Scavenger-Supported Photocatalytic Evidence of an Extended Type I Electronic Structure of the TiO2@Fe2O3 Interface.

Heterostructures of TiO2@Fe2O3 with a specific electronic structure and morphology enable us to control the interfacial charge transport necessary for their efficient photocatalytic performance. In spite of the extensive research, there still remains a profound ambiguity as far as the band alignment at the interface of TiO2@Fe2O3 is concerned. In this work, the extended type I heterojunction between anatase TiO2 nanocrystals and α-Fe2O3 hematite nanograins is proposed. Experimental evidence supporting this conclusion is based on direct measurements such as optical spectroscopy, X-ray photoemission spectroscopy, scanning electron microscopy, high-resolution transmission electron microscopy (HRTEM), and the results of indirect studies of photocatalytic decomposition of rhodamine B (RhB) with selected scavengers of various active species of OH•, h•, e-, and •O2-. The presence of small 6-8 nm Fe2O3 crystallites at the surface of TiO2 has been confirmed in HRTEM images. Irregular 15-50 nm needle-like hematite grains could be observed in scanning electron micrographs. Substitutional incorporation of Fe3+ ions into the TiO2 crystal lattice is predicted by a 0.16% decrease in lattice parameter a and a 0.08% change of c, as well as by a shift of the Raman Eg(1) peak from 143 cm-1 in pure TiO2 to 149 cm-1 in Fe2O3-modified TiO2. Analysis of O 1s XPS spectra corroborates this conclusion, indicating the formation of oxygen vacancies at the surface of titanium(IV) oxide. The presence of the Fe3+ impurity level in the forbidden band gap of TiO2 is revealed by the 2.80 eV optical transition. The size effect is responsible for the absorption feature appearing at 2.48 eV. Increased photocatalytic activity within the visible range suggests that the electron transfer involves high energy levels of Fe2O3. Well-programed experiments with scavengers allow us to eliminate the less probable mechanisms of RhB photodecomposition and propose a band diagram of the TiO2@Fe2O3 heterojunction.

Phase Analysis and Thermoelectric Properties of Cu-Rich Tetrahedrite Prepared by Solvothermal Synthesis.

Because of the large Seebeck coefficient, low thermal conductivity, and earth-abundant nature of components, tetrahedrites are promising thermoelectric materials. DFT calculations reveal that the additional copper atoms in Cu-rich Cu14Sb4S13 tetrahedrite can effectively engineer the chemical potential towards high thermoelectric performance. Here, the Cu-rich tetrahedrite phase was prepared using a novel approach, which is based on the solvothermal method and piperazine serving both as solvent and reagent. As only pure elements were used for the synthesis, the offered method allows us to avoid the typically observed inorganic salt contaminations in products. Prepared in such a way, Cu14Sb4S13 tetrahedrite materials possess a very high Seebeck coefficient (above 400 µVK-1) and low thermal conductivity (below 0.3 Wm-1K-1), yielding to an excellent dimensionless thermoelectric figure of merit ZT ≈ 0.65 at 723 K. The further enhancement of the thermoelectric performance is expected after attuning the carrier concentration to the optimal value for achieving the highest possible power factor in this system.

Biopolymeric hydrogels - nanostructured TiO2 hybrid materials as potential injectable scaffolds for bone regeneration.

The present work aims at development of novel hybrid materials from genipin crosslinked collagen or collagen/chitosan hydrogels containing various types of TiO2 nanoparticles characterized with different anatase/rutile ratios. Collagen and chitosan were selected as hydrogel components since they are biopolymers being, like collagen, the major compound present in extracellular matrix or exhibit structural similarity to glycosaminoglycans, like chitosan. TiO2 nanoparticles were introduced to the hydrogel matrices to improve their mechanical properties as well as bioactivity. A series of twelve novel hybrid materials were prepared and their physicochemical, mechanical and biological properties were evaluated. It was found that TiO2 nanostructures introduced to the hydrogels have significant influence on the swelling properties of the synthesized hybrids and their impact is strongly dependent on the type of matrices. The surfaces of hybrid materials were found to be more hydrophilic than these of corresponding hydrogel matrix. It was also observed that, the storage modulus values of the hybrids based on collagen-chitosan hydrogel are comparable to these for plain hydrogels what indicates that the mechanical properties of the materials obtained are satisfactory for possible biomedical application. The in vitro cell culture studies have shown that prepared materials are biocompatible as they can support mitochondrial activity of MEFs as well as MG-63 cells. In vitro experiments performed under simulated body fluid (SBF) conditions have revealed that all studied TiO2 nanoparticles present in hydrogel matrices, regardless of anatase/rutile ratio, successfully induced formation of apatite-like structures. The hybrid materials developed here are promising candidates for preparation of bioactive, injectable scaffolds for tissue engineering.

Chitosan derivatives as novel potential heparin reversal agents.

In emergency cases anticoagulant action of heparin needs to be stopped instantaneously, which is usually achieved by intravenous administration of protamine sulfate (PS). However, PS shows many adverse effects. The objective of the present work was to find out if chitosan (Ch) and a cationically modified chitosan, N-(2-hydroxypropyl)-3-trimethylammonium chitosan chloride (HTCC), may be applied for heparin reversal. For chitosan the efficiency of unfractionated heparin (UFH) binding decreases with increasing pH while for cationically modified chitosan heparin binding is efficient even for high pH values. Complexation of UFH and low-molecular-weight heparin (LMWH) by cationically modified chitosan in the aqueous solution at pH = 7.4 was studied. Complexes of the modified chitosan with UFH are smaller and of lower dispersity than those with PS. Cationically modified chitosan was found to bind both UFH and LMWH. The complex formation capability of cationically modified chitosan is comparable to that of PS.

pH-sensitive genipin-cross-linked chitosan microspheres for heparin removal.

Chitosan hydrogel microspheres were obtained by cross-linking chitosan in its inverse emulsion using genipin as cross-linker. The genipin-cross-linked chitosan microspheres (ChGp) swell significantly in water at pH values below 6.5 and shrink to a smaller extent at pH values above 6.5. ChGp microspheres bind heparin in water. The kinetics of heparin binding was found to be pH dependent and was faster and more efficient at a lower pH. That can be also controlled by the weight of ChGp microspheres used. Rate and efficiency of heparin adsorption at pH 7.4, which is typical of blood, could be increased by quaternization of ChGp microspheres using glycidyltrimethylammonium chloride (GTMAC). The polymeric material obtained thus can be potentially useful for heparin removal in biomedical applications.