Ionic Liquid-Based Microemulsions in Catalysis

The design and properties of surface-active ionic liquids that are able to form stable microemulsions with heptane and water are presented, and their promise as reaction media for thermomorphic palladium-catalyzed cross-coupling reactions is demonstrated

Nonspecific Colloidal-Type Interaction Explains Size-Dependent Specific Binding of Membrane-Targeted Nanoparticles

Emerging biomedical applications such as molecular imaging and drug delivery often require directed binding of nanoparticles to cell-membrane receptors. The specific apparent affinity of such ligand-functionalized particles is size-dependent, an observation so far solely attributed to multivalent receptor ligand interaction. We question the universality of this explanation by demonstrating that the binding kinetics also depends on weak, attractive colloidal-type interaction between nanoparticles and a lipid membrane. Applying label-free single-particle imaging, we correlate binding of nanoparticles targeted to a cell-mimetic lipid membrane with the distribution of nontargeted particles freely diffusing close to the membrane interface. This analysis shows that already a weak, k(B) T-scale attraction present between 50 nm gold nanoparticles and the membrane renders these particles an order of magnitude higher avidity compared to 20 nm particles. A stronger emphasis on nonspecific particle membrane interaction might thus be required to accurately predict nanoparticle targeting and other similar processes such as cellular uptake of exosomes and viruses

GSTM1, GSTT1 and GSTP1 gene polymorphism in polymorphous light eruption.

Background  Polymorphous light eruption (PLE) is the most common chronic and idiopathic photodermatosis. PLE is assumed to represent an immunological hypersensitivity reaction to a radiation-induced cutaneous antigen involving reactive oxygen species (ROS) on the basis of a genetic predisposition. Among others, cellular protection against ROS is provided by glutathione S-transferases (GSTs). Different variants of the GST enzymes may influence the activity and efficiency of detoxification and biotransformation of unknown UV-induced skin-antigens and other factors that may play an important role in the pathogenesis of PLE. Methods  In this study the relationship between isoenzymes of the GST genes GSTM1, GSTT1 and GSTP1 and possible protective or predisposing effects on PLE was examined in 29 patients and 144 controls. Diagnosis of PLE was based on the presence of characteristic clinical features. Results  No association between the functional polymorphisms of the GST gene family and PLE was found. Prevalence of certain GST isoenzymes or polymorphisms in patients with PLE did not differ from healthy controls. Conclusion  Our data do not support prevalence of GST isoenzymes or polymorphisms as a protective effect against PLE. Especially a higher carrier frequency of GSTP1 Val(105) as a protective factor against PLE which has been published before could not be proved. The GST genotypes GSTM1, GSTT1 and GSTP1 (including SNPs) seem to have no relevant association with PLE

Papular-purpuric gloves and socks syndrome.

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Theoretical and Experimental Design of Heavy Metal-Mopping Magnetic Nanoparticles

Herein, we show a comprehensive experimental, theoretical, and computational study aimed at designing macromolecules able to adsorb a cargo at the nanoscale. Specifically, we focus on the adsorption properties of star diblock copolymers, i.e., macromolecules made by a number f of H-T diblock copolymer arms tethered on a central core; the H monomeric heads, which are closer to the tethering point, are attractive toward a specific target, while the T monomeric tails are neutral to the cargo. Experimentally, we exploited the adaptability of poly(2-oxazoline)s (POxs) to realize block copolymer-coated nanoparticles with a proper functionalization able to interact with heavy metals and show or exhibit a thermoresponsive behavior in aqueous solution. We here present the synthesis and analysis of the properties of a high molecular mass block copolymer featured by (i) a polar side chain, capable of exploiting electrostatic and hydrophilic interaction with a predetermined cargo, and (ii) a thermoresponsive scaffold, able to change the interaction with the media by tuning the temperature. Afterward, the obtained polymers were grafted onto iron oxide nanoparticles and the thermoresponsive properties were investigated. Through isothermal titration calorimetry, we then analyzed the adsorption properties of the synthesized superparamagnetic nanoparticles for heavy metal ions in aqueous solution. Additionally, we use a combination of scaling theories and simulations to link equilibrium properties of the system to a prediction of the loading properties as a function of size ratio and effective interactions between the considered species. The comparison between experimental results on adsorption and theoretical prediction validates the whole design process

Core-Shell Structure of Monodisperse Poly(ethylene glycol)-Grafted Iron Oxide Nanoparticles Studied by Small-Angle X-ray Scattering

The promising applications of core-shell nanoparticles in the biological and medical field have been well investigated in recent years. One remaining challenge is the characterization of the structure of the hydrated polymer shell. Here we use small-angle X-ray scattering (SAXS) to investigate iron oxide core-poly(ethylene glycol) brush shell nanoparticles with extremely high polymer grafting density. It is shown that the shell density profile can be described by a scaling model that takes into account the locally very high grafting density near the core. A good fit to a constant density region followed by a star-polymer-like, monotonously decaying density profile is shown, which could help explain the unique colloidal properties of such densely grafted core-shell nanoparticles. SAXS experiments probing the thermally induced dehydration of the shell and the response to dilution confirmed that the observed features are associated with the brush and not attributed to structure factors from particle aggregates. We thereby demonstrate that the structure of monodisperse core-shell nanoparticles with dense solvated shells can be well studied with SAXS and that different density models can be distinguished from each other. (Graph Presented)

T2 signal intensity as an imaging biomarker for patients with superficial Fibromatoses of the hands (Dupuytren’s disease) and feet (Ledderhose disease) undergoing definitive electron beam irradiation

Electron beam therapy is a definitive radiation treatment option for superficial fibromatoses of the hands and feet. Because objective criteria for treatment response remain poorly defined, we sought to describe changes in electron beam treated lesions on MRI. The study included 1 male and 9 female patients with a total of 37 superficial fibromatoses; average age was 60.7 years. Standard 6 MeV electron beam treatment included 3 Gy per fraction for 10 or 12 treatments using split-course with 3-month halfway break. Pre- and post-treatment MRIs were evaluated to determine lesion size (cm3), T2 signal intensity and contrast enhancement (5-point ordinal scales) by a fellowship trained musculoskeletal radiologist. MRI findings were correlated with clinical response using a composite 1-5 ordinal scale, Karnofsky Performance Scale and patient-reported 10-point visual analog scale for pain. Mean volume decreased from 1.5 to 1.2 cm (p = 0.01, paired t-test). Mean T2 hyperintensity score decreased from 3.0 to 2.1 (p < 0.0001, Wilcoxon signed-rank). Mean enhancement score available for 22 lesions decreased from 3.8 to 3.0 (p < 0.0001, Wilcoxon signed-rank). Performance scores improved from 78.9 ± 13.7 to 84.6 ± 6.9 (p = 0.007, paired t-test). Pain scores decreased from 3.0 ± 3.3 to 1.1 ± 2.0 (p = 0.0001, paired t-test). Post-treatment T2 signal correlated weakly with performance and pain (Spearman's ρ = -0.37 and 0.16, respectively). MRI is valuable for evaluating patients undergoing electron beam therapy for superficial fibromatoses: higher pretreatment T2 intensity may predict benefit from radiotherapy. T2 hypointensity may be a better marker than size for therapeutic effect