Direct linkage between dimethyl sulfide production and microzooplankton grazing, resulting from prey composition change under high partial pressure of carbon dioxide conditions.

Oceanic dimethyl sulfide (DMS) is the enzymatic cleavage product of the algal metabolite dimethylsulfoniopropionate (DMSP) and is the most abundant form of sulfur released into the atmosphere. To investigate the effects of two emerging environmental threats (ocean acidification and warming) on marine DMS production, we performed a large-scale perturbation experiment in a coastal environment. At both ambient temperature and ∼ 2 °C warmer, an increase in partial pressure of carbon dioxide (pCO2) in seawater (160-830 ppmv pCO2) favored the growth of large diatoms, which outcompeted other phytoplankton species in a natural phytoplankton assemblage and reduced the growth rate of smaller, DMSP-rich phototrophic dinoflagellates. This decreased the grazing rate of heterotrophic dinoflagellates (ubiquitous micrograzers), resulting in reduced DMS production via grazing activity. Both the magnitude and sign of the effect of pCO2 on possible future oceanic DMS production were strongly linked to pCO2-induced alterations to the phytoplankton community and the cellular DMSP content of the dominant species and its association with micrograzers.

Synthesis of PAMAM dendrimer derivatives with enhanced buffering capacity and remarkable gene transfection efficiency.

In this study, we introduced histidine residues into l-arginine grafted PAMAM G4 dendrimers to enhance proton buffering capacity and evaluated the physicochemical characteristics and transfection efficacies in vitro. The results showed that the synthesized PAMAM G4 derivatives effectively delivered pDNA inside cells and the transfection level improved considerably as the number of histidine residues increased. Grafting histidine residues into the established polymer vector PAMAM G4-arginine improved their proton buffering capacity. The cytotoxicity of PAMAM G4 derivatives was tested and it was confirmed that they displayed relatively lower cytotoxicity compared to PEI25KD in various cell lines. Also, confocal microscopy results revealed that PAMAM G4 derivatives effectively delivered pDNA into cells, particularly into the nucleus. These PAMAM dendrimer derivatives conjugated with histidines and arginines may provide a promising polymeric gene carrier system.

Water-collecting capability of radial-wettability gradient surfaces generated by controlled surface reactions.

In this work, we developed a controlled oxidation reaction of vinyl-terminated self-assembled monolayers (SAMs) to carboxylic acid-terminated ones to generate radially inward wettability gradient surfaces. The hydrophobicity was introduced on a silicon wafer by SAMs of 10-undecenyltrichlorosilane, and after the initial drop in oxidation, followed by the dilution-by-dropping method, radial-wettability gradient surfaces having hydrophilic centers and hydrophobic exteriors were generated. This direct drop reaction on the SAMs did not require an elastomeric stamp to be fabricated, which allowed for facile tuning of the gradients in terms of sizes and shapes. The fabricated wettability gradient surfaces possessed a water-collecting capability toward the hydrophilic center, which was inactive on previous linear wettability gradient surfaces.

Experimental considerations on the cytotoxicity of nanoparticles.

Engineered nanoparticles are one of the leading nanomaterials currently under investigation due to their applicability in various fields, including drug and gene delivery, biosensors, cancer treatment and diagnostic tools. Moreover, the number of commercial products containing nanoparticles released on the market is rapidly increasing. Nanoparticles are already widely distributed in air, cosmetics, medicines and even in food. Therefore, the unintended adverse effect of nanoparticle exposure is a growing concern both academically and socially. In this context, the toxicity of nanoparticles has been extensively studied; however, several challenges are encountered due to the lack of standardized protocols. In order to improve the experimental conditions of nanoparticle toxicity studies, serious consideration is critical to obtain reliable and realistic data. The cell type must be selected considering the introduction route and target organ of the nanoparticle. In addition, the nanoparticle dose must reflect the realistic concentration of nanoparticles and must be loaded as a well-dispersed form to observe the accurate size- and shape-dependent effect. In deciding the cytotoxicity assay method, it is important to choose the appropriate method that could measure the toxicity of interest without the false-negative or -positive misinterpretation of the toxicity result.

Long-term stability of cell micropatterns on poly((3-(methacryloylamino)propyl)-dimethyl(3-sulfopropyl)ammonium hydroxide)-patterned silicon oxide surfaces.

In this work, we compared the long-term stability and integrity of cell patterns on newly reported, zwitterionic poly((3-(methacryloylamino)propyl)dimethyl(3-sulfopropyl)ammonium hydroxide) (poly(MPDSAH)) films with those on widely used, poly(poly(ethylene glycol) methyl ether methacrylate) (poly(PEGMEMA)) ones. The micropatterns of both polymers were formed on a silicon oxide surface by a combination of micropattern generation of a photoresist, vapor deposition of a silane-based polymerization initiator, and surface-initiated, atom transfer radical polymerization (SI-ATRP) of each monomer, MPDSAH or PEGMEMA. The successful formation of the silane initiator SAMs, and poly(MPDSAH) and poly(PEGMEMA) micropatterns was confirmed by X-ray photoelectron spectroscopy (XPS) and imaging ellipsometry. Onto each substrate patterned with poly(MPDSAH) or poly(PEGMEMA), NIH 3T3 fibroblast cells were seeded, and the cell micropatterns were generated by the selective adhesion of cells on the cell-adhesive region of the patterned surfaces. The cell pattern formed on the poly(MPDSAH)-patterned surface was observed to have a superior ability of finely maintaining its original, line-shaped structure up to for 20 days, when compared with the cell pattern formed on the poly(PEGMEMA)-patterned surface. In order to verify the relationship between the integrity of the cell micropatterns and the stability of the underlying non-biofouling polymer layers, we also investigated the long-term stability of the polymer films themselves, immersed in the cell culture media, for one month, in the aid of ellipsometry, contact goniometry, and XPS.

