Solution and Film Self-Assembly Behavior of a Block Copolymer Composed of a Poly(ionic Liquid) and a Stimuli-Responsive Weak Polyelectrolyte.

Cu(0)-mediated atom transfer radical polymerization was used to synthesize a poly(ionic liquid), poly[4-vinylbenzyl-3-butylimidazolium bis(trifluoromethylsulfonyl)imide] (PVBBImTf2N), a stimuli-responsive polyelectrolyte, poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA), and a novel block copolymer formed from these two polymers. The synthesis of the block copolymer, poly[2-(dimethylamino) ethyl methacrylate]-block-[poly(4-vinylbenzyl-3-butylimidazolium bis(trifluoromethylsulfonyl)imide] (PDMAEMA-b-PVBBImTf2N), was examined to evaluate the control of "livingness" polymerization, as indicated by molecular weight, characterizations of degree of polymerization, and 1HNMR spectroscopy. 2D DOSY NMR measurements revealed the successful formation of block copolymer and the connection between the two polymer blocks. PDMAEMA-b-PVBBImTf2N was further characterized for supramolecular interactions in both the bulk and solution states through FTIR and 1H NMR spectroscopies. While the block copolymer demonstrated similar intermolecular behavior to the PIL homopolymer in the bulk state as indicated by FTIR, hydrogen bonding and counterion interactions in solution were observed in polar organic solvent through 1H NMR measurements. The DLS characterization revealed that the PDMAEMA-b-PVBBImTf2N block copolymer forms a network-like aggregated structure due to a combination of hydrogen bonding between the PDMAEMA and PIL group and electrostatic repulsive interactions between PIL blocks. This structure was found to collapse upon the addition of KNO3 while still maintaining hydrogen bonding interactions. AFM-IR analysis demonstrated varied morphologies, with spherical PDMAEMA in PVBBImTf2N matrix morphology exhibited in the region approaching the film center. AFM-IR further revealed signals from silica nano-contaminates, which selectively interacted with the PDMAEMA spheres, demonstrating the potential for the PDMAEMA-b-PVBBImTf2N PIL block copolymer in polymer-inorganic nanoparticle composite applications.

Chemically Edge-Carboxylated Graphene Enhances the Thermal Conductivity of Polyetherimide-Graphene Nanocomposites.

In this work, we demonstrate that edge oxidation of graphene can enable larger enhancement in thermal conductivity (k) of graphene nanoplatelet (GnP)/polyetherimide (PEI) composites relative to oxidation of the basal plane of graphene. Edge oxidation offers the advantage of leaving the basal plane of graphene intact, preserving its high in-plane thermal conductivity (kin > 2000 W m-1 K-1), while, simultaneously, the oxygen groups introduced on the graphene edge enhance interfacial thermal conductance through hydrogen bonding with oxygen groups of PEI, enhancing the overall polymer composite thermal conductivity. Edge oxidation is achieved in this work by oxidizing graphene in the presence of sodium chlorate and hydrogen peroxide, thereby introducing an excess of carboxyl groups on the edge of graphene. Basal plane oxidation of graphene, on the other hand, is achieved through the Hummers method, which distorts the sp2 carbon-carbon network of graphene, dramatically lowering its intrinsic thermal conductivity, causing the BGO/PEI (BGO = basal-plane oxidized graphene or basal-plane-functionalized graphene oxide) composite's k value to be even lower than pristine GnP/PEI composite's k value. The resulting thermal conductivity of the EGO/PEI (EGO = edge-oxidized graphene or edge-functionalized graphene oxide) composite is found to be enhanced by 18%, whereas that of the BGO/PEI composite is diminished by 57%, with respect to the pristine GnP/PEI composite with 10 wt % GnP content. Two-dimensional Raman mapping of GnPs is used to confirm and distinguish the location of oxygen functional groups on graphene. The superior effect of edge bonding presented in this work can lead to fundamentally novel pathways for achieving high thermal conductivity polymer composites.

