pH-tunable nanoparticles composed of copolymers of lactide and allyl-glycidyl ether with various functionalities for the efficient delivery of anti-cancer drugs.

The designing of biocompatible nanocarriers for the efficient delivery of their cargos to the desired targets remains a challenge. In this regard, the most promising strategy relies on the construction of pH- or thermo-responsive nanoparticles (NPs). However, it is also important to preserve the balance between the responsiveness of the carrier and their stability in physiological conditions. Therefore, we described a new family of copolymers of lactide and allyl-glycidyl ether which were subsequently modified by thiol-ene reaction to functionalize the resulting copolymer with acetylcysteine (ACC) or thioglycolic acid (tGA) moieties. Subsequently, these copolymers were used to obtain blank and doxorubicin (DOX) loaded NPs with an average diameter of about 50-100 nm. Interestingly, the NPs were stable in different pH conditions, however, the presence of ACC or tGA units in the polymeric chain allows for the reduction of the undesired burst release due to the supramolecular interactions between polymeric pedant groups and DOX. The release tests of DOX from NPs showed that DOX release rate decrease depending on the pH values and the copolymer functionalization in order of non-modified NPs > ACC-modified NPs > tGA functionalized NPs. Most importantly, the MTT assay showed that all blank NPs are non-toxic against the normal L929 cell line. Subsequently, the antitumor efficiency of the obtained NPs was tested towards L929 (murine fibroblast cell line), HeLa (cervical cancer), and AGS (human gastric adenocarcinoma cancer) cells. The results demonstrated that DOX-loaded NPs efficiently induce the reduction in the viability of the HeLa and AGS cell, and this reduction in the viability was even below 20 % for the AGS cells. Together with their biocompatibility, the obtained NPs offer a novel route for the preparation of nanocarriers for the controlled and efficient delivery of anticancer drugs.

Self-reduction of the native TiO2 (110) surface during cooling after thermal annealing - in-operando investigations.

We investigate the thermal reduction of TiO2 in ultra-high vacuum. Contrary to what is usually assumed, we observe that the maximal surface reduction occurs not during the heating, but during the cooling of the sample back to room temperature. We describe the self-reduction, which occurs as a result of differences in the energies of defect formation in the bulk and surface regions. The findings presented are based on X-ray photoelectron spectroscopy carried out in-operando during the heating and cooling steps. The presented conclusions, concerning the course of redox processes, are especially important when considering oxides for resistive switching and neuromorphic applications and also when describing the mechanisms related to the basics of operation of solid oxide fuel cells.

Local surface conductivity of transition metal oxides mapped with true atomic resolution.

The introduction of transition metal oxides for building nanodevices in information technology promises to overcome the scaling limits of conventional semiconductors and to reduce global power consumption significantly. However, oxide surfaces can exhibit heterogeneity on the nanoscale e.g. due to relaxation, rumpling, reconstruction, or chemical variations which demands for direct characterization of electronic transport phenomena down to the atomic level. Here we demonstrate that conductivity mapping is possible with true atomic resolution using the tip of a local conductivity atomic force microscope (LC-AFM) as the mobile nanoelectrode. The application to the prototypical transition metal oxide TiO2 self-doped by oxygen vacancies reveals the existence of highly confined current paths in the first stage of thermal reduction. Assisted by density functional theory (DFT) we propose that the presence of oxygen vacancies in the surface layer of such materials can introduce short range disturbances of the electronic structure with confinement of metallic states on the sub-nanometre scale. After prolonged reduction, the surfaces undergo reconstruction and the conductivity changes from spot-like to homogeneous as a result of surface transformation. The periodic arrangement of the reconstruction is clearly reflected in the conductivity maps as concluded from the simultaneous friction force and LC-AFM measurements. The second prototype metal oxide SrTiO3 also reveals a comparable transformation in surface conductivity from spot-like to homogeneous upon reduction showing the relevance of nanoscale inhomogeneities for the electronic transport properties and the utility of a high-resolution LC-AFM as a convenient tool to detect them.

TiO2--a prototypical memristive material.

Redox-based memristive switching has been observed in many binary transition metal oxides and related compounds. Since, on the one hand, many recent reports utilize TiO(2) for their studies of the memristive phenomenon and, on the other hand, there is a long history of the electronic structure and the crystallographic structure of TiO(2) under the impact of reduction and oxidation processes, we selected this material as a prototypical material to provide deeper insight into the mechanisms behind memristive switching. In part I, we briefly outline the results of the historical and recent studies of electroforming and resistive switching of TiO(2)-based cells. We describe the (tiny) stoichiometrical range for TiO(2 - x) as a homogeneous compound, the aggregation of point defects (oxygen vacancies) into extended defects, and the formation of the various Magnéli phases. Furthermore, we discuss the driving forces for these solid-state reactions from the thermodynamical point of view. In part II, we provide new experimental details about the hierarchical transformation of TiO(2) single crystals into Magnéli phases, and vice versa, under the influence of chemical, electrical and thermal gradients, on the basis of the macroscopic and nanoscopic measurements. Those include thermogravimetry, high-temperature x-ray diffraction (XRD), high-temperature conductivity measurements, as well as low-energy electron diffraction (LEED), x-ray photoelectron spectroscopy (XPS), and LC-AFM (atomic force microscope equipped with a conducting tip) studies. Conclusions are drawn concerning the relevant parameters that need to be controlled in order to tailor the memristive properties.

The new high-temperature surface structure on reduced TiO2(001).

Scanning tunnelling microscopy, ultraviolet photoelectron spectroscopy and current imaging tunnelling spectroscopy (STM/UPS/CITS) were used to study the topographic and electronic structure of a high-temperature structure formed on the TiO(2)(001) surface after heating at 1173 K. The STM images revealed different domain-like ordering and periodicity on the surface in comparison to those observed previously. The UPS studies showed the presence of a surface state at energy about 1.1 eV below the Fermi level. This result was confirmed by the CITS data showing pronounced periodic maxima of the electron local density of states at energy around 1.1-1.2 eV below the Fermi level and located on top of every row of the new high-temperature structure. The CITS results recorded for small grains, which coexist with the observed structure, showed that their chemical composition is closer to the Ti(2)O(3) material than to TiO(2-x) for x << 1.