Crystallographic and magnetic properties of HfFe6Ge6-type REFe6Sn4Ge2 compounds (RE = Y, Gd–Er)

The REFe₆Sn₄Ge₂ (RE = Y, Gd–Er) compounds have been synthesized and studied by powder X-ray diffraction and magnetisation measurements. These compounds crystallize in the hexagonal HfFe₆Ge₆ structure although the parent ternary compounds REFe₆X₆ (X = Ge, Sn) display more complicated orthorhombic crystal structure. This evolution is discussed and interpreted on the basis of the relaxation of some RE–X contacts in the quaternary compounds. The iron sublattice order antiferromagnetically above room temperature (554 ≤ T_N ≤ 560 K) while the paramagnetic RE compounds display a second transition at low temperature (7.3 ≤ T_t ≤ 42.7 K). The magnetisation versus field curves display a metamagnetic behaviour at 4.2 K. The corresponding value of the magnetisation suggests a non-collinear ordering of the RE sublattice.     

Camptothecin and thiocamptothecin: the role of sulfur in shifting the hydrolysis equilibrium towards the closed lactone form

Adverse effects have limited the clinical potential of 20‐(S)‐camptothecin (CPT) and led to a growing interest in the development of CPT analogues that exhibit less severe drawbacks, while maintaining their therapeutic activity. Recently, a thiopyridone isostere of CPT, 20‐(S)‐thiocamptothecin (TCPT), was developed that resulted more potent than the parent compound in H460, HT29 and IGROV‐1 cell lines. The improved activity of TCPT over CPT might be due to the greater stability of the lactone ring. Here, reversible hydrolysis to the ring‐open carboxylate forms of CPT and TCPT was studied by HPLC, both in the presence and absence of human serum albumin (HSA). The amount of TCPT that exists in the lactone form at equilibrium in buffer solution (24 h) was found to be significantly higher than CPT, and the same trend was observed in the presence of HSA. Specifically, HSA caused a shift in the hydrolysis equilibrium of TCPT towards the carboxylate form, but the proportion of lactone form remained higher than that observed for CPT under the same conditions, and also in the presence of a higher excess of the protein. The role of the sulfur atom in the stability of the open and closed lactone derivatives was investigated by theoretical calculations using stabilization energies and comparison between experimental and calculated absorption spectra. Our results suggest that, in aqueous solution, more ionic species (anionic and enolic forms) are present for TCPT. This study provides further insights into the effects of oxygen/sulfur replacement in the CPT pyridone ring.     

Dynamics and mechanisms of interfacial photoinduced electron transfer processes of third generation photovoltaics and photocatalysis

Photoinduced electron transfer (PET) across molecular/bulk interfaces has gained attention only recently and is still poorly understood. These interfaces offer an excellent case study, pertinent to a variety of photovoltaic systems, photo- and electrochemistry, molecular electronics, analytical detection, photography, and quantum confinement devices. They play in particular a key role in the emerging fields of third-generation photovoltaic energy converters and artificial photosynthetic systems aimed at the production of solar fuels, creating a need for a better understanding and theoretical treatment of the dynamics and mechanisms of interfacial PET processes. We aim to achieve a fundamental understanding of these phenomena by designing experiments that can be used to test and alter modern theory and computational modeling. One example illustrating recent investigations into the details of the ultrafast processes that form the basis for photoinduced charge separation at a molecular/bulk interface relevant to dye-sensitized solar cells is briefly presented here: Kinetics of interfacial PET and charge recombination processes were measured by fs and ns transient spectroscopy in a heterogeneous donor-bridge-acceptor (D-B-A) system, where D is a Ru(II)(terpyridyl-PO3)(NCS)3 complex, B an oligo-p-phenylene bridge, and A nanocrystalline TiO2. The forward ET reaction was found to be faster than vibrational relaxation of the vibronic excited state of the donor. Instead, the back ET occurred on the micros time scale and involved fully thermalized species. The D-A distance dependence of the electron transfer rate was studied by varying the number of p-phenylene units contained in the bridge moiety. The remarkably low damping factor beta = 0.16 angstroms(-1) observed for the ultrafast charge injection from the dye excited state into the conduction band of TiO2 is attributed to the coupling of electron tunneling with nonequilibrium vibrations redistributed on the bridge, giving rise to polaronic transport of charges from the donor ligand to the acceptor solid oxide surface.     

Functionalized lactic acid macromonomers via polycondensation as an alternative to ring opening polymerization

Engineered polylactic acid (PLA) nanoparticles synthesized from oligo(lactic acid) macromonomers have been studied over the last decades for controlled drug delivery. These macromonomers are typically produced via ring-opening polymerization (ROP) of the cyclic dimer lactide, initiated by 2-hydroxyethyl methacrylate (HEMA). This reaction route, despite leading to well-defined macromonomers, relies on the production of lactide from lactic acid, which burdens the ROP overall cost for more than 30%. In this work, we report the synthesis of PLA-based macromonomers by direct polycondensation of lactic acid in the presence of HEMA as a valuable alternative to ROP. In particular, we compare the two processes side by side, focusing on the production of three HEMA-LA_n macromonomers, with n = 2, 4, and 6. Detailed kinetic models are developed for both reaction systems, and the corresponding parameters are estimated by fitting the experimental data. Through these models, the reaction kinetics as well as the time evolution of the entire chain length distributions of the products from polycondensation and ROP could be reliably predicted. This way, we demonstrated that polycondensation is a valuable alternative to ROP only for macromonomers with an average chain length of up to 4 and that ROP remains the main route to longer chains, when a strict control over the chain length distribution is required.     

