Micellar core-shell-type acrylic-polyurethane hybrid materials with self-polishing property

Abstract

Marine fouling can be a serious problem in the shipping industry, since it increases the surface roughness of the hull and hence its frictional resistance to its movement through water. Antifouling paint can be defined as preventing the attachment of marine organisms onto surfaces. However, the most commonly used antifouling coating which is the tributyltin-based self-polishing copolymer causes the severe pollution of marine environment. Ammonium salt-based paints include tertiary amines as biocides which have effective biocidal and biodegradable properties without accumulation in the sea environment. However, ammonium salt-based coatings were too sensitive to seawater and became swollen. In this study, polyurethane-acrylic copolymers were synthesized by radical polymerization. These hybrid materials were found to form core–shell structures in aqueous media. Synthesis and properties of copolymers were investigated by Fourier transform-infrared spectrometer, proton-nuclear magnetic resonance, transmission electron microscopy, and dynamic light scattering. The polishing rate of self-polishing copolymer was determined from the reduction in dry film thickness after artificial seawater immersion under a dynamic condition.     

Nanocatalyst-based assay using DNA-conjugated Au nanoparticles for electrochemical DNA detection

Compared to enzymes, Au nanocatalysts show better long-term stability and are more easily prepared. Au nanoparticles (AuNPs) are used as catalytic labels to achieve ultrasensitive DNA detection via fast catalytic reactions. In addition, magnetic beads (MBs) are employed to permit low nonspecific binding of DNA-conjugated AuNPs and to minimize the electrocatalytic current of AuNPs as well as to take advantage of easy magnetic separation. In a sandwich-type electrochemical sensor, capture-probe-conjugated MBs and an indium-tin oxide electrode modified with a partially ferrocene-modified dendrimer act as the target-binding surface and the signal-generating surface, respectively. A thiolated detection-probe-conjugated AuNP exhibits a high level of unblocked active sites and permits the easy access of p-nitrophenol and NaBH 4 to these sites. Electroactive p-aminophenol is generated at these sites and is then electrooxidized to p-quinoneimine at the electrode. The p-aminophenol redox cycling by NaBH 4 offers large signal amplification. The nonspecific binding of detection-probe-conjugated AuNPs is lowered by washing DNA-linked MB-AuNP assemblies with a formamide-containing solution, and the electrocatalytic oxidation of NaBH 4 by AuNPs is minimized because