Versatility of the dipolar filter selection: from 1H nuclear spin diffusion experiment to the measurement of nuclear Overhauser effect in homopolymer melts

Dipolar filters select ¹H magnetization according to local dipolar dephasing, which corresponds to site mobility in systems with heterogeneous molecular mobility. Combined with a conventional exchange experiment, it is usually applied to polymeric samples exhibiting structures on the nanometer length scale associated with a strong dynamic contrast. There, the resulting ¹H nuclear spin diffusion experiment yields the size of the structure. When the same experiment is applied to homopolymer melts exhibiting a weak dynamic contrast and dynamic heterogeneities on significant shorter length scales, the recorded magnetization decay is in agreement with decays expected from a heterogeneous nanostructure. However, dipolar filters actually can also select mobile parts of the repeat unit, e.g. the end of the alkyl side chains and the subsequent magnetization transfer then can occur via cross relaxation due to non coherent zero-quantum transitions (nuclear Overhauser effect, NOE). The difficulties of distinguishing these two cases are examined and it is demonstrated that NOE experiments exploiting magnetization selection via the dipolar filter allow quantifying the local dynamics of the side chains. This opens new possibilities for measurements of local dynamics in non isotopically labeled homopolymer melts.     

Uptake of silver nanoparticles by monocytic THP-1 cells depends on particle size and presence of serum proteins

Human health risks by silver nanoparticle (AgNP) exposure are likely to increase due to the increasing number of NP-containing products and demonstrated adverse effects in various cell lines. Unfortunately, results from (toxicity) studies are often based on exposure dose and are often measured only at a fixed time point. NP uptake kinetics and the time-dependent internal cellular concentration are often not considered. Macrophages are the first line of defense against invading foreign agents including NPs. How macrophages deal with the particles is essential for potential toxicity of the NPs. However, there is a considerable lack of uptake studies of particles in the nanometer range and macrophage-like cells. Therefore, uptake rates were determined over 24 h for three different AgNPs sizes (20, 50 and 75 nm) in medium with and without fetal calf serum. Non-toxic concentrations of 10 ng Ag/mL for monocytic THP-1 cells, representing realistic exposure concentration for short-term exposures, were chosen. The uptake of Ag was higher in medium without fetal calf serum and showed increasing uptake for decreasing NP sizes, both on NP mass and on number basis. Internal cellular concentrations reached roughly 32/10 %, 25/18 % and 21/15 % of the nominal concentration in the absence of fetal calf serum/with fetal calf serum for 20-, 50- and 75-nm NPs, respectively. Our research shows that uptake kinetics in macrophages differ for various NP sizes. To increase the understanding of the mechanism of NP toxicity in cells, the process of uptake (timing) should be considered.