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Bioactive ions (Mg, Sr, Zn) doped carbonated hydroxyapatite powders (dHAp) and pure carbonated hydroxyapatite (HAp) powders were prepared by wet chemical precipitation method. The bioactive ions were incorporated into the HAp matrix by co-precipitation from solution containing the appropriate amount of chloride salt of different ions. The morphology of pure HAp was mainly needle-like in nanometre size and the particles were disordered showing quasi-amorphous structure. The ion doping changed the morphology of particles, the dHAp particles had distorted spheroid shapes. Owing to the ion addition, the crystallinity of particles decreased. Particle aggregations can also be observed in both types of samples. HAp and dHAp loaded biopolymer polyvinylpyrrolidone (PVP) composite materials have also been developed by novel electrospinning technique. It has been shown that both the HAp and dHAp particles can be successfully incorporated into the PVP fibre web matrix and simultaneously the bioceramic powders were attached to the surface of polymer fibres. The surface of fibres was not fully covered with the particles. The ceramic powder addition to the polymer solution caused the polymer fibres to become more entangled and the diameters of fibres varied over a wider range compared to the base polymer fibres without bioceramic powder addition.

Turquoise covered mosaic objects - especially masks - were attractive components of treasures transported to Europe from Mexico after the fall of the Aztec Empire in the 1500s. According to our present knowledge, the mosaic masks were manufactured for ritual purpose. The main material of mosaics, the turquoise was a high-prestige semi-precious stone among Mexican native people. During the 20

New complexes of Pd(II) with cationic phthalimido-functionalized N-heterocyclic carbene (NHC), the cis-Diacetonitrile(chloro)[1-(2′-phthalamidoethyl)-3-methylimidazolin-ylidene]palladium(II) Hexafluorophosphate (and its CD3CN derivative) had been successfully used as catalyst in the Suzuki–Miyaura cross-coupling reaction. This complex have been studied by structural (XRD), spectroscopic (infrared, far-infrared and Raman) and theoretical (DFT and normal coordinate calculations) methods. Palladium is bound to two acetonitrile ligands and one-one chloride ion and phthalimido-functionalized imidazolium salt, [3-methyl-1-(2′-phthalimidoethyl) imidazolium] (L = ligand) in a square–planar cis arrangement. The molecular structure of the [PdCl(NCCH3)2L]+ was obtained by XRD and DFT geometry optimization. The two acetonitrile ligands exhibited two different Pd-N bonds a shorter one 2.080 A (opposite to Cl ion) and a longer one 2.120 A (trans to heterocyclic ligand). The cationic [PdCl(NCCH3)2L+] complex has as much as 132 fundamental modes and practically all of them have been assigned. The complex has no symmetry elements, but interpretation has been performed on the basis of local symmetries of its fragments. Tans-conformation of the bridging –CH2-CH2– group has been established from vibrational spectra, and this local structure avoided interaction of phthalimido moiety with the palladium center. Special attention has been paid for understanding and interpretation of the characteristic imidazolium ring vibrations connected to the strong electron donor phthalimido ring at 1553, 1397, 1347, 1218, 1149, 1118, 845, 748, 666, 629, 471, 245, 212, 124 and 104 cm−1 which bands are up shifted comparing to those of 2,3-dialkyl substituted ring modes. Clear differences were established between the fundamentals and force constants of the two differently coordinated acetonitrile. The more strongly coordinated CH3CN(1) has Raman bands at 2336, 958 and 279 cm−1 while the other CH3CN(2) has at 2321, 936 and 266 cm−1 like antisymmetric CN, CC and Pd-N stretching modes, respectively. The Pd-N stretching modes were assigned with the help of spectral and calculated data of CD3CN complex. For acetonitrile (1) the light and heavy stretching modes were 279 and 275 cm−1, respectively exhibiting 4 cm−1 isotope shift whyle those for acetonitrile (2) were as 266 and 264 cm−1 with less isotope shift. Rather small but different 1.630 and 1.493 Ncm−1 Pd-N stretching force constants were fitted for stronger and weaker bonded acetonitrile as compared to those of 3.931 Ncm−1 for [Pd(NCCH3)2]2+, and 4.050 Ncm−1 for cis-PtCl2(NCCH3)2. In contrast, the strongly weakened Pd-N bonds the Pd-Cl bond is enhanced and exhibiting relative high 2.03 Ncm−1 force constants in comparison with 1.53 Ncm−1 of [PdCl4]2- anion. The enhanced Pd-Cl bond strength is escorted by strong weakening of Pd-acetonitrile coordination. Surprisingly, from DFT calculation and spectroscopic data higher Pd-N force constant was obtained for the Pd-N bond with longer bond length and opposite, lower force constant for shorter Pd-N bond. These unusual discrepancies between bond lengths and bond force constants can be explained with the presence of electron-rich σ-donating ligand opposite to acetonitrile (1) which lead to enhancement of Pd-N bond. These specific properties of coordination sphere of [PdCl(NCCH3)2L]+ complex providing possibilities for easily releasing acetonitrile ligands during catalytic processes and give reasonable structural explanation of its high catalytic activity.

