Highly efficient in situ oxidization of metal ions in porous media with high power laser.

Metal ions in ground are hard to remove and constitute a serious environmental challenge. This paper reports a new laser-based method for in situ soil decontamination at high efficiency, in which a focused CO2 laser is used to oxidize metal contaminants from soil and fuse them with silica (base materials of soil), thus preventing undesired transport of metal ions within soil. Three types of metal ions (copper, nickel, and cadmium) adsorbed on porous silica plates are exposed to continuous laser irradiation. The lithographic mode of operation allows the accurate quantitation of laser effects. The effects of power, speed, frequency, and energy consumption on the efficiency of oxidation have been examined with high accuracy. The affected area increases with increases in laser power and decreases in scan speed and frequency. This method is promising for large scale in situ soil recovery due to high efficient oxidation of metal ions by high power laser.

Decreased bacterial growth on titanium nanoscale topographies created by ion beam assisted evaporation.

Titanium is one of the most widely used materials for orthopedic implants, yet it has exhibited significant complications in the short and long term, largely resulting from poor cell-material interactions. Among these many modes of failure, bacterial infection at the site of implantation has become a greater concern with the rise of antibiotic-resistant bacteria. Nanostructured surfaces have been found to prevent bacterial colonization on many surfaces, including nanotextured titanium. In many cases, specific nanoscale roughness values and resulting surface energies have been considered to be "bactericidal"; here, we explore the use of ion beam evaporation as a novel technique to create nanoscale topographical features that can reduce bacterial density. Specifically, we investigated the relationship between the roughness and titanium nanofeature shapes and sizes, in which smaller, more regularly spaced nanofeatures (specifically 40-50 nm tall peaks spaced ~0.25 µm apart) were found to have more effect than surfaces with high roughness values alone.

Cold atmospheric plasma (CAP) surface nanomodified 3D printed polylactic acid (PLA) scaffolds for bone regeneration.

Three-dimensional (3D) printing is a new fabrication method for tissue engineering which can precisely control scaffold architecture at the micron-scale. However, scaffolds not only need 3D biocompatible structures that mimic the micron structure of natural tissues, they also require mimicking of the nano-scale extracellular matrix properties of the tissue they intend to replace. In order to achieve this, the objective of the present in vitro study was to use cold atmospheric plasma (CAP) as a quick and inexpensive way to modify the nano-scale roughness and chemical composition of a 3D printed scaffold surface. Water contact angles of a normal 3D printed poly-lactic-acid (PLA) scaffold dramatically dropped after CAP treatment from 70±2° to 24±2°. In addition, the nano-scale surface roughness (Rq) of the untreated 3D PLA scaffolds drastically increased (up to 250%) after 1, 3, and 5min of CAP treatment from 1.20nm to 10.50nm, 22.90nm, and 27.60nm, respectively. X-ray photoelectron spectroscopy (XPS) analysis showed that the ratio of oxygen to carbon significantly increased after CAP treatment, which indicated that the CAP treatment of PLA not only changed nano-scale roughness but also chemistry. Both changes in hydrophilicity and nano-scale roughness demonstrated a very efficient plasma treatment, which in turn significantly promoted both osteoblast (bone forming cells) and mesenchymal stem cell attachment and proliferation. These promising results suggest that CAP surface modification may have potential applications for enhancing 3D printed PLA bone tissue engineering materials (and all 3D printed materials) in a quick and an inexpensive manner and, thus, should be further studied. STATEMENT OF SIGNIFICANCE: Three-dimensional (3D) printing is a new fabrication method for tissue engineering which can precisely control scaffold architecture at the micron-scale. Although their success is related to their ability to exactly mimic the structure of natural tissues and control mechanical properties of scaffolds, 3D printed scaffolds have shortcomings such as limited mimicking of the nanoscale extracellular matrix properties of the tissue they intend to replace. In order to achieve this, the objective of the present in vitro study was to use cold atmospheric plasma (CAP) as a quick and inexpensive way to modify the nanoscale roughness and chemical composition of a 3D printed scaffold surface. The results indicated that using CAP surface modification could achieve a positive change of roughness and surface chemistry. Results showed that both hydrophilicity and nanoscale roughness changes to these scaffolds after CAP treatment played an important role in enhancing bone cell and mesenchymal stem cell attachment and functions. More importantly, this technique could be used for many 3D printed polymer-based biomaterials to improve their properties for numerous applications.