Mesoporous Silica Nanoparticles: Properties and Strategies for Enhancing Clinical Effect.

Due to the theragnostic potential of mesoporous silica nanoparticles (MSNs), these were extensively investigated as a novel approach to improve clinical outcomes. Boasting an impressive array of formulations and modifications, MSNs demonstrate significant in vivo efficacy when used to identify or treat myriad malignant diseases in preclinical models. As MSNs continue transitioning into clinical trials, a thorough understanding of the characteristics of effective MSNs is necessary. This review highlights recent discoveries and advances in MSN understanding and technology. Specific focus is given to cancer theragnostic approaches using MSNs. Characteristics of MSNs such as size, shape, and surface properties are discussed in relation to effective nanomedicine practice and projected clinical efficacy. Additionally, tumor-targeting options used with MSNs are presented with extensive discussion on active-targeting molecules. Methods for decreasing MSN toxicity, improving site-specific delivery, and controlling release of loaded molecules are further explained. Challenges facing the field and translation to clinical environments are presented alongside potential avenues for continuing investigations.

Chemical and Microstructural Characterization of pH and [Ca2+] Dependent Sol-Gel Transitions in Mucin Biopolymer.

Mucus is responsible for controlling transport and barrier function in biological systems, and its properties can be significantly affected by compositional and environmental changes. In this study, the impacts of pH and CaCl2 were examined on the solution-to-gel transition of mucin, the primary structural component of mucus. Microscale structural changes were correlated with macroscale viscoelastic behavior as a function of pH and calcium addition using rheology, dynamic light scattering, zeta potential, surface tension, and FTIR spectroscopic characterization. Mucin solutions transitioned from solution to gel behavior between pH 4-5 and correspondingly displayed a more than ten-fold increase in viscoelastic moduli. Addition of CaCl2 increased the sol-gel transition pH value to ca. 6, with a twofold increase in loss moduli at low frequencies and ten-fold increase in storage modulus. Changing the ionic conditions-specifically [H+] and [Ca2+] -modulated the sol-gel transition pH, isoelectric point, and viscoelastic properties due to reversible conformational changes with mucin forming a network structure via  non-covalent cross-links between mucin chains.

Computational and experimental approach to understanding the structural interplay of self-assembled end-terminated alkanethiolates on gold surfaces.

Applications of self-assembled monolayers (SAMs) on surfaces are prevalent in modern technologies and drives the need for a better understanding of the surface domain architecture of SAMs. To explore structural interaction at the interface between gold surfaces and a hydroxyl-terminated alkanethiol, 11-hydroxy-1-undecanethiol, (C11TH) we have employed a combined computational and experimental approach. Density functional theory (DFT) calculations were carried out on the thiol-gold interface using both the Perdew-Burke-Ernzerhof (PBE) and van der Waals (optB86b) density functionals. Our ab initio molecular dynamics (AIMD) simulations revealed that the interface consists of four different distinguished phases, each with different C11TH orientations. Experiments involved deposition of C11TH SAMs onto gold, with the resultant surfaces examined with X-ray photoelectron spectroscopy (XPS) and ellipsometry. Weighted average projected density of states (PDOS) of the different phases were photoionization cross section corrected and these were confirmed by experimental XPS data. Computed molecular parameters including tilt angles and the thickness of SAMs also agreed with the XPS and ellipsometry results. Hydrogen bonding arising from the terminal hydroxyl groups is the primary factor governing the stability of the four phases. Experimental results from XPS and ellipsometry along with DFT simulation results provide insights into the formation of the different orientations of SAM on Au(111) which will guide future efforts in the self-assembled SAMs architecture for other thiols or metal substrates.

Constant pH simulations of pH responsive polymers.

Polyacidic polymers can change structure over a narrow range of pH in a competition between the hydrophobic effect, which favors a compact state, and electrostatic repulsion, which favors an extended state. Constant pH molecular dynamics computer simulations of poly(methacrylic acid) reveal that there are two types of structural changes, one local and one global, which make up the overall response. The local structural response depends on the tacticity of the polymer and leads to different cooperative effects for polymers with different stereochemistries, demonstrating both positive and negative cooperativities.