Magnetic nanoporous silica particles (MNS) with spherical morphology and 100 nm particle with advanced characteristics suitable for nanomedicine purposes were synthesized. The obtained nanoparticles were modified with SO3H groups in a two-step post synthesis procedure. An anticancer drug, mitoxantrone (MTX), and an anti-inflammatory drug, prednisolone (PRD), were loaded on the silica support. The mitoxantrone loaded MNS-SO3H nanoparticles were coated by chitosan and then prednisolone was infused in the chitosan layer. A second layer of alginate was then applied around the prednisolone and mitoxantrone containing formulation. All materials were characterized by XRD, N2 physisorption, Mossbauer spectroscopy, magnetization measurements and transmission electron microscopy in order to demonstrate that by the applied preparation method around 11 nm sized maghemite crystals embedded in spherical mesoporous silica nanoparticles were obtained with high pore volume and surface area. Thermal gravimetric analysis, ATR FT-IR spectroscopy and in vitro release experiments proved that MTX and PRD were successfully loaded on the silica matrix. Alginate coating further improved the release properties by preventing the burst release of MTX and PRD. The cytotoxicity properties of the drugs loaded formulations and their ability to retain the intrinsic pharmacological properties of the encapsulated drugs were investigated on a panel of human tumor cell lines.

It is reported for first time, that silver modified nanoporous MCM-41 or SBA-15 silicas are promising carriers for the preparation of poplar propolis loaded dermal formulations. MCM-41 or SBA-15 were successfully modified with 5–15 nm sized silver nanoparticles by direct or post synthesis methods. The formed silver nanoparticles are stabilized in the channels or on the outer surface of nanoporous supports. Poplar propolis molecules were loaded into the mesoporous channels by impregnation. The parent and poplar propolis loaded formulations were characterized by powder XRD, N2 physisorption, thermal analysis and ATR FT-IR spectroscopy. In vitro release of poplar propolis and silver was studied in phosphate buffer at pH = 5.5 which is typical for dermal formulations. Adsorption of poplar propolis on nanoporous silica particles significantly improves its water solubility. Moreover propolis loaded silver-silica systems show significantly better antibacterial and antifungal activities than poplar propolis and silver-modified carriers themselves.

Effects of modification of PtO x -TiO 2 photocatalysts by tin were elucidated by exploring relationships between the structural properties of variously prepared tin-loaded catalysts and their catalytic activity in methanol photocatalytic reforming. Tin free and amorphous tin-oxide decorated TiO 2 samples were prepared by sol-gel method from titanium-isopropoxide. In other approach, Sn was loaded onto the sol-gel prepared TiO 2 by impregnation followed by calcination. Pt was introduced by impregnation followed by either reduction in H 2 at 400 °C or calcination at 300 °C. TEM, XRD and Raman spectroscopic measurements proved that TiO 2 existed in the form of aggregates of polycrystalline anatase with primary particle size of 15–20 nm in all samples. Photocatalytic hydrogen production was influenced by the combined effect of many parameters. Both the presence of Sn and the way of Pt co-catalyst formation played important role in the activity of these photocatalysts. The Sn introduction by both sol-gel method and impregnation clearly enhanced the photocatalytic activity. 1 H MAS NMR measurements revealed that the Sn introduction reduced the amount of the terminal Ti-OH groups of relatively basic character considered to be unfavorable for the photocatalytic reaction. Presence of SnO x decreased the signal of the undesirable vacancies observed by ESR. Furthermore surface SnO x enhanced the dispersion of Pt. Formation of the Pt co-catalyst by calcination was more favorable than by H 2 treatment. In case of the calcined samples in situ reduction of the Pt nanoparticles at the beginning of the photocatalytic reaction was found to be favorable for the hydrogen production. The relatively modest photocatalytical activity obtained after high temperature H 2 treatment could be related to at least two processes in this system: (i) creation of unfavorable oxygen vacancies and (ii) segregation of SnO x to the surface of the Pt cocatalyst as the result of the air exposure of the alloy type Pt-Sn nanoparticles formed during the H 2 treatment, resulting in a decreased number of active sites for reduction of H + .

The strength and geometry of adsorption of substituted phenylpyruvates on silver surface was studied by means of surface enhanced Raman spectroscopy (SERS) using silver sol. 2′-nitrophenylpyruvates were used as starting materials in a newly developed heterogeneous catalytic asymmetric cascade reaction to produce substituted quinoline derivatives. Substituents on the aromatic ring of the starting materials had significant influence on the yield of the desired quinoline derivatives. Product selectivity of the transformation of nitrophenylpyruvates were enhanced by the acid added. The geometry and the strength of the adsorption are assumed to play an important role in the outcome of this reaction, so we have tried to find correlation between the structure of adsorbed phenylpyruvates and their catalytic performance. Based on the results of our spectroscopic measurements, the enol form is predominant in the series of phenylpyruvates in solid form and methanol solutions. Stronger adsorption of phenylpyruvates in acidic media through oxygen atoms was indicated by the increased enhancement in the SERS spectrum. The nitro group of 2′-nitrophenylpyruvates has no direct role in the adsorption on Ag surface. This observation has explained why the hydrogenation of the keto group (presumably via the enol form) occurs preferentially and why the formation of the undesired indole derivatives requiring reduction of the nitro group is suppressed. The SERS behavior has helped to get a closer look on the first step of adsorption of starting materials contributing to a better understanding of the cascade reaction studied, thus providing a better flexibility in catalyst design.

This paper describes the preparation of gallium-68 ( 68 Ga) isotope labeled porous zirconia (ZrO 2 ) nanoparticle (NP) platform of nearly 100 nm diameter and its first pharmacokinetic and biodistribution evaluation accomplished with a microPET/CT (μPet/CT) imaging system. Objectives of the investigations were to provide a nanoparticle platform which can be suitable for specific delivery of various therapeutic drugs using surface attached specific molecules as triggering agents, and at the same time, suitable for positron emission tomography (PET) tracing of the prospective drug delivery process. Radiolabeling was accomplished using DOTA bifunctional chelator. DOTA was successfully adsorbed onto the surface of nanoparticles, while the 68 Ga-radiolabeling method proved to be simple and effective. In the course of biodistribution studies, the 68 Ga-labeled DOTA-ZrNPs showed proper radiolabeling stability in their original suspension and in blood serum. μPet/CT imaging studies confirmed a RES-biodistribution profile indicating stable nano-sized labeled particles in vivo . Results proved that the new method offers the opportunity to examine further specifically targeted and drug payload carrier variants of zirconia NP systems using PET/CT imaging.