Osteoconductive conjugation of bone morphogenetic protein-2 onto titanium/titanium oxide surfaces coated with non-biofouling poly(poly(ethylene glycol) methacrylate).

This paper describes a method for introducing osteoconductivity onto titanium, a widely used material for implants, as well as maintaining its non-biofouling ("bioinert") property, in the aim of increasing bioactivity of titanium for its wider applications to biomedical areas. Titanium substrates were coated with a non-biofouling poly(poly(ethylene glycol) methacrylate) (pPEGMA) by surface-initiated polymerization, and bone morphogenetic protein-2 (BMP-2) was chemically conjugated to the activated pPEGMA films. The non-biofouling property and increased bioactivity of titanium were confirmed by the maintenance of the cellular response of mesenchymal stem cells on the titanium substrates: the BMP-2-conjugated pPEGMA films induced the adhesion and differentiation of mesenchymal stem cells, while non-conjugated pPEGMA films showed the excellent resistance against the adhesion of the cells.

The control of cell adhesion and detachment on thin films of thermoresponsive poly[(N-isopropylacrylamide)-r-((3-(methacryloylamino)propyl)-dimethyl(3-sulfopropyl)ammonium hydroxide)].

This paper describes the formation of poly(N-isopropylacrylamide) (PNIPAAm) and poly[(N-isopropylacrylamide)-r-((3-(methacryloylamino)propyl)-dimethyl(3-sulfopropyl)ammonium hydroxide)] (P(NIPAAm-r-MPDSAH)) films on a glass surface via surface-initiated, atom transfer radical polymerization as a cell-culture platform. The films of PNIPAAm with various thicknesses and of P(NIPAAm-r-MPDSAH) with various ratios of NIPAAm and MPDSAH are formed to investigate the behaviors of cell adhesion and detachment. In the case of the PNIPAAm-grafted glass surfaces, the optimal film thickness, achieving the effective control of both cell adhesion and detachment, is estimated to be 11-13 nm for NIH 3T3 fibroblast cells. The adhesion and detachment behaviors of NIH 3T3 fibroblast cells are further tuned by incorporating the hydrophilic and non-biofouling MPDSAH moiety into the PNIPAAm system. The cell adhesion and detachment are controlled best, when the ratio of NIPAAm and MPDSAH is 75:1 (NIPAAm:MPDSAH).

Highly efficient non-biofouling coating of zwitterionic polymers: poly((3-(methacryloylamino)propyl)-dimethyl(3-sulfopropyl)ammonium hydroxide).

This work describes the formation of highly efficient non-biofouling polymeric thin films of poly((3-(methacryloylamino)propyl)-dimethyl(3-sulfopropyl)ammonium hydroxide), (poly(MPDSAH)). The poly(MPDSAH) films were generated from the self-assembled monolayers terminating in an initiator of atom transfer radical polymerization (ATRP) by the surface-initiated ATRP of MPDSAH. The poly(MPDSAH) films on a gold surface were characterized by ellipsometry, FT-IR spectroscopy, contact angle goniometery, and X-ray photoelectron spectroscopy. The copper complexes and unpolymerized monomers trapped inside the polymer brushes were completely washed out by soaking the poly(MPDSAH)-coated substrate in water at 40 degrees C for 4 days. The amount of proteins nonspecifically adsorbed onto the poly(MPDSAH) films was evaluated by surface plasmon resonance spectroscopy: the adsorption of proteins was <0.6 ng/cm(2) on the surfaces for all the model proteins. The ability of the poly(MPDSAH) films to resist the nonspecific adsorption of proteins was comparable to that of the best known systems.

Surface-initiated, ring-opening metathesis polymerization: formation of diblock copolymer brushes and solvent-dependent morphological changes.

In this article, we report the formation of diblock copolymer brushes on a gold surface by surface-initiated, ring-opening metathesis polymerization (SI-ROMP) with the newly developed ruthenium catalyst [(H2IMes)(3-Br-py)2(Cl)2Ru=CHPh]. Taking advantage of the highly improved activity of the ruthenium catalyst and the rapid initiation step of ROMP, we successfully formed thin films of well-defined block copolymers with 5-norbornene-2-endo,3-endo-dimethanol and norbornene carboxylic acid methyl esters (44:56 endo/exo). The catalyst was found to be active enough to polymerize endo isomers of norbonene derivatives from the surface as well as to form diblock copolymer brushes. SI-ROMP of diblock copolymers from the surface was confirmed by ellipsometry, infrared spectroscopy, and X-ray photoelectron spectroscopy. After the formation, the polymer-grafted substrates were immersed in various solvents, and the selective swelling characteristics of polymer brushes were investigated by atomic force microscopy.