National Institute Of Materials Physics - Romania

This is the first report on an efficient, "environmentally friendly" chemical reduction method for the synthesis of aminated hyaluronic acid-based silver nanoparticles on the modified surface of titanium dioxide nanoparticles aimed for biological applications. Silver nanoparticles exhibit well-known physical-chemical and optical prop-erties appropriate for different biological applications. Modifying the nanoparticles leads to a change in their expected bioactivity. This represents an important topic for the current research. We have developed a novel aminated hyaluronic acid (HA-EDA)-based protocol to obtain silver nanoparticles, in which HA-EDA was used for the first time as a reducing and stabilizing agent. The effect of the size of silver nanoparticles on the titanium dioxide surface and the chemical composition of the obtained materials were investigated by TEM, XRD, XPS, ATR-FTIR, Raman spectroscopy, NMR and H2-TPR analyses. The antioxidant, in vitro biocompatibility, and antimicrobial activity of the fabricated composites have been evaluated. The results prove that the prepared materials exhibit antimicrobial, antioxidant, and anti-inflammatory activity, thus providing protection against infection and supporting tissue regeneration, these two key effects being of paramount importance for promoting wound healing.

The effectiveness of mesoporous SnO2 nickel-decoration as a method for obtaining active electrode materials for bioethanol electrochemical oxidation and the way in which the embedment of a small amount of Black Pearls (BP) affects the electrocatalytic performances of Ni/SnO2 systems were investigated. XPS analysis reveals the presence of NiO, Ni(OH)(2) and Ni2O3 chemical species which favors the oxidation of bioethanol and improves the COx tolerance. Nickel deposition in a reducing environment does not affect the Sn chemistry and the mesoporosity but significantly increases S-BET. A slight amount of BP enhances the S-BET value and a induces a small contribution of larger pores appears. Tafel slopes of 80 mV decade(-1) were estimated for bioethanol oxidation at Ni/SnO2, which favorably compare to those reported in the literature. It was also found that BP incorporation leads to a decrease of the Tafel slope to 70 mV decade(-1), without deleteriously affecting the stability of the electrocatalyst during long-term polarization. EIS results suggested that this improvement might be the combined effect of a lower electrical resistance, a higher specific surface area and a certain contribution from larger pores, which could lead to a better access of the bioethanol species to the electrocatalyst surface.

Two hybrid materials, based on 7-amino-4-(trifluoromethyl)coumarin and 7-amino-4-methyl-coumarin that attach covalently to graphene oxide (GO) have been synthesized in two steps: i) increasing the number of carboxyl groups required for functionalization with aminocoumarin derivatives by derivatization of the hydroxyls groups with chloroacetic acid, transforming GO into GO-COOH material; ii) activation of carboxylic groups using the carbodiimide-promoted reaction. The obtained composites were characterized by numerous methods that highlighted their successful obtaining. The antimicrobial activity was evaluated on resistant Mycobacterium tuberculosis strains, as well as on ESKAPE pathogens ((Enterococcus faecium, Staphylococcus aureus, Klebsiella pneumoniae, Acinetobacter baumannii, Pseudomonas aeruginosa, and Enterobacter spp.) in planktonic and biofilm growth states. The biocompatibility of the materials has been assayed using 3-(4, 5-dimethylthiazol-2-yl)2, 5-diphenyltetrazolium bromide assay as well as by measuring the level of nitric oxide/total reactive oxygen species and superoxide release in treated cells. The results have shown that materials exhibited improved inhibitory activity against resistant M. tuberculosis strains in comparison with GO, but also against planktonic and adherent strains. Also, the tested composites have been proved to be biocompatible on the MRC-5 fibroblast cells, demonstrating their promising potential to develop novel agents effective against multidrug resistant pathogens, including M. tuberculosis, as well as by the activation of a pro-inflammatory and of an oxidative response in the mammalian cells.