SBA-16 and MCM-41 silica materials were synthesized and modified by post-synthesis method with different amounts of Zn (2 and 4 wt.%). Quercetin, a flavonol compound, was loaded by incipient wetness impregnation method on the pure silica and Zn-modified mesoporous MCM-41 and SBA-16 supports. The parent and drug loaded formulations were characterized by powder XRD, N2 physisorption, thermal analysis, TEM, UV Vis and FT-IR spectroscopies. The formation of Zn:quercetin complex was studied by FT-IR spectroscopy and quantum-chemical calculations. Loading of quercetin on mesoporous carriers made the sustained delivery of the bioactive compound possible in a buffer with pH = 5.5, typical of dermal formulations. The results from the release experiments are in good accordance with the interaction energy between the bioactive molecule and non-modified and Zn-modified mesoporous materials, predicted by the quantum-chemical calculations. For the first time the formation of the most stable Zn quercetin complexes loaded on the mesoporous silica materials were determined. The obtained mesoporous delivery systems with Zn-quercetin complex are promising as dermal formulations.

Silica nanoparticles incorporating magnetic iron oxides (MS) with sizes around 20 nm were developed. The MS material was modified with NH2-groups and then grafted by PEG chains. The anticancer drug miltefosine was loaded into the NH2-modified and PEGylated MS nanoparticles by impregnation procedure resulting in 11–28% of drug content. PEG chains were also conjugated to the miltefosine loaded MS-NH2 nanocarrier. The amount of loaded drug and the release properties depend on whether PEGylation of the nanoparticles was performed before or after the drug loading step. The parent and drug loaded samples were characterized by XRD, N2 physisorption, thermal gravimetric analysis, magnetic measurements, XPS and ATR FT-IR spectroscopy. ATR FT-IR spectroscopic data and DFT calculations supported the interaction between the mesoporous silica surface and miltefosine molecules. The in vitro release profile at pH = 7.0 showed sustained drug release and dependence on the experimental design. Free and formulated miltefosine samples were further investigated for antiproliferative activity against malignant HUT-78 cell line. Formulated miltefosine showed superior cytotoxic effect on the tested cells as compared to the free drug. In addition, the MTT assay of the cytotoxic potential of non-loaded silica nanocomposites showed no intrinsic cytotoxicity associated with the carriers.

Recent investigations have revealed very promising analytical and medical applications of poly(ethyleneimine) (PEI) capped gold nanoparticles (Au NPs). One simple way for their synthesis utilizes the dual nature of PEI molecules, which can simultaneously act as reducing and stabilizing agents via their amine groups. However, the formation mechanism of these kinds of NPs as well as the dependence of their morphology and charge on the pH and electrolyte additives has not been explored yet. In the present paper, the role of these factors on the PEI assisted one-pot synthesis of gold nanoassemblies was studied systematically using IR and UV–Vis spectroscopy as well as DLS, electrophoretic mobility and TEM techniques. It was shown that these nanomaterials cannot be considered as simple PEI coated Au NPs. Instead, the gold particles are embedded in a rather specific polymer matrix, the structure of which ranges from a slightly cross-linked, positively charged thin polymer layer at low pH, to an extended, negatively charged and coherent amorphous polymer film in alkaline medium, provided that adequate type and concentration of supporting electrolyte is also present. These observations were rationalized through the unique pH and salt dependent mechanism of the initial gold(III)/amine complexation and that of the subsequent oxidation and cross-linking processes of the PEI molecules. This crucially determines the following nucleation and growth as well as the morphology, charge and size of the polymer entrapped gold NPs. The presented results may have important implications in novel applications of gold nanoassemblies.

Prednisolone loaded mesoporous silica nanocomposites with different amounts of maghemite core were prepared to design a drug delivery system suitable for drug administration in magnetic field. Textural investigations evidenced that 80–150 nm sized spherical particles with 3–3.5 nm pore size are formed by the applied synthesis method, varying with the amount of incorporated magnetic particles. Mossbauer spectroscopic results proved the presence of small maghemite nanoparticles inside the silica structure. Fourier transform infrared and Raman spectroscopic measurements provided data about the interaction between the drug and the silica, and revealed the polymorphic nature of prednisolone. Spectroscopic data suggested weak bonding between silanol groups of the mesoporous silica nanoparticles and prednisolone molecules. By the applied drug loading method polymorphic transformation of the parent Form I prednisolone occurred. In vitro release process at pH 7 showed lower solubility of polymorphic Form II compared to Form I. Slower release of prednisolone was observed by silica loaded formulations, reaching total amount in 10 h. The effect of prednisolone polymorphs loaded in silica carrier on its pharmacokinetic properties was studied for the first time.

Silver loaded nanosized zeolite Beta was prepared by a simple, mechanochemical method. Sulfadiazine (SD) drug was also deposited on silver Beta zeolite by the same method to get a bicomponent, sustained release antibacterial formulation. FT-IR spectroscopic investigations evidenced the incorporation of silver ions into the zeolite framework, i.e. occurrence of solid-state ion exchange (SSIE). The mechanism of SSIE was studied by thermo-gravimetric-mass spectrometric analysis. Formation of metallic silver nanoparticles stabilized on the surface of zeolite particles was supported by X-ray powder diffraction and UV spectroscopic methods. Our experiments revealed that Beta zeolite nanoparticles were able to store and release the loaded SD, together with the supported Ag. In vitro release studies in phosphate buffer (pH=5.5) demonstrated that the concomitant presence of Ag and sulfadiazine influenced the release kinetics of both components. The potential of combined antibacterial action of the novel silver-based zeolite-sulfadiazine composite as drug delivery system has been tested using Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa and Streptococcus pyogenes strains as model. The presence of silver in the developed formulations led to enhanced bactericidal effect on the studied strains.