Understanding the Role of Polymer Surface Nanoscale Topography on Inhibiting Bacteria Adhesion and Growth.

Catheter-associated infections, most of which are caused by microbial biofilms, are still a serious issue in healthcare and are associated with significant morbidity, mortality, and excessive medical costs. Currently, the use of nanostructured materials, especially materials with nanofeatured topographies, which have more surface area, altered surface energy, enhanced select protein adsorption, and selectively increased desirable cell functions while simultaneously decreasing competitive cell functions, seem to be among the most promising ways for reducing initial bacteria attachment, biofilm formation, and infections. In this study, polydimethylsiloxane (PDMS), a commonly used polymeric catheter material, was formulated to mimic the nanopatterned topography of natural tissue by using a template method with nanotubular anodized titanium. Results showed that increased PDMS surface nanoscale roughness alone can inhibit both Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) bacteria adhesion and growth for up to 2 days, the time length of the current study. Additionally, increased fibroblast and endothelial cell adhesion on nano-PDMS indicated that this nanoscale topography had no toxic effects toward mammalian cells. Mechanistically, this study also developed a model for the first time to correlate bacteria responses to nanoscale roughness with initial protein and biomolecule adsorption (specifically, casein protein and glucose, which are unique biomolecules that mediate bacteria functions). Data revealed that the increase in nanoscale roughness and associated energy contributed to greater select casein adsorption during the first several minutes of culture, which is critical for decreasing bacteria attachment and growth. In contrast, no significant differences for glucose adsorption between samples before and after nanofabrication were identified. These results together indicated that the present biomimetic nanopatterned PDMS surface without any chemical or antibiotic modification has the potential to combat catheter-associated infections and should be further investigated.

Large-area preparation of high-quality and uniform three-dimensional graphene networks through thermal degradation of graphene oxide-nitrocellulose composites.

We demonstrate a simple method to prepare high-quality and uniform three-dimensional (3D) graphene networks through thermal degradation of graphene oxide (GO)-nitrocellulose composites over a large area. The nitrocellulose simultaneously acts as a support and aids in the reduction of GO by exothermic decomposition. The graphene networks have tunable porous morphology where the pore size can be controlled by adjusting the concentration of GO in the composite. This new technique is a very simple method to obtain 3D graphene networks and has the potential to produce 3D graphene-modified substrates for use in energy storage and conversion applications, in supporting frameworks of catalyst, and in sensors. In this report, the prepared 3D graphene networks were directly used as the electrodes of supercapacitors without using a binding agent and/or conducting additive with a high specific capacitance of 162.5 F g(-1) at 0.5 A g(-1) current density.

pH-Dependent Activity of Dextran-Coated Cerium Oxide Nanoparticles on Prohibiting Osteosarcoma Cell Proliferation.

Cerium oxide nanoparticles (or nanoceria) have demonstrated great potential as antioxidants in various cell culture models. Despite such promise for reducing reactive oxygen species and an ability for surface functionalization, nanoceria has not been extensively studied for cancer applications to date. Herein, we engineered the surface of nanoceria with dextran and observed its activity in the presence bone cancer cells (osteosarcoma cells) at different pH values resembling the cancerous and noncancerous environment. We found that dextran coated nanoceria was much more effective at killing bone cancer cells at slightly acidic (pH 6) compared to physiological and basic pH values (pH 7 and pH 9). In contrast, minimal toxicity was observed for healthy (noncancerous) bone cells when cultured with nanoceria at pH = 6 after 1 day of treatment in the concentration range of 10-1000 µg/mL. Although healthy bone cancer cell viability decreased after treatment with high ceria nanoparticle concentrations (250-1000 µg/mL) for longer time periods at pH 6 (3 days and 5 days), approximately 2-3 fold higher healthy bone cell viabilities were observed compared to osteosarcoma cell viability at similar conditions. Very low toxicity was observed for healthy osteoblasts cultured with nanoceria for any concentration at any time period at pH 7. In this manner, this study provides the first evidence that nanoceria can be a promising nanoparticle for treating bone cancer without adversely affecting healthy bone cells and thus deserves further investigation.