Effects of carbonaceous nanoparticles from low-emission and older diesel engines on human skin cells

Diesel exhaust particles (DEP) are major constituents of ambient air pollution and are associated with respiratory and cardiovascular diseases as well skin cell alterations in vitro. The epidermal cells are among the first cell populations exposed to chemical pollutants, including DEP, and are an important source of pro-inflammatory mediators. We evaluated the effects of carbonaceous soot particles from current low-emission (Euro IV) diesel engines on the oxidative and inflammatory response of normal human skin cells and compared the results with those induced by carbonaceous soot particles from an older diesel engine (BS) operating under black smoke conditions. We observed that both soot nanoparticles were spontaneously internalised by keratinocytes and distributed mostly around the cell nucleus. Moreover, at the same mass concentration, Euro IV soot particles exhibited a much higher oxidative, pro-fibrotic and toxic potential on these cell types than soot particles from the older diesel engine. These results are in agreement with and confirm our previous findings on human macrophage cells and strengthen the assumption that, at the same mass concentration, soot particles produced under low emission conditions are more cytotoxic than particles from the older diesel engine. This effect could be assigned to the defective surface structure of Euro IV diesel soot, rendering it highly active. Our findings highlight that the reduction of soot emission in terms of mass does not automatically lead to a reduction of the dangerous effects and show that soot particles from different diesel engines possess different biological behaviour towards human cells.     

Barium Titanate Nanoparticles: Highly Cytocompatible Dispersions in Glycol-chitosan and Doxorubicin Complexes for Cancer Therapy

In the latest years, innovative nanomaterials have attracted a dramatic and exponentially increasing interest, in particular for their potential applications in the biomedical field. In this paper, we reported our findings on the cytocompatibility of barium titanate nanoparticles (BTNPs), an extremely interesting ceramic material. A rational and systematic study of BTNP cytocompatibility was performed, using a dispersion method based on a non-covalent binding to glycol-chitosan, which demonstrated the optimal cytocompatibility of this nanomaterial even at high concentration (100 μg/ml). Moreover, we showed that the efficiency of doxorubicin, a widely used chemotherapy drug, is highly enhanced following the complexation with BTNPs. Our results suggest that innovative ceramic nanomaterials such as BTNPs can be realistically exploited as alternative cellular nanovectors.     

One-step synthesis of nanograss-free TiO2 nanotubes using DTPA-enriched electrolytes

A single-step anodic fabrication of TiO₂ nanotubes (TNT) without a surface layer of nanograss was attained in electrolytes containing diethylenetriamine-pentaaceticacid (DTPA) as chelating agent. The role of DTPA concentration and anodization voltage on the final TNT morphology was studied. We discuss chemical aspects of the DTPA effect over the surface of TNTs as well as the physical properties of TNT samples prepared under several anodization conditions. We demonstrate that the DTPA concentration has a significant effect on the final surface morphology of TNTs, leading to a surface free of nanograss. Furthermore, we propose a mechanism that explains this phenomenon.     

On how Pachycondyla apicalis ants suggest a new search algorithm

In this paper we present a new optimization algorithm based on a model of the foraging behavior of a population of primitive ants (Pachycondyla apicalis). These ants are characterized by a relatively simple but efficient strategy for prey search in which individuals hunt alone and try to cover a given area around their nest. The ant colony search behavior consists of a set of parallel local searches on hunting sites with a sensitivity to successful sites. Also, their nest is periodically moved. Accordingly, the proposed algorithm performs parallel random searches in the neighborhood of points called hunting sites. Hunting sites are created in the neighborhood of a point called nest. At constant intervals of time the nest is moved, which corresponds to a restart operator which re-initializes the parallel searches. We have applied this algorithm, called API, to numerical optimization problems with encouraging results.     

Activation of microglial cells by PrP and beta-amyloid fragments raises intracellular calcium through L-type voltage sensitive calcium channels

The prion protein (PrP) and the amyloid beta (Abeta) precursor protein (APP) are two normal proteins constitutively synthesised in human brain. An altered form of PrP accumulates in Creutzfeldt-Jakob disease, while Abeta is involved in the pathogenesis of Alzheimer's disease. Synthetic fragments of both proteins, PrP106-126 and beta25-35 (beta25-35), have been demonstrated to induce neurodegeneration and microglia activation. This study was undertaken to compare PrP106-126 and beta25-35 capability of activating human resting microglial cells. Our results show that both peptides are able to induce microglial activation and to elicit an increase in [Ca2+]i levels in cells loaded with calcium-green 1. Inhibitors of L-type voltage-sensitive calcium channels (verapamil, nifedipine and diltiazem) prevented the increase in [Ca2+]i concentration as observed after treatment with PrP106-126 and beta25-35, thus indicating a transmembrane calcium influx through these channels. In addition, verapamil abolished the proliferative effect of both PrP106-126 and beta25-35.