The problems related with low solubility and instability in physiological environment of flavonoids are currently a challenge for their potential application for prevention and therapy of major chronic diseases, including cardiovascular and neurodegenerative diseases, cancer etc. Promising approach to overcome these drawbacks is incorporation of these compounds into mesoporous silica carriers. In this study we develop SBA-16 silica nanoparticles modified by a post-synthesis method with Mg (4 wt.%) or Ag (4 wt.%) as a carriers for simultaneous delivery of poorly soluble biological active compounds and essential micronutrients or antimicrobial agents. Hesperetin, a natural flavonone, and morin, a natural flavonol, belong to the big family of flavonoids were loaded by incipient wetness impregnation on the parent and Ag- or Mg-modified mesoporous supports. The initial, modified and drug loaded SBA-16 materials were characterized by powder XRD, N2 physisorption, thermogravimetric analysis and SEM measurements. The interactions between metals, silica surface and flavonoids were studied by ATR-FTIR and UV–Vis spectroscopies. Improved release profiles are observed for flavonoids loaded in mesoporous materials in comparison with pure flavonoids. Loading of flavonoids in parent and modified mesoporous carriers made the sustained delivery of the bioactive compound possible. A comparative study on anti-proliferative effect of the tested flavonoids loaded into modified silica carriers vs. free drug was investigated on a panel of three human cell lines. The evaluation of the antioxidant capacity shows that loading of the flavonoids into parent and modified silica supports can improve their activity against free radicals, which could be explained by the improved solubility of the loaded flavonoids in comparison with the pure ones. The obtained mesoporous delivery systems are promising as oral formulations for delivery of flavonoids, essential microelements and antimicrobial agents.

Silica@zirconia core@shell oxide nanoparticles of approx. 50 nm diameter were developed in view of an application as a novel carrier with adjuvant activities for cancer vaccines. To this end, the aim was to cover the surface of the nanocarrier by potent single stranded DNA (ssDNA) type immune stimulators used in cancer vaccination. Prior to characterizing the binding of ssDNA to the nanocarrier surface, the adsorption of deoxynucleoside monophosphate building blocks (dNMPs) was studied. After optimization of conditions for synthesis, solvent exchange and surface modification, the effects and possible interference of several buffers, such as HEPES, PIPES, MOPS and MOPSO, were also investigated. Formation of a new compound was revealed by UV–VIS spectroscopy during the recording of zeta potential vs. pH titration curves in the presence of HEPES and PIPES buffer in the neutral-acidic pH region. We identified this new species as gold ions etched from the electrode of the zeta cuvette, stabilized by the buffers via chelation, which is then followed by their conversion into gold nanoparticles.

Colloidal stabile nanoerythrosomes with 200 nm average diameter were formed from hemoglobin-free erythrocyte ghost membrane via sonication and membrane extrusion. The incorporation of extra lipid (1,2-dipalmitoyl-sn-glycero-3-phosphocholine, DPPC), added to the sonicated ghosts, caused significant changes in the thermotropic character of the original membranes. As a result of the increased DPPC ratio the chain melting of the hydrated DPPC system and the characteristic small angle X-ray scattering (SAXS) of the lipid bilayers appeared. Significant morphological changes were followed by transmission electron microscopy combined with freeze fracture method (FF-TEM). After the ultrasonic treatment the large entities of erythrocyte ghosts transformed into nearly spherical nanoerythrosomes with diameters between 100 and 300 nm and at the same time a great number of 10–30 nm large membrane proteins or protein clusters were dispersed in the aqueous medium. The infrared spectroscopy (FT-IR) pointed out, that the sonication did not cause changes in the secondary structures of the membrane proteins under our preparation conditions. About fivefold of extra lipid – compared to the lipid content of the original membrane – caused homogeneous dispersion of nanoerythrosomes however the shape of the vesicles was not uniform. After the addition of about tenfold of DPPC, monoform and monodisperse nanoerythrosomes became typical. The outer surfaces of these roughly spherical objects were frequently polygonal, consisting of a net of pentagons and hexagons.

International audience; We carried out detailed petrographic, major and trace element geochemical, microstructural and FTIR analyses on eight characteristic ultramafic xenoliths from Nyos and Barombi Mbo Lakes in the continental sector of the Cameroon Volcanic Line (CVL). The studied xenoliths are spinel lherzolites showing lithologies similar to the other xenoliths reported previously along the CVL. They have protogranular and porphyroclastic textures. One of the Barombi xenolith contains amphibole, which had not been previously reported in this locality. Amphibole is common in the Nyos xenoliths suite. Peridotite xenoliths from both localities show some chemical heterogeneity, but Barombi xenoliths generally are less depleted in basaltic elements with respect to Nyos xenoliths. Trace element compositions of Nyos spinel lherzolites show a moderately depleted initial (premetasomatic) composition and variable enrichment in REE. Evidence for both modal and cryptic metasomatism is present in Nyos xenoliths. Rare earth element patterns of clinopyroxene suggest that interaction between mafic melts and the upper mantle occurred beneath the Nyos locality. Barombi Mbo xenoliths, on the other hand, record a small degree of partial melting. The Barombi Mbo xenoliths have weak, dominantly orthorhombic olivine crystal preferred orientations, whereas Nyos ones have strong axial-[010] patterns, which may have formed in response to transpression. Nominally anhydrous mantle minerals (NAMs) of the Barombi Mbo xenoliths show generally higher bulk concentrations of ‘water’ (70–127 ppm) than Nyos xenoliths (32–81 ppm). The Barombi Mbo xenoliths could originate from a juvenile segment of the lithospheric mantle, which had been originally part of the asthenosphere. It became a part of the lithosphere in response to thermal relaxation following the extension, forming a weakly deformed lower lithospheric mantle region along the CVL. The Nyos xenoliths, however, represent a shallow lithospheric mantle bearing imprints of several depletion and enrichment events probably prior or following the extension (at ∼30 Ma).