Bioluminescent magnetic nanoparticles as potential imaging agents for mammalian spermatozoa.

BACKGROUND: Nanoparticles have emerged as key materials for developing applications in nanomedicine, nanobiotechnology, bioimaging and theranostics. Existing bioimaging technologies include bioluminescent resonance energy transfer-conjugated quantum dots (BRET-QDs). Despite the current use of BRET-QDs for bioimaging, there are strong concerns about QD nanocomposites containing cadmium which exhibits potential cellular toxicity. RESULTS: In this study, bioluminescent composites comprised of magnetic nanoparticles and firefly luciferase (Photinus pyralis) are examined as potential light-emitting agents for imaging, detection, and tracking mammalian spermatozoa. Characterization was carried out using infrared spectroscopy, TEM and cryo-TEM imaging, and ζ-potential measurements to demonstrate the successful preparation of these nanocomposites. Binding interactions between the synthesized nanoparticles and spermatozoon were characterized using confocal and atomic/magnetic force microscopy. Bioluminescence imaging and UV-visible-NIR microscopy results showed light emission from sperm samples incubated with the firefly luciferase-modified nanoparticles. Therefore, these newly synthesized luciferase-modified magnetic nanoparticles show promise as substitutes for QD labeling, and can potentially also be used for in vivo manipulation and tracking, as well as MRI techniques. CONCLUSIONS: These preliminary data indicate that luciferase-magnetic nanoparticle composites can potentially be used for spermatozoa detection and imaging. Their magnetic properties add additional functionality to allow for manipulation, sorting, or tracking of cells using magnetic techniques.

Fetuin-A adsorption and stabilization of calcium carbonate nanoparticles in a simulated body fluid.

Fetuin-A is a serum glycoprotein identified as a calcification inhibitor, and a key player in bone formation and human metabolic processes. A study on binding mechanisms of Fetuin-A with calcium carbonate nanoparticles in a simulated body fluid (DMEM) environment is presented. Observed interactions between Fetuin-A and the CaCO3 nanoparticles reveal an initial adsorption process, followed by a stabilization stage, and then a solubilization period for the Fetuin-A/CaCO3 complex. FTIR and XPS are used to monitor functional group and elemental composition changes during the initial adsorption process between Fetuin-A and the CaCO3 nanoparticles. Distinctive Fetuin-A/CaCO3 complex structures-also known as mineralo-protein particles-are imaged with TEM and SEM. DLS and UV-Vis methods are used to further characterize the in situ binding mechanisms. Results of this study can guide the design of complex organic-inorganic hybrid materials, improve current drug delivery methods, and provide insight in monitoring and controlling interactions between Fetuin-A and external calcium ions.

SILAC-based quantitative proteomic analysis of human lung cell response to copper oxide nanoparticles.

Copper (II) oxide (CuO) nanoparticles (NP) are widely used in industry and medicine. In our study we evaluated the response of BEAS-2B human lung cells to CuO NP, using Stable isotope labeling by amino acids in cell culture (SILAC)-based proteomics and phosphoproteomics. Pathway modeling of the protein differential expression showed that CuO NP affect proteins relevant in cellular function and maintenance, protein synthesis, cell death and survival, cell cycle and cell morphology. Some of the signaling pathways represented by BEAS-2B proteins responsive to the NP included mTOR signaling, protein ubiquitination pathway, actin cytoskeleton signaling and epithelial adherens junction signaling. Follow-up experiments showed that CuO NP altered actin cytoskeleton, protein phosphorylation and protein ubiquitination level.

Janus magnetic nanoparticles with a bicompartmental polymer brush prepared using electrostatic adsorption to facilitate toposelective surface-initiated ATRP.