Gold nanoparticle-M2e conjugate coformulated with CpG induces protective immunity against influenza A virus.

AIM: This study aimed to develop a novel influenza A vaccine by conjugating the highly conserved extracellular region of the matrix 2 protein (M2e) of influenza A virus to gold nanoparticles (AuNPs) and to test the vaccine in a mouse influenza challenge model. MATERIALS & METHODS: Citrate-reduced AuNPs (diameter: 12 nm) were synthesized, and characterized by transmission electron microscopy and dynamic light scattering. M2e was conjugated to AuNPs through thiol-gold interactions to form M2e-AuNP conjugates. Particle stability was confirmed by UV-visible spectra, and M2e conjugation was further characterized by x-ray photoelectron spectroscopy. Mice were immunized with M2e-AuNPs with or without CpG (cytosine-guanine rich oligonucleotide) as an adjuvant with appropriate control groups. Sera was collected and M2e-specific immunoglobulin (IgG) was measured, and immunized mice were challenged with PR8-H1N1 influenza virus. RESULTS: M2e-capped AuNPs could be lyophilized and stably resuspended in water. Intranasal vaccination of mice with M2e-AuNP conjugates induced M2e-specific IgG serum antibodies, which significantly increased upon addition of soluble CpG as adjuvant. Upon challenge with lethal PR8, mice vaccinated with M2e-AuNP conjugates were only partially protected, while mice that received soluble CpG as adjuvant in addition to M2e-AuNP were fully protected. CONCLUSION: Overall, this study demonstrates the potential of using the M2e-AuNP conjugates with CpG as an adjuvant as a platform for developing an influenza A vaccine.

Photoinitiated chemical vapor deposition of cytocompatible poly(2-hydroxyethyl methacrylate) films.

Poly(2-hydroxyethyl methacrylate) (pHEMA) is a widely utilized biomaterial due to lack of toxicity and suitable mechanical properties; conformal thin pHEMA films produced via chemical vapor deposition (CVD) would thus have broad biomedical applications. Thin films of pHEMA were deposited using photoinitiated CVD (piCVD). Incorporation of ethylene glycol diacrylate (EGDA) into the pHEMA polymer film as a crosslinker, confirmed via Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy, resulted in varied swelling and degradation behavior. 2-Hydroxyethyl methacrylate-only films showed significant thickness loss (up to 40%), possibly due to extraction of low-molecular-weight species or erosion, after 24 h in aqueous solution, whereas films crosslinked with EGDA (9.25-12.4%) were stable for up to 21 days. These results differ significantly from those obtained with plasma-polymerized pHEMA, which degraded steadily over a 21-day period, even with crosslinking. This suggests that the piCVD films differ structurally from those fabricated via plasma polymerization (plasma-enhanced CVD). piCVD pHEMA coatings proved to be good cell culture materials, with Caco-2 cell attachment and viability comparable to results obtained on tissue-culture polystyrene. Thus, thin film CVD pHEMA offers the advantage of enabling conformal coating of a cell culture substrate with tunable properties depending on method of preparation and incorporation of crosslinking agents.

Dynamically stabilized growth of polar oxides: the case of MgO(111).

By using MgO(111) as a model system for polar oxide film growth, we show by first-principles calculations that H acts as a surfactant, i.e., the H changes its position and bonding during the growth process, remaining in the surface region. Continuous presence of H during the growth of MgO(111) film efficiently removes the microscopic dipole moment, thus enabling the growth of perfect fcc-ordered MgO(111) films. These theoretical predictions are confirmed experimentally by molecular beam epitaxy single crystal growth of MgO(111) on SiC(0001).