The protein mediated approach is a common method for the synthesis of photoluminescent gold quantum clusters (GQCs), where proteins, acting as reducing and stabilizing agents, react with gold salts through cysteine residues. For the better understanding of the phenomenon, the aqueous phase reaction of HAuCl4 and l -cysteine has been investigated at the supramolecular level by various experimental techniques and molecular mechanics simulations. We have observed the formation of a novel photoluminescent product, ( AuCys ) n β , which shows emission in the orange region of the spectrum. Small- and wide-angle X-ray scattering (SWAXS) measurements have revealed the presence of nanosized lamellae, which have an internal multilayer superlattice structure with a characteristic periodic distance of 1.3 nm. Based on the results, the layers are built up by zigzag shaped (AuCys)n polymer chains connected through aurophilic bonds. The aurophilic network is stabilized via salt bridges and hydrogen bonds, which are also responsible for the interlayer interactions. Here, the evolution of the multilayer structure has been monitored by the combined application of photoluminescence spectroscopy and time-resolved SAXS. It has been concluded that there is a strong correlation between the emission and the scattering intensity, which suggests that the two- and three-dimensional aggregation of the building blocks to form sheets and multilayers are simultaneous processes. Furthermore, we have revealed that the formation and behavior of ( AuCys ) n β show significant differences to that of Au- l -glutathione compounds described earlier despite the similarity of l -cysteine and l -glutathione. These results evidence that l -cysteine and gold species form building blocks that can be applied expansively in supramolecular and cluster chemistry.

The newly developed zinc-rich hybrid paints are composed of polypyrrole (PPy) and polystyrene-sulfonate (PSS) modified alumina hydrate and either purified or functionalized multi-walled carbon nanotubes (MWCNTs). Preparation of the nano-size particles, i.e., in situ polymerization and deposition of PPy-PSS complexes on the mixture of alumina hydrate and MWCNTs is presented. Characterization of the particles by cyclic voltammetry (CV), Fourier-transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM) as well as their dispersions by rheology investigation is detailed in this part of the work. High electrochemical reversibility, increasing electrical conductivity and Coulombic efficiency of the particles with greater relative amount of the MWCNTs were evinced. Thin layer polymer deposition was found continuous on alumina and the MWCNTs and varied compactness of the PPy films and charge-delocalization over their network were witnessed depending on the proportion of incorporated PSS. Different micron-scale dispersity of the particles, compactness and ramification of particle clusters as well as their aggregation at nano-scale and flocculation at micron-scale were disclosed resulting in either kinetically three-dimensional (3D) interacting or non-percolating distribution. Corrosion protection performance of the hybrid coatings was examined whereas characteristics of the protection mechanism is substantially analysed from many perspectives, which all detailed in 2nd part of this study.

This study demonstrates that the unpolarized attenuated total reflectance Fourier transform infrared spectroscopy (ATR FTIR) is a practical and quick tool to distinguish different types of sediments in landslide-affected areas, and potentially other types of physical environments too. Identification and quantification of minerals by ATR FTIR is implemented on a set of powdered natural sediments from a loess landslide (Kulcs, Hungary). A protocol including sample preparation, analytical conditions and evaluation of sediment ATR spectra is outlined in order to identify and estimate major minerals in sediments. The comparison of the defined FTIR parameters against qualitative and quantitative results of X-ray diffraction and thermal analysis was used to validate the use of ATR FTIR spectroscopy for the considered sediments. The infrared band areas and their ratios (water/carbonates; silicates/carbonates; kaolinite) appear to be the most sensitive parameters to identify strongly weathered sediments such as paleosols and red clays which most likely facilitate sliding and could form sliding zones. The effect of grain size and orientation of anisotropic minerals on the wave number and intensity of some major absorption bands is also discussed.

Solid, nanoporous silica-based spherical mesoporous MCM-41 and KIL-2 with interparticle mesoporosity as well as nanosized zeolite BEA materials differing in morphology and pore size distribution, were used as carriers for the preparation of resveratrol-loaded delivery systems. Two preparation methods have been applied: (i) loading by mixing of resveratrol and mesoporous carrier in solid state and (ii) deposition in ethanol solution. The parent and the resveratrol loaded carriers were characterized by XRD, TEM, N2 physisorption, thermal analysis, and FT-IR spectroscopy. The influence of the support structure on the adsorption capacity and the release kinetics of this poorly soluble compound were investigated. Our results indicated that the chosen nanoporous silica supports are suitable for stabilization of trans-resveratrol and reveal controlled release and ability to protect the supported compound against degradation regardless of loading method. The solid-state dry mixing appears very effective for preparation of drug formulations composed of poorly soluble compound. - Graphical abstract: trans-Resveratrol was stabilized in the pores of BEA zeolite, MCM-41and KIL2 mesoporous silicas. - Highlights: • BEA, KIL-2 and MCM-41 materials were used as carriers for resveratrol loading. • Resveratrol encapsulation in ethanol solution and solid state procedure were applied. • The solid-state preparation appears very effective formore » stabilization of trans-resveratrol.« less