Utilizing the inherent negative charge of mica surfaces, amine-functionalized magnetic nanoparticles (Fe3O4/NH2) were electrostatically adsorbed onto the mica such that surface-initiated ATRP could be used to grow poly(n-isopropylacrylamide) (PNIPAM) from the exposed hemisphere. By reducing the solution pH, a positive charge generated on the mica was used to release the nanoparticles from the substrate. A second ATRP reaction was carried out to grow poly(methacrylic acid) (PMAA) from the initiated surfaces. As a result, the Fe3O4/NH2 core has a polymer shell with one hemisphere PMAA and the other hemisphere PNIPAM-b-PMAA resulting in the PMAA-Fe3O4-PNIPAM-b-PMAA bicompartmental polymer Janus nanoparticles. Elemental and functional group compositions were confirmed using ATR-FTIR, XPS, and EDS. Imaging with AFM, SEM, and TEM showed the evolution of the Janus nanoparticle morphology. This study demonstrates a facile and innovative scheme involving a noncovalent solid protection technique combined with sequential, surface-confined controlled radical polymerizations for the production of multicomponent nanocomposites.

The effects of water and microstructure on the mechanical properties of bighorn sheep (Ovis canadensis) horn keratin.

The function of the bighorn sheep horn prompted quantification of the various parametric effects important to the microstructure and mechanical property relationships of this horn. These parameters included analysis of the stress-state dependence with the horn keratin tested under tension and compression, the anisotropy of the material structure and mechanical behavior, the spatial location along the horn, and the wet-dry horn behavior. The mechanical properties of interest were the elastic moduli, yield strength, ultimate strength, failure strain and hardness. The results showed that water has a more significant effect on the mechanical behavior of ram horn more than the anisotropy, location along the horn and the type of loading state. All of these parametric effects showed that the horn microstructure and mechanical properties were similar to those of long-fiber composites. In the ambient dry condition (10 wt.% water), the longitudinal elastic modulus, yield strength and failure strain were measured to be 4.0 G Pa, 62 MPa and 4%, respectively, and the transverse elastic modulus, yield strength and failure strain were 2.9 GPa, 37 MPa and 2%, respectively. In the wet condition (35 wt.% water), horn behaves more like an isotropic material; the elastic modulus, yield strength and failure strain were determined to be 0.6G Pa, 10 MPa and 60%, respectively.

XPS study on the use of 3-aminopropyltriethoxysilane to bond chitosan to a titanium surface.

Chitosan, a biopolymer found in the exoskeletons of shellfish, has been shown to be antibacterial, biodegradable, osteoconductive, and has the ability to promote organized bone formation. These properties make chitosan an ideal material for use as a bioactive coating on medical implant materials. In this study, coatings made from 86.4% de-acetylated chitosan were bound to implant-quality titanium. The chitosan films were bound through a three-step process that involved the deposition of 3-aminopropyltriethoxysilane (APTES) in toluene, followed by a reaction between the amine end of APTES with gluteraldehyde, and finally, a reaction between the aldehyde end of gluteraldehyde and chitosan. Two different metal treatments were examined to determine if major differences in the ability to bind chitosan could be seen. X-ray photoelectron spectroscopy (XPS) was used to examine the surface of the titanium metal and to study the individual reaction steps. The changes to the titanium surface were consistent with the anticipated reaction steps, with significant changes in the amounts of nitrogen, silicon, and titanium that were present. It was demonstrated that more APTES was bound to the piranha-treated titanium surface as compared to the passivated titanium surface, based on the amounts of titanium, carbon, nitrogen, and silicon that were present. The metal treatments did not affect the chemistry of the chitosan films. Using toluene to bond APTES on titanium surfaces, rather than aqueous solutions, prevented the formation of unwanted polysiloxanes and increased the amount of silane on the surface for forming bonds to the chitosan films. Qualitatively, the films were more strongly attached to the titanium surfaces after using toluene, which could withstand the ultrahigh vacuum environment of XPS, as compared to the aqueous solutions, which were removed from the titanium surface when exposed to the ultrahigh vacuum environment of XPS.