Hydrothermally formed mesoporous SnO2 was used as a support for nickel chemical deposition and, after subsequent thermal treatment, a high specific surface area (36 m(2) g(-1)) Ni/SnO2 material was obtained. XPS analysis has shown that in the Sn 3d region the spectrum is similar to that of pristine SnO2, whereas Ni species are present on the surface as NiO, Ni2O3 and Ni(OH)(2). Mixing Ni/SnO2 with a small amount of Black Pearls (BP) leads to a significant enhancement of the resulting Ni/SnO2-BP composite activity for nitrite anodic oxidation, presumably due to the higher surface area (115 m(2) g(-1)), to better electrical conductivity and to a certain contribution of the BP to an increase in surface density of the active sites. Ni/SnO2-BP also outperforms pristine BP (in terms of Tafel slopes and electron-transfer rates), most likely due to the fact that the Ni(ii)/Ni(iii) couple can act as an electrocatalyst for nitrite oxidation. A voltammetric method is proposed for the determination of nitrite, over a concentration range of three orders of magnitude (0.05 to 20 mM), with good reproducibility, high stability and excellent sensitivity. The high upper limit of the dynamic range of the analytically useful response might provide a basis for the reliable quantification of nitrite in wastewater.

This work reports the design and synthesis of novel oxadiazole-decorated azobenzenes, structural analysis of the resulting compounds and behavior under light irradiation. The synthetic strategy involved constructing amino functionalized heterocyclic key intermediates which were used either to yield electrophilic diazonium salts able to react with phenol moieties or as nucleophilic partners in Bayer-Mills reaction with nitroso-substituted derivatives. The amino-derived oxadiazole intermediates were investigated by absorption and emission spectroscopy providing blue and green emitted light. The target oxadiazole-decorated azobenzenes were structurally characterized, including solid-state structures, and subsequently used in irradiation experiments in order to take advantage of the azo group known to provide photoswitching abilities. We noticed quenching of the emissive properties in presence of the azo group; however, all compounds were very stable to repeated cycles of light irradiation. In addition, according to structural diversification we could obtain half-lives of the meta stable isomers within hours to hundreds of hours range. The experimental results were very well correlated with DFT calculations. The synthesis of novel oxadiazole-decorated azobenzenes using amino functionalised heterocyclic intermediates used either to provide electrophilic diazonium salts able to react with phenols or as nucleophilic partners in Bayer-Mills reaction is reported in this work. The oxadiazole-decorated azobenzenes were used in irradiation experiments to determine the parameters that characterize a photoswitch, yielding appealing results. The experimental results were very well correlated with DFT calculations.+image

Water and sunlight are the cleanest, most renewable, and abundant resources on Earth. Developing inexpensive, scalable photocatalysts that are highly stable for hydrogen (H-2) production has long been a cherished dream of humanity. Herein, we report on one-dimensional lepidocrocite-based sub-nanofilaments (NFs), approximate to 5 x 7 & Aring;(2) in cross-section, that generate H-2 from 80:20 v/v water/methanol mixtures when illuminated by simulated sunlight. The NFs were stable in the mixtures for times >4,300 h, 300 h of which were under irradiation. Apparent quantum yields as high as 11.7% were obtained. Based on deuterated water results, we conclude that water is the H-2 source. Further, no carbon dioxide (CO2) due to photocatalytic degradation of methanol was detected. Therefore, the NFs have strong green credentials and lucrative economic prospects for large scale up. We expect these NFs will lead to new lines for developing cheap and ultra-stable materials to produce H-2 photochemically for a long time.

Currently, the treatment of wounds is still a challenge for healthcare professionals due to high complication incidences and social impacts, and the development of biocompatible and efficient medicines remains a goal. In this regard, mesoporous materials loaded with bioactive compounds from natural extracts have a high potential for wound treatment due to their nontoxicity, high loading capacity and slow drug release. MCM-41-type mesoporous material was synthesized by using sodium trisilicate as a silica source at room temperature and normal pressure. The synthesized mesoporous silica was characterized by using Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), N2 absorption-desorption (BET), Dynamic Light Scattering (DLS) and Fourier transform infrared spectroscopy (FT-IR), revealing a high surface area (BET, 1244 m2/g); pore diameter of approx. 2 nm; and a homogenous, ordered and hexagonal geometry (TEM images). Qualitative monitoring of the desorption degree of the Salvia officinalis (SO) extract, rich in ursolic acid and oleanolic acid, and Calendula officinalis (CO) extract, rich in polyphenols and flavones, was performed via the continuous recording of the UV-VIS spectra at predetermined intervals. The active ingredients in the new composite MCM-41/sage and marigold (MCM-41/SO & CO) were quantified by using HPLC-DAD and LC-MS-MS techniques. The evaluation of the biological composites' activity on the wound site was performed on two cell lines, HS27 and HaCaT, naturally involved in tissue-regeneration processes. The experimental results revealed the ability to stimulate collagen biosynthesis, the enzymatic activity of the main metalloproteinases (MMP-2 and MMP-9) involved in tissue remodeling processes and the migration rate in the wound site, thus providing insights into the re-epithelializing properties of mesoporous composites.