Gelatinous polymer matrix microparticles containing silver nanoparticles (AgNPs) were prepared by a novel method to obtain quasi non-swelling anti-fouling paint additives with slow-release characteristics. A w/o type dispersion were elaborated with the aqueous phase of gelatin, urea, silver-nitrate and formaldehyde dispersed in linseed oil. Gelatin was cross-linked by formaldehyde, together with urea for limiting the swelling of the product. Silver-nitrate was reduced with the assistance of gelatin and formaldehyde into homogenously dispersed AgNPs. The microparticles and embedded AgNPs were visualized by scanning and transmission electronmicroscopy. Encapsulated AgNPs with ∼18 nm crystallite size were identified by X-ray powder diffraction. Characterization of gelatin–urea–formaldehyde polymer matrices was carried out by attenuated total reflectance FTIR spectroscopy. Silver dissolution from microparticles and paints with AgNP-containing microparticles was measured by inductively coupled plasma spectrometer and resulted in highly sustained release, compared to unmodified gelatin microparticles and paints containing uncapsulated silver salts. A 7-month-long fouling experiment run in natural sweetwater media showed that solvent-based acrylic paint with AgNPs-containing gelatinous microparticles as additives offered resistance against biofouling at low Ag-release ratio.

The effect of 5th generation polyamidoamine (PAMAM G5) dendrimers on multilamellar dipalmitoylphosphocholine (DPPC) vesicles was investigated. PAMAM was added in two different concentrations to the lipids (10(-3) and 10(-2) dendrimer/lipid molar ratios). The thermal behavior of the evolved systems was characterized by DSC; while the structure and the morphology were investigated with small- and wide-angel X-ray scattering (SWAXS), freeze-fracture electron microscopy (FFTEM) and phosphorus-31 nuclear magnetic resonance ((31)P NMR) spectroscopy, respectively. IR spectroscopy was used to study the molecular interactions between PAMAM and DPPC. The obtained results show that the dendrimers added in 10(-3) molar ratio to the lipids generate minor perturbations in the multilamellar structure and thermal character of liposomes, while added in 10(-2) molar ratio dendrimers cause major disturbance in the vesicular system. The terminal amino groups of the dendrimers are in strong interaction with the phosphate headgroups and through this binding dendrimers disrupt the regular multilamellar structure of DPPC. Besides highly swollen, fragmented bilayers, small vesicles are formed.

Innovative zinc-rich hybrid paint coatings were developed using nano-size particles composed of alumina hydrate modified with polystyrene-sulfonate (PSS) doped polypyrrole (PPy) and either purified or functionalised multi-walled carbon nanotubes (MWCNTs). General properties of the particles and their dispersions were characterised in 1st part of the work. Corrosion protection characteristics of the hybrids were examined on low-carbon steel panels by immersion and salt-spray chamber tests. Immersion tests were monitored by electrochemical impedance spectroscopy (EIS). Primers were analysed by glow-discharge optical emission spectroscopy (GD OES) and surface of the steel substrates was investigated by X-ray photoelectron (XPS) and FT-Raman spectroscopy. Improved barrier and galvanic function of the hybrids over traditional zinc-rich paints (ZRPs) were evidenced by performance metrics. Optimal protection characteristics were found when content of the particles was close to the statistical and kinetic percolation thresholds. Advanced protection mechanism of the hybrids is discussed on function of the nano-size filler benefiting the utilisation of sacrificial current output of the anodic zinc along with taking into account aspects of the multiple percolation theory. The interpretation given in this work is intended to facilitate design of next generation of corrosion protecting metal-rich coatings.

A sandy soil of pH = 5.0 artificially contaminated with 15 mg/kg As in form of arsenate ions [iAs(V)] corresponding to the permissible value in force in Hungary was incubated for 4 weeks after amendment with different peanut shell-derived activated charcoal (AC) materials at an application rate of 2 wt%. Composite formation with silicate materials and adsorption mechanism for As were corroborated by attenuated total-reflection Fourier-transform infrared spectroscopy. Moreover, 0.01 M oxalic acid (OA) was also applied to investigate further enhancement through protonation of iAs(V) and/or AC. Assessment of As stabilization was achieved by a fit-to-purpose BCR sequential soil extraction procedure (extraction of the water-soluble and carbonatic fraction with 0.11 M acetic acid solution and the easily reducible one by 0.5 M hydroxylamine hydrochloride). Arsenic phytoavailability was estimated by leaching with 0.02 M EDTA solution (pH = 4.65). Samples were analyzed by inductively coupled plasma sector field mass spectrometer applying high resolution mode. Total-reflection X-ray fluorescence spectrometer was used to check data accuracy. The largest As stabilization rate (approximately 30%) compared to the reference soil treatment was obtained when granular Florisil®-AC was applied. Stabilization efficiency did not improve by using OA. A 5 wt% AC application rate for the Florisil® composite resulted in a similar As distribution to the 2 wt% one also at a 30 mg/kg iAs(V) dosage. The amounts of immobilized As increased almost proportionally with the higher AC application rate by doubling the iAs(V) dose. Similarly, studies conducted on solutions proved that As adsorption onto ACs was slightly exponential.

The UV–Visible and Surface Enhanced Raman Spectroscopy (SERS) behavior of silver sol (a typical SERS agent) were studied in the presence of different bifunctional thiols such as p-aminothiophenol, p-mercaptobenzoic acid, p-nitrothiophenol, p-aminothiophenol hydrochloride, and 2-mercaptoethylamine hydrochloride in diluted aqueous solution. Our results confirm that the p-aminothiophenol induced aggregation of citrate stabilized silver colloid originates from its electrostatic nature, as well as the azo-bridge formation cannot be the reason of the observed time dependent UV–Visible spectra. Based on our parallel SERS and electrospray ionization mass spectrometry measurements, we have concluded that certain amount of oxidized form of the probe molecule has to be present for the so-called b2-mode enhancement in the SERS spectrum of p-aminothiophenol. Our findings seem to support the idea that the azo-bridge formation is responsible for the b2-mode enhancement in the SERS spectrum of p-aminothiophenol.

Attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) combined with curve fitting procedures was used to characterize the poly(ethylene glycol) (PEG) layer of a pharmacologically relevant liposomal drug delivery system. The hydration of the polymer layer was described based on the ratio of the trans and gauche configurations of the C–O–C bond of the PEG molecules, which show a minimum at ∼6 mol% PEG-lipid molar ratio. The latter corresponds to highest bilayer stability, and coincides with the transition from the mushroom to the brush configuration of the PEG structure. This preliminary study showed that the ATR-FTIR technique is capable of qualitatively describing the hydration of the PEG-layer of stealth liposomes, which is in connection with the structure of the polymer on the liposomal surface.

Objective In this contribution a simple method is elaborated for the preparation of Pt/SnOx–TiO2 catalysts which are active in the photocatalytic reforming of methanol. The region of low tin content (Sn/Ti atomic ratio: 0–0.015) is explored. Tin content related activity changes of the catalysts are discussed in terms of the results of structural characterization. Methods Tin-modified anatase TiO2 samples were obtained from sol–gel method by use of Ti-isopropoxide, SnCl4 or Sn(OBu)4 and citric acid in absolute ethanol solution followed by calcinations at 400 °C in air. After loading Pt by impregnation the catalytic activity has been tested irradiating the slurry of the catalysts suspended in mixture of water and methanol by means of two different light sources, one working exclusively in the visible region and one in a broader spectral range including a UV-component, respectively. Hydrogen production activity has been correlated with structural data obtained from different characterization techniques such as ESR spectroscopy, XRD, XPS, SEM and Raman spectroscopy as well as diffuse reflectance UV–Vis spectrophotometry. Results According to ESR spectroscopic measurements the presence of oxygen vacancies was responsible for the slight visible light absorption. XRD, XPS, SEM and Raman spectroscopic results indicated that highly dispersed SnOx accumulated in the surface region of TiO2, no tin incorporation into the lattice was observed. The fundamental band gap was not influenced by the presence of tin. Loading of the tin-modified samples by 0.5 wt% Pt increased the hydrogen production in comparison to 0.5 wt% Pt/TiO2 samples. Conclusions The improvement in the catalytic activity was explained by formation of new tin related charge carrier traps leading to (i) prevention of electron–hole recombination and (ii) additional modification of the adsorption of reactants. Details of the two different working mechanisms are described. Practice implication The increased hydrogen production over the tin modified samples provides a promising step toward practical usage of light for hydrogen production.

Novel organic–inorganic hybrid nanotubes containing silica and ethane (EtSNT), ethylene (ESNT) and acetylene (ASNT) units, as well as brominated ESNT (Br-ESNT) and glycine-modified Br-ESNT (Gly-ESNT) have been studied by IR and Raman spectroscopy. The results are compared with the spectral features for conventional silica nanotubes (SNT) and amorphous silica. Bands peculiar to organic moieties have been detected and assigned. Assignment of the silicate backbone vibrations was based on the results of normal coordinate calculations. Furthermore, characteristic silicate, so-called ‘nanotube’ vibrations have been identified and their band positions have been summarized to serve as a future reference for such compounds. SiOSi antisymmetric stretchings were observed in the range 1000–1110 cm−1, while the symmetric stretchings appeared between 760 and 960 cm−1 for EtSNT, ESNT and Br-ESNT. Force constants have been refined for models of the repeating structure units: O3SiOSi(OSi)3 for SNT and SiCHnCHnSi(OSi)3 for organosilica nanotubes (n = 2, EtSNT; n = 1, ESNT and n = 0, ASNT). The calculated SiO stretching force constants were increased from 4.79 to 4.88 and 5.11 N cm−1 for EtSNT, ESNT and ASNT, respectively. The force constants have been compared with those for several silicates and SiO bond length are predicted and discussed.

Spherical MCM-41 silica nanosized particles were synthesized and post synthesis modified by 3-aminopropyltriethoxysilane (APTES) in order to prepare amino-functionalized carrier. Both types of silica particles were loaded with indometacin and further coated with carbopol. The preservation of morphology and pore structure of the particles was observed by XRD, TEM and N2 physisorption. FTIR spectroscopy revealed the interaction between carboxyl groups of indometacin and the amino groups of the functionalized MCM-41. Amino-functionalization of the carrier resulted in higher degree of indometacin loading in comparison to the parent MCM-41, 39% vs. 30%, respectively. The coating of drug loaded amino-MCM-41 silica particles with carbopol significantly reduced the initial burst release of indometacin. Both silica carriers demonstrated no cytotoxicity on HL-60 (acute myeloid leukemia) and K-562 (chronic myeloid leukemia) cell lines.

The thermotropic and structural effects of low molecular weight poly(malic acid) (PMLA) on fully hydrated multilamellar dipalmitoylphosphatidylcholine (DPPC)–water systems were investigated using differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS), and freeze-fracture transmission electron microscopy (FFTEM). Systems of 20 wt% DPPC concentration and 1 and 5 wt% PMLA to lipid ratios were studied. The PMLA derivatives changed the thermal behavior of DPPC significantly and caused a drastic loss in correlation between lamellae in the three characteristic thermotropic states (i.e., in the gel, rippled gel and liquid crystalline phases). In the presence of PBS or NaCl, the perturbation was more moderate. The structural behavior on the atomic level was revealed by FTIR spectroscopy. The molecular interactions between DPPC and PMLA were simulated via modeling its measured infrared spectra, and their peculiar spectral features were interpreted. Through this interpretation, the poly(malic acid) is inferred to attach to the headgroups of the phospholipids through hydrogen bonds between the free hydroxil groups of PMLA and the phosphodiester groups of DPPC.