Biocompatibility of plasma enhanced chemical vapor deposited poly(2-hydroxyethyl methacrylate) films for biomimetic replication of the intestinal basement membrane.

It is recognized that topographical features such as ridges and grooves can dramatically influence cell phenotype, motivating the development of substrates with precisely biomimetic topography for study of the influence on cultured cells. Intestinal basement membrane topography has been precisely replicated using plasma enhanced chemical vapor deposition (CVD) of poly(2-hydroxyethyl methacrylate) (pHEMA) on native tissue. The ability for CVD pHEMA to coat and retain the complex architecture of the intestinal basement membrane at the micrometer scale was demonstrated using electron microscopy and surface chemical analysis (XPS). The suitability of CVD pHEMA as a cell culture substrate was assessed. Caco-2 cells maintained a high (>85%) viability on CVD pHEMA. Cell attachment and proliferation on CVD pHEMA were similar to those observed on materials traditionally used for cell culture and microfabrication purposes. Results indicate that CVD pHEMA is useful for development of precise (micrometer-scale) topographically biomimetic substrates for cell culture.

Chemical and physical modifications to poly(dimethylsiloxane) surfaces affect adhesion of Caco-2 cells.

Polydimethylsiloxane (PDMS) silicone elastomer is extensively used in soft lithography processes to fabricate microscale or nano scale systems for microfluidic or cell culture applications. Though PDMS is biocompatible, it is not an ideal material for cell culture due to its poor cell adhesion properties. In this study, PDMS surfaces were modified to promote intestinal cell adhesion, in the interest of testing feasibility of using microfabricated PDMS systems for high throughput drug screening. Modification techniques included changing chemical composition of PDMS (i.e., varying curing to mixing agent ratio, and oxidization of PDMS surface by oxygen plasma), surface treatment of PDMS by coating with charged molecules (i.e., poly-D-lysine, L-alpha-phosphatidylcholine, and a layer bylayer coating), and deposition of extracellular matrix (ECM) proteins (i.e., laminin, fibronectin, and collagen). The influence of these modifications on PDMS properties, including elastic modulus and surface properties (wettability, chemical composition, topography, and protein adsorption) were characterized. Modification techniques were all found to change PDMS properties and influence the attachment and proliferation of Caco-2 cells over three days of culture to varying degrees. Generally, Caco-2 cells preferred to attach on collagen-coated, fibronectin-coated, and fibronectin-coated oxygen-plasma treated PDMS. The results highlight the importance of considering multiple physical and chemical factors that may be influenced by biomaterial modification and result in altered cell attachment to microfabricated systems, including surface hydrophobicity, chemical composition, stiffness, and topography. This study provides a foundation for further miniaturization, utilizing soft lithography techniques, of Caco-2 cell-based system for high-throughput screening of drug intestinal absorption during lead optimization in drug discovery. The understanding of different surface modifications on adjusting cell adhesion on PDMS allows systemic design of Biomicroelectromechanical Systems (BioMEMS) with tunable cell adhesion properties.

Cross-Linking and Degradation Properties of Plasma Enhanced Chemical Vapor Deposited Poly(2-hydroxyethyl methacrylate).

Plasma Enhanced Chemical Vapor Deposition (PECVD) of poly-2-hydroxyethyl methacrylate (pHEMA) biocompatible, biodegradable polymer films were produced alone and cross-linked with ethylene glycol diacrylate (EGDA). Degree of cross-linking was controlled via manipulation of the EGDA flow rate, which influenced the amount of swelling and the extent of degradation of the films in an aqueous solution over time. Noncross-linked pHEMA films swelled 10% more than cross-linked films after 24 h of incubation in an aqueous environment. Increasing degree of film cross-linking decreased degradation over time. Thus, PECVD pHEMA films with variable cross-linking properties enable tuning of gel formation and degradation properties, making these films useful in a variety of biologically significant applications.