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Substrate-induced self-assembly of donor-acceptor type compounds with terminal thiocarbonyl groups
(2013)
Two types of conjugated thiocarbonyl-terminated compounds have been synthesized and their ability to be adsorbed on surfaces of the different nature, namely, glass, polytetrafluoroethylene (PTFE), and gold has been studied. Different morphology of the films prepared by thermal vacuum evaporation and drop-casting from solutions has been observed depending on the surface used. It has been found that gold surface has a unique property to influence self-assembly of both monolayer and larger aggregates or crystals of the compounds, in contrast to glass and PTFE substrates. It was found that thiocarbonyl group is able to be chemisorbed to the gold surface. However, it was concluded that in spite of the fact that the thiocarbonyl groups are important for the chemical interaction with the gold surface, physical adsorption on the substrate surface, compoundcompound and compound–solvent (when using solution) interactions are of great significance to drive self-assembly of the final film.
To investigate the imaging performance of an elastin-specific molecular magnetic resonance imaging (MRI) probe with respect to the extracellular matrix (ECM) in an experimental hepatic cancer model. Twelve rabbits with hepatic VX2 tumors were examined using 3 T MRI 14, 21, and 28 days after tumor implantation for two subsequent days (gadobutrol, day 1; elastin-specific probe, day 2). The relative enhancement (RE) of segmented tumor regions (central and margin) and the peritumoral matrix was calculated using pre-contrast and delayed-phase T1w sequences. MRI measurements were correlated to histopathology and element-specific and spatially resolved mass spectrometry (MS). Mixed-model analysis was performed to assess the performance of the elastin-specific probe. In comparison to gadobutrol, the elastin probe showed significantly stronger RE, which was pronounced in the tumor margin (day 14–28: P ≤ 0.007). In addition, the elastin probe was superior in discriminating between tumor regions (χ2(4) = 65.87; P < 0.001). MRI-based measurements of the elastin probe significantly correlated with the ex vivo elastinstain (R = .84; P <0 .001) and absolute gadolinium concentrations (ICP-MS: R = .73, P <0 .01). LA-ICP-MS imaging confirmed the colocalization of the elastin-specific probe with elastic fibers. Elastin-specific molecular MRI is superior to non-specific gadolinium-based contrast agents in imaging the ECM of hepatic tumors and the peritumoral tissue.
Terrestrial mud volcanoes are unique structures driven by tectonic pressure and fluids from the deep subsurface. These structures are mainly found in active tectonic zones, such as the area near the Los Bajos Fault in Trinidad. Here we report a chemical and microbiological characterization of three mud volcanoes, which included analyses of multiple liquid and solid samples from the mud volcanoes. Our study confirms previous suggestions that at least some of the mud volcano fluids are a mixture of deeper salt-rich water and surficial/precipitation water. No apparent water quality differences were found between sampling sites north and south of a major geological fault line. Microbiological analyses revealed diverse communities, both aerobic and anaerobic, including sulfate reducers, methanogens, carbon dioxide fixing and denitrifying bacteria. Several identified species were halophilic and likely derived from the deeper salt-rich subsurface water, while we also cultivated pathogenic species from the Vibrionaceae, Enterobacteriaceae, Shewanellaceae, and Clostridiaceae. These microorganisms were likely introduced into the mud volcano fluids both from surface water or shallow ground-water, and perhaps to a more minor degree by rain water. The identified pathogens are a major health concern that needs to be addressed.
Among new types of plasma processes, the underwater plasma is one of the most attractive methods for functionalization of polymer surfaces. The interesting features of plasma solution system are that the material surfaces to be modified remain in contact with the plasma-moderated solution. The role of plasma-moderated liquids, allows the reach of the reactive species through solution onto the geometrically hindered sites. The UV radiation produced in plasma formation helps in generating additional excited, ionized, and dissociated molecules and species in the reaction solution. An interesting feature of the technique is its flexibility to use a wide variety of additives as or in solution system. This allows us to create a selective or monotype functionalization of material surfaces. Such system was studied for the selective hydroxyl functionalization of polypropylene surface. The oxidation of polymer surfaces and the introduction of O-containing functional groups by underwater plasma was found to exceed concentrations typically achieved in oxygen low-pressure gas discharge plasmas up-to two-folds (maximal 56 O/100 C). The fraction of OH groups among all O-containing moieties amounts from 25 to 40% in comparison to that in the gas plasma of about 10% OH groups. Addition of hydrogen peroxide into this same system increases the fraction of C—O bonds up to 75% (27-OH/100 O). A study was focused to optimize the role of hydrogen peroxide on the efficiency of oxidation and selectivity with chemical derivatization with respect to the formation of mono-sort hydroxyl functionalities, calculated using a chemical derivatization technique.