The ROS-generating photosensitizer-free NaYF4:Yb,Tm@SiO2upconverting nanoparticles for photodynamic therapy application.

In this work we adapt rare-earth-ion-doped NaYF4nanoparticles coated with a silicon oxide shell (NaYF4:20%Yb,0.2%Tm@SiO2) for biological and medical applications (for example, imaging of cancer cells and therapy at the nano level). The wide upconversion emission range under 980 nm excitation allows one to use the nanoparticles for cancer cell (4T1) photodynamic therapy (PDT) without a photosensitizer. The reactive oxygen species (ROS) are generated by Tm/Yb ion upconversion emission (blue and UV light). Thein vitroPDT was tested on 4T1 cells incubated with NaYF4:20%Yb,0.2%Tm@SiO2nanoparticles and irradiated with NIR light. After 24 h, cell viability decreased to below 10%, demonstrating very good treatment efficiency. High modification susceptibility of the SiO2shell allows for attachment of biological molecules (specific antibodies). In this work we attached the anti-human IgG antibody to silane-PEG-NHS-modified NaYF4:20%Yb,0.2%Tm@SiO2nanoparticles and a specifically marked membrane model by bio-conjugation. Thus, it was possible to perform a selective search (a high-quality optical method with a very low-level organic background) and eventually damage the targeted cancer cells. The study focuses on therapeutic properties of NaYF4:20%Yb,0.2%Tm@SiO2nanoparticles and demonstrates, upon biological functionalization, their potential for targeted therapy.

Nutrient loss from three small-size watersheds in the southern Baltic Sea in relation to agricultural practices and policy.

Agriculture is the major contributor of waterborne nutrient fluxes into the Baltic Sea, one of the world's most eutrophication-sensitive areas. Poland, as a large, densely populated state ohf the Baltic Region, with dominating agricultural land use, largely contributes to riverborne loads of N and P. The aim of our study was to examine the input of nutrients from three small first-order agricultural watersheds (Bladzikowski Stream, Gizdepka river and Mrzezino canal) in the Pomerania region, into the Bay of Puck, inner part of the Gulf of Gdansk. This study attempts to give a partial answer as to the question if inputs of nutrients from the 3 analysed watersheds comply with the targets of the Baltic Sea Action Plan (BSAP) and Country Allocated Reduction Targets (CART). The impact of agricultural practices was assessed on the basis of farm questionnaires and calculations of nutrient balances for the examined farms. The nutrient concentrations in the soil and drainage ditches were examined, followed by an assessment of nutrient concentrations in the watercourses at the sampling points located close to the estuaries. The average mineral N fertiliser consumption (109 kg N/ha) in the analysed watersheds was higher than Poland's average. The average N and P surpluses for surveyed farms (96.4 kg/ha and 4.4 kg/ha, respectively) were higher than the EU mean in case of N and markedly lower in case of P. We used Principal Component Analysis which confirmed that there were correlations between nutrient surpluses and nutrient concentrations in streams and/or drainage ditches. The N-NO3 and Pmin concentrations were also correlated to precipitation. The average N concentrations in the analysed watercourses were equal to 1.53 mg/L for Gizdepka, 1.88 mg/L for Mrzezino canal and 3.52 mg/L for Bladzikowski Stream. The mean P concentrations observed in the investigated watercourses were markedly higher than 0.1 mg/L. With regard to BSAP objectives, as well as CART set for Poland, the average nutrient concentrations in rivers should be approximately at the level of 2.5 mg N/L and 0.07 mg P/L.

Synthesis, characterization and application of plasmonic hollow gold nanoshells in a photothermal therapy-New particles for theranostics.

This article describes the work on synthesis, surface functionalization and characterization of hollow gold nanoshells (HGNs), and their application in a photothermal tumor therapy. The studied gold nanoshells were synthesized using a method based on a reduction of HAuCl4 onto silver nanoparticle templates. A selected aptamer - AS1411 - selective towards nucleolin, with a terminal thiol group was conjugated to HGNs. Surface functionalization of synthesized nanoparticles was necessary to gain the affinity to tumor cells, thus allowing the selective delivery of the modified nanoparticles to target cells. As expected, an increased selectivity of nanoconjugates towards tumor cells (A375) in a comparison to normal ones (HaCaT) was observed (2.67 times). In the framework of our studies the biological activity of the obtained nanoconjugates was evaluated using MTT assay. For this aim, both normal and tumor cell cultures respresenting skin tissue were exposed to gold nanoparticles solutions. It was found, that HGN-AS1411 conjugates cause less than 10% loss in a cell viability in the case of both cell lines at the highest tested concentration. The potential of the developed nanoconjugates as agents in PTT of skin cancer was investigated in a subsequent stage of our research. It was found, that A375 cell viability amounted to less than 40% for 75µM of nanoconjugates (expressed as a concentration of Au atoms) as a result of the laser irradiation of this cell culture after desired accumulation of the tested nanoconjugates inside A375 cells.