Two new families of zinc/cobalt/aluminum-based pigments, with a unique composition, were obtained through the polyol method. The hydrolysis process of a mixture of Co(CH3COO)(2), Zn(acac)(2) and Al(acac)(3) (acac(-) = acetylacetonate ion) in 1,4-butanediol afforded dark blue gels (wPZn(x)Co(1-x)Al), in the presence of a supplementary amount of water, and light green powders (PZnxCo1-xAl), respectively, for the water-free procedure (x = 0, 0.2, 0.4). The calcination of the precursors yielded dark green (wZn(x)Co(1-x)Al) and blue (ZnxCo1-xAl) products. XRD measurements and Rietveld refinement indicate the co-existence of three spinel phases, in different proportions: ZnxCo1-xAl2O4, Co3O4 and the defect spinel, ?-Al2.67O4. The Raman scattering and XPS spectra are in agreement with the compositions of the samples. The morphology of wZn(x)Co(1-x)Al consists of large and irregular spherical particle aggregates (ca. 5-100 mm). Smaller agglomerates (ca. 1-5 mm) with a unique silkworm cocoon-like hierarchical morphology composed of cobalt aluminate cores covered with flake-like alumina shells are formed for ZnxCo1-xAl. TEM and HR-TEM analyses revealed the formation of crystalline, polyhedral particles of 7-43 nm sizes for wZn(x)Co(1-x)Al, while for ZnxCo1-xAl, a duplex-type morphology, with small (7-13 nm) and larger (30-40 nm) particles, was found. BET assessment showed that both series of oxides are mesoporous materials, with different pore structures, with the water-free samples exhibiting the largest surface areas due, most likely, to the high percent of aluminum oxide. A chemical mechanism is proposed to highlight the role of the water amount and the nature of the starting compounds in the hydrolysis reaction products and, further, in the morpho-structural features and composition of the resulting spinel oxides. The CIE L*a*b* and C* colorimetric parameters indicate that the pigments are bright, with a moderate degree of luminosity, presenting an outstanding high blueness.

Iron-doped Co3O4 oxides prepared by a surfactant-assisted method exhibited good catalytic activity in malic acid conversion, and the oxygen defects associated with the presence of Co2+ played a key role in catalyst activation for pyruvic acid production. The most active catalyst, for which the malic acid conversion was 70% and the pyruvic acid yield was 24%, has an inverse spinel type structure (Fe3+ replaces Co2+ from tetrahedral sites, while Fe2+ replaces Co3+ from octahedral sites) as well as a small energy difference between the highest occupied orbital and the lowest unoccupied orbital (low band-gap, E-g). The catalyst with the highest Co2+ loading showed the highest yield of pyruvic acid.

Photocatalytic conversion of H2O, CO2 and N-2 represents one promising approach to harvest and store solar energy, for which efficient visible light responsive semiconductors are inevitable. Often, the presence of a small amount of an additional component called a "cocatalyst", is required to synergistically enhance the performance of the photocatalyst. Tremendous efforts were made in the past to identify inexpensive materials to be used as cocatalysts, for which metal oxides (MOs) are one of the traditional choices. Among alternative categories of materials investigated, the recently discovered MXenes display enormous potential owing to their unique 2D layered structure, tuneable composition, abundant surface functionalities and superior electronic conductivity. Specifically, MOs and MXenes encompass a variety of distinct as well as analogous characteristics that allows them to be tailored to different extents. Unfortunately, a comprehensive overview covering the synthetic, structural and photocatalytic aspects of MOs and MXenes is not available as of now. Herein, we intend to summarize the progress achieved so far in these two families of materials to be used as cocatalysts for the photoconversion of H2O, CO2 and N-2. Followed by a general introduction, we briefly outline the fundamental principles and the role of cocatalysts in photocatalytic reactions. A discussion regarding the use of MOs and MXenes as cocatalysts for the conversion of H2O, CO2 and N-2 is then provided in separate sections. Critical assessment regarding structure and morphology control, surface properties and stability concerns can not only help to recognize the challenges that limit further advancement, but can also highlight the future research directions of these materials for the effective transformation of H2O, CO2 and N-2.