A new, simple, and “green” method was developed for the surface modification of 20 nm diameter Stober silica particles with 3-aminopropyl(diethoxy)methylsilane in ethanol. The bulk polycondensation of the reagent was inhibited and the stability of the sol preserved by adding a small amount of glacial acetic acid after appropriate reaction time. Centrifugation, ultrafiltration, and dialysis were compared in order to choose a convenient purification technique that allows the separation of unreacted silylating agent from the nanoparticles without destabilizing the sol. The exchange of the solvent to acidic water during the purification yielded a stable colloid, as well. Structural and morphological analysis of the obtained aminopropyl silica was performed using transmission electron microscopy (TEM), dynamic light scattering (DLS) and zeta potential measurements, Fourier-transform infrared (FTIR), 13 C and 29 Si MAS nuclear magnetic resonance (NMR) spectroscopies, as well as small angle X-ray scattering (SAXS). Our investigations revealed that the silica nanoparticle surfaces were partially covered with aminopropyl groups, and multilayer adsorption followed by polycondensation of the silylating reagent was successfully avoided. The resulting stable aminopropyl silica sol (ethanolic or aqueous) is suitable for biomedical uses due to its purity.

This paper is focused on studying corrosion protection of cold-rolled steel with alkyd paint coatings comprising nano-size alumina and either polystyrene-sulphonate (PSS) modified or sulphonated multi-walled carbon nanotube (MWCNT) supported polypyrrole (PPy). Single layer coatings (in thickness of 40 ± 5 μm) comprising PPy deposited alumina and PSS modified MWCNT supported PPy afforded viable protection during the 1 M sodium chloride test. The coatings containing PSS modified and weakly sulphonated MWCNTs (at volume fractions of 9.9 × 10−4 and 2.5 × 10−4) with PPy volume fractions of 3.5 × 10−3 and 2.5 × 10−3 provided effective corrosion prevention during the 1 M sodium chloride and hydrochloric acid solution tests. While inhibitor particles were characterised by infrared spectroscopy, corrosion products formed at the paint–steel interface were studied by X-ray photoelectron spectroscopy. Apart from the electron microscopy observations, rheology study of three-dimensional structure of the inhibitor particles was performed in dispersions at similar compositions to those used for the paint formulations. Thus, protection mechanism relating to both types of immersion tests is discussed in terms of properties of the inhibitor particles and their microstructure in the coatings.

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.

This study presents the exploitation of an alternative reaction route of deamination of arylamines to perform in situ derivatisation of multi-walled carbon nanotubes (MWCNTs) with polyphenyl (PPh) species of various masses. As a result of consecutive derivatisation, high conversion of PPh grafting of the MWCNTs was realised with the collateral outgrowth of physical modification with adsorbed additional PPhs. Applied derivatisation process exceeds the monolayer coverage related superficial saturation limitations in the overall grafting yield of the nanotubes. Thus, a linear relationship was recognized between the overall quantities of chemisorbed PPhs composed of D 5 -phenylene oligomers and the applied excess of diazonium activated reagents, corresponding to 2 H MAS NMR spectroscopy results. According to mass spectrometry (MS) investigations, uniform thermal decomposition of the chemisorbed PPhs modified MWCNTs was found besides the more intense and altered decomposition characteristic-featured adsorbate-chemisorbate PPhs contained MWCNTs during sequential pyrolysis under inert atmosphere. This is attributed to the pyrolysis provoked isomerisation, decomposition and the formation of adsorbed and chemisorbed PPh moieties. As a result, a mediated and an even more pronounced degradation in the order of graphitic lattice of the MWCNTs were evidenced in the adsorbate-chemisorbate and the chemisorbate PPhs contained samples by FT-Raman spectroscopy and transmission electron microscopy (TEM), respectively. 2 H MAS NMR supplied results of relevant amount of deuterium in the chemisorbate PPh contained sample without traces of aromatic related MS detected volatile products, these allow us to conclude about a thermally stable derivatisation that is interpreted as an endohedral modification of the nanotubes.

This study unveils a chemical functionalization provoked phase transformation in the naphthalene modified multi-walled carbon nanotubes (MWCNTs) and the associated formation of amorphous carbonaceous particles of various size and morphology. Functionalized nanotubes were prepared by a sulfonation-oxidization and a highly corrosive oxidative sulfation reaction then characterized by means of thermogravimetry/mass spectrometry, X-ray photoelectron spectroscopy, scanning and transmission electron microscopy and Raman spectroscopy. In spite of the small change in the composition of sulfonation and sulfation reaction mixtures, conventional sulfonation with oleum resulted in lower sulfonation and higher oxidative conversion of MWCNTs accompanied with a mediated exohedral amorphization of the nanotubes, induced by the yield of sp 3 hybridization defect introduction. On the other hand, the newly applied oxidative sulfation reaction provided severe oxidative etching, cutting and shortening of MWCNTs with a subsequent high conversion of sulfate derivatisation of oxidized functionalities, which induced complete collapse and phase transformation of the nanotubes. Amorphization and phase transformation of oxidative sulfated MWCNTs have led to the formation of highly dispersed nano- and micron-size amorphous carbon spheres, rods and flake-like structures. Water based colloidal systems of excellent stability were prepared from the oxidative sulfated carbonaceous material. Consequently, the employed highly corrosive sulfation reaction is capable to provide highly functionalized carbonaceous nano and micro-size particles from MWCNTs.