Evaluating UV/H 2 O 2 exposure as a DEHP degradation treatment for plasticized PVC

Millions of tons of plasticized poly(vinyl chloride) (PVC) materials are disposed every year. A biologically sustainable and green method for removal of toxic plasticizers from polymer systems after disposal is highly desired since plasticizers can leach out into the environment over decades. Here we compare the surface and bulk structural changes of DEHP‐plasticized PVC after two treatments intended to degrade bis‐2‐ethylhexyl phthalate (DEHP) in PVC plastic: short wave (254 nm) UV with and without the addition of 35 wt % H 2 O 2. Sum frequency generation vibrational spectroscopy (SFG) reveals the addition of aqueous H 2 O 2 decreases CH 3 signals on the surface of the films up to 8 h, due to increased molecular disorder and the removal of alkyl chains. Secondary ion mass spectrometry demonstrates that the degradation of DEHP after 8 h of reaction is similar with and without the use of H 2 O 2 . However, FTIR results reveal that the introduction of H 2 O 2 reduces bulk DEHP degradation and leads to competing radical chain scission reactions with PVC. Therefore, simple short wave UV exposure may be an effective means to degrade DEHP within and on PVC plastic and the addition of H 2 O 2 is only beneficial if additional degradation of PVC is needed. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131 , 40649.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/106825/1/app40649-sup-0001-suppinfo01.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/106825/2/app40649.pd

Reversible Surface Wettability by Silanization

The chemistry and wettability of oxygen containing surfaces can be conveniently modified by silanization with various organosilanes which form SiO bonds on the surface. This work shows that a superhydrophobic nanoporous polymer coating can be reverted to its previous hydrophilic state by removing the fluoroalkyl silane with fluoride anions using tetrabutyl ammonium fluoride. This leads to a completely reversible process of silanization and desilanization which can be performed in less than 2 min for each step as proven by droplet shape analysis and secondary ion mass spectrometry. Additionally, the desilanization solution can be applied spatially by an automated liquid dispenser or manually by a brush, leading to patterns with different wettability, such as droplet microarrays or liquid channels

Surface Functionalization and Patterning by Multifunctional Resorcinarenes

Plant phenolic compounds and catecholamines have been widely used to obtain substrate-independent precursor nanocoatings and adhesives. Nevertheless, there are downsides in using such phenolic compounds for surface modification such as formation of nonuniform coatings, need for multistep modification, and restricted possibilities for postfunctionalization. In this study, inspired by a strong binding ability of natural polyphenols found in plants, we used three different macrocyclic polyphenols, known as resorcin[4]­arenes, to modify the surface of different substrates by simple dip-coating into the dilute solution of these compounds. Eight hydroxyl groups on the large rim of these resorcin[4]­arenes provide multiple anchoring points to the surface, whereas the lower rim decorated with different appending groups introduces the desired chemical and physical functionalities to the substrate’s surface. Deposition of a uniform and transparent resorcinarene layer on the surface was confirmed by several surface characterization techniques. Incubation of the modified substrates in different environments indicated that the stability of the resorcinarene layer was dependent on the type of substrate and the pH value. The most stable resorcinarene layer was formed on amine-functionalized substrates. The surface was modified with alkenyl functional groups in one step using a resorcinarene compound possessing four alkenyl appending groups on its small rim. Thiol–ene photoclick chemistry was used to site-selectively postfunctionalize the surface with hydrophilic and hydrophobic micropatterns, which was confirmed by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry. Thus, we demonstrate that resorcin[4]­arenes extend the scope of applications of plant polyphenol and mussel-inspired precursors to tailor-made multifunctional nanocoatings, suitable for a variety of potential applications in biotechnology, biology, and material science

A combined high-throughput and high-content platform for unified on-chip synthesis, characterization and biological screening

Acceleration and unification of drug discovery is important to reduce the effort and cost of new drug development. Diverse chemical and biological conditions, specialized infrastructure and incompatibility between existing analytical methods with high-throughput, nanoliter scale chemistry make the whole drug discovery process lengthy and expensive. Here, we demonstrate a chemBIOS platform combining on-chip chemical synthesis, characterization and biological screening. We developed a dendrimer-based surface patterning that enables the generation of high-density nanodroplet arrays for both organic and aqueous liquids. Each droplet (among > 50,000 droplets per plate) functions as an individual, spatially separated nanovessel, that can be used for solution-based synthesis or analytical assays. An additional indium-tin oxide coating enables ultra-fast on-chip detection down to the attomole per droplet by matrix-assisted laser desorption/ionization mass spectrometry. The excellent optical properties of the chemBIOS platform allow for on-chip characterization and in-situ reaction monitoring in the ultraviolet, visible (on-chip UV-Vis spectroscopy and optical microscopy) and infrared (on-chip IR spectroscopy) regions. The platform is compatible with various cell-biological screenings, which opens new avenues in the fields of high-throughput synthesis and drug discovery

Identification of Zirconia Particle Uptake in Human Osteoblasts by ToF-SIMS Analysis and Particle-Size Effects on Cell Metabolism

As the use of zirconia-based nano-ceramics is rising in dentistry, the examination of possible biological effects caused by released nanoparticles on oral target tissues, such as bone, is gaining importance. The aim of this investigation was to identify a possible internalization of differently sized zirconia nanoparticles (ZrNP) into human osteoblasts applying Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS), and to examine whether ZrNP exposure affected the metabolic activity of the cells. Since ToF-SIMS has a low probing depth (about 5 nm), visualizing the ZrNP required the controlled erosion of the sample by oxygen bombardment. This procedure removed organic matter, uncovering the internalized ZrNP and leaving the hard particles practically unaffected. It was demonstrated that osteoblasts internalized ZrNP within 24 h in a size-dependent manner. Regarding the cellular metabolic activity, metabolization of alamarBlue by osteoblasts revealed a size- and time-dependent unfavorable effect of ZrNP, with the smallest ZrNP exerting the most pronounced effect. These findings point to different uptake efficiencies of the differently sized ZrNP by human osteoblasts. Furthermore, it was proven that ToF-SIMS is a powerful technique for the detection of zirconia-based nano/microparticles that can be applied for the cell-based validation of clinically relevant materials at the nano/micro scale

Formation of Gold Nanoclusters from Goldcarbonyl Chloride inside the Metal-Organic Framework HKUST-1

Gas-phase infiltration of the carbonylchloridogold(I), Au(CO)Cl precursor into the pores of HKUST-1 ([Cu$_3$(BTC)$_2$(H$_2$O)$_2$], Cu-BTC) SURMOFs (surface-mounted metal-organic frameworks; BTC = benzene-1,3,5-tricarboxylate) leads to Au(CO)Cl decomposition within the MOF through hydrolysis with the aqua ligands on Cu. Small Au$_x$ clusters with an average atom number of x ≈ 5 are formed in the medium-sized pores of the HKUST-1 matrix. These gold nanoclusters are homogeneously distributed and crystallographically ordered, which was supported by simulations of the powder X-ray diffractometric characterization. Au$_x$@HKUST-1 was further characterized by scanning electron microscopy (SEM) and infrared reflection absorption (IRRA) as well as Raman spectroscopy, time-of-flight secondary ion mass spectrometry (ToF-SIMS), X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma optical emission spectroscopy (ICP-OES)

Estimation of neural network model parameters from local field potentials (LFPs)

publishedVersio