulations of dry SLG and dry and wetted SLGO and electron microscopy imaging show marked differences in the properties of the materials that can explain variations in previously observed results for the pH dependent behavior of SLGO and electrical conductivity of chemically modified graphene-polymer composites. Understanding the physicochemical responses of graphene and graphene oxide architecture and performing selected chemistry will ultimately facilitate greater tunability of their performance.

Kaolin is an important industrial raw material and a basis of a range of different products. Microbial spoilage is a detrimental process observed especially in kaolin slurries, leading to low quality products and economic loss. Although the alteration of kaolin slurries in ceramic industry was observed, the process and the microbial background have not been analyzed in details. This study provides the first data using a cultivation independent molecular biological approach (PCR-DGGE) regarding the bacterial composition of an altered kaolin slurry. The results show that potential exopolymer (EPS) producer bacteria (e.g. Acinetobacter, Pseudomonas) appear in the altered kaolin slurry, which may have an important role in the modification of kaolin slurries.

We report the adsorption of phenol and dopamine probe molecules, from aqueous solution with NaCl, on commercial multiwall carbon nanotubes (MWCNT) and on their carboxylated derivative. The nanotubes were fully characterized by high resolution transmission electron microscopy (HRTEM), small angle X-ray scattering (SAXS), potentiometric titration, electrophoretic mobility, and nitrogen adsorption (77K) measurements. The experimental pollutant isotherms, evaluated using the Langmuir model, showed that only 8-12% and 21-32% of the BET surface area was available for phenol and dopamine, respectively, which is far below the performance of activated carbons. Influence of the pH was more pronounced for the oxidized MWCNT, particularly with dopamine. The strongest interaction and the highest adsorption capacity occurred at pH 3 with both model pollutants on both types of nanotubes. Although the surface area available for adsorption is far lower in MWCNTs than in activated carbons, it is nonetheless substantial. In particular, delayed release of toxic molecules that are either adsorbed on the surface or trapped in the inner bore of such systems could constitute an environmental hazard. The need for further adsorption studies with regard to their environmental aspects is therefore pressing, particularly for MWCNTs in their functionalized state., (Copyright © 2011 Elsevier Inc. All rights reserved.)

The adsorption of water vapor at the surface of magnetite nanoparticles has been investigated both by experimental and by computer simulation methods. The water vapor adsorption/desorption isotherm has been measured on freshly prepared magnetite nanocrystals of the size below 10 nm. The change of the isosteric heat of adsorption with the surface coverage has been determined from the temperature dependence of this isotherm using the isosteric method. The adsorption isotherm has also been determined by performing a set of grand canonical Monte Carlo simulations at 300 K. X-ray photoelectron spectroscopy results as well as the temperature and coverage dependence of the isosteric heat of adsorption clearly indicates that dissociative chemisorption of the water molecules in the first adsorption layer occurs at the bare magnetite surface, resulting in a high density of surface hydroxyl groups. This dissociative chemisorption is followed by a multilayer physisorption of water at higher pressures. Computer simulation results can reproduce excellently both the adsorption isotherm and the isosteric heat of adsorption beyond the first chemisorbed layer of water. Results of the computer simulations reveal that physisorbed water forms several well-distinguished molecular layers on the magnetite surface; however, these layers are not built up sequentially. Instead, the building up of several molecular layers occurs simultaneously. The adsorption of the water molecules in this range appears to be a nucleation-like process, resulting in a rather rough external surface of the adsorption layer.

Magnetite nanoparticles were coated with surfactant double layers in order to prepare water based magnetic fluids (MFs). The effects of head group (sulfonate, carboxylate) and alkyl chain length (11-17 C atoms) and the combination of surfactants were studied. Adsorption, dynamic light scattering (DLS) and electrophoretic mobility measurements were performed. The quantity of surfactant varied between 0.3 and 0.5 g, i.e. their specific amount ranges over 1.5-2 mmol g(-1) magnetite in MFs. The adsorption isotherm of Na oleate on magnetite proved the double layer formation with 2 mmol g(-1) saturation value in good harmony with the empirical doses. The effect of diluting MFs, pH and salt concentration was studied. The pH-dependent stability and the salt tolerance of MFs were different owing to the dissociation of the outermost hydrophilic groups and the hydrophobic interactions scaling with the alkyl chain length of surfactant. The hydrophobic interactions are favored only for oleic and myristic acid double layers. In these MFs, aggregation cannot be observed even in fairly dilute systems up to the physiological salt concentration around neutral pH 6-8 favored in biomedical application. The stable oleic and myristic acid double layers can hinder effectively the aggregation of magnetite particles due to the combined steric and electrostatic stabilization.

The interactions between the cationic polymer chitosan (a copolymer, consisting mainly of 2-amino-2-deoxy-D-glucopyranose and, to a lesser extent, of 2-acetamido-2-deoxy-D-glucopyranose, Chit) and iron(III) were investigated. The solution properties were studied by pH-metry, UV-Vis spectrophotometry and viscometry. Solid state iron(III)-Chit samples were also prepared and characterized by IR-spectroscopy and electronmicroscopy. In aqueous solutions, the precipitation pH of the FeO(OH) is significantly shifted towards the higher pH-s in presence of Chit. However, the additivity of the pH-metric titration curves, the lack of variation both in tin presence and absence of iron(III), indicate that there is no specific coordination chemical interaction between the Chit and ferric ions. It is well established that spherical FeO(OH) particles with afew nm diameter, morphologically similar to the core of the iron(III)-storage protein ferritin, are formed during the hydrolysis of iron(III) even in the absence of complexing agents. Such isolated FeO(OH) spheres were observed in samples obtained from solutions containing iron(III) and Chit. The fact, that visible precipitation of FeO(OH) can only be observed, when the Chit itself precipitates from aqueous solutions (i.e., pH approximately 7), indicates that the role of Chit in these systems is to inhibit the aggregation of the subcolloidal FeO(OH) particles. These observations are in strong contrast with those obtained for interactions between iron(III) and various anionic biopolymers, such as heparin, hyaluronate, dextran sulfate and chondroitin sulphate A and C, and suggest that coordination chemical interactions play very important role in determining the nanostructure of composite materials containing iron(III) and polysaccharides.

The pH-dependent adsorption of humic acid (HA) on magnetite and its effect on the surface charging and the aggregation of oxide particles were investigated. HA was extracted from brown coal. Synthetic magnetite was prepared by alkaline hydrolysis of iron(II) and iron(III) salts. The pH-dependent particle charge and aggregation, and coagulation kinetics at pH approximately 4 were measured by laser Doppler electrophoresis and dynamic light scattering. The charge of pure magnetite reverses from positive to negative at pH approximately 8, which may consider as isoelectric point (IEP). Near this pH, large aggregates form, while stable sols exist further from it. In the presence of increasing HA loading, the IEP shifts to lower pH, then at higher loading, magnetite becomes negatively charged even at low pHs, which indicate the neutralization and gradual recharging positive charges on surface. In acidic region, the trace HA amounts are adsorbed on magnetite surface as oppositely charged patches, systems become highly unstable due to heterocoagulation. Above the adsorption saturation, however, the nanoparticles are stabilized in a way of combined steric and electrostatic effects. The HA coated magnetite particles form stable colloidal dispersion, particle aggregation does not occur in a wide range of pH and salt tolerance is enhanced.

Humic acid was fractionated into eight different molecular size components using ultrafiltration. Solid-state CPMAS 13C NMR demonstrated that fractions larger than 100,000 Daltons were primarily aliphatic in character, while fractions smaller than 30,000 Daltons were predominantly aromatic in character. Solid-state 19F NMR examination of the sorptive uptake of hexafluorobenzene (HFB) by HA and each of the fractions gave spectroscopic evidence for the existence of at least three sorption sites in the smaller molecular size fractions, while two predominant sorption sites could be established in the larger molecular size fractions. Sorbed HFB displayed higher mobility in the smaller, more aromatic fractions while HFB in the larger, more aliphatic fractions displayed lower mobility. The relative mobilities of HFB in each sorption domain suggest that the rigid domain may be composed of aliphatic carbon rather than aromatic carbon moieties. In larger size fractions, this domain may be the result of rigid, glassy regions composed of aliphatic molecules or side chains.

The interactions between the cationic polymer chitosan (Chit) and iron(III) were investigated. The solution properties were studied by pH-metry, viscometry and dynamic light scattering. Solid state iron(III)-Chit samples were also prepared and characterized by IR spectroscopy and electron microscopy. In aqueous solutions, the precipitation pH of the iron(III) oxyhydroxide (FeOOH) is significantly shifted towards the higher pH values in the presence of Chit indicating that some interaction takes place between the iron(III) and the polymer. However, the additivity of the pH-metric titration curves, the lack of variation both in the viscometric and IR spectra of Chit in the presence and absence of iron(III), indicate the lack of direct complexation between the Chit and ferric ions. Isolated FeOOH nanospheres of 5-10 nm diameter were observed on the transmission electron microscopic pictures of samples obtained from solutions containing iron(III) and Chit, while from DLS measurements hydrodynamic units with a few hundred nm in diameter were identified. Our data support that Chit acts as steric stabilizer and inhibits the macroscopic aggregation of the subcolloidal FeOOH particles. Thus the iron(III)-Chit interactions offer a simple and economic way to fabricate nanometric size FeOOH spheres, morphologically similar to the core of iron(III)-storage protein, ferritin.

For modelling the interactions of proteins/peptides with hard metal ions the complex formation of salicylglycine (SalGly) with Ca(II), Mg(ll) and AI(III) ions was studied in aqueous solution using pHpotentiometric and UV-vis spectroscopic techniques. Al(lll) ion was found to form more stable complexes with SalGiy than Ca(ll) or Mg(ll) ions. While AI(III) ion forms various 1:1 complexes of different protonation states in the pH range 2-7, Ca(ll), Mg(ll) ions seem to interact with SalGly only in the basic pH range and form mixed hydroxo species MLH(-1) at pH approximately 8. According to the UV-vis spectroscopic measurements in the species MLH(-1) the carboxylate-O(-) atom and the phenolate-O(-) coordinate to the metal ions. SaIGiy is able to keep Al(lll) in solution through inner and outer sphere coordination to metastable amorphous AI(OH)(3) particles. Deprotonation of the peptide amide Nil does not occur in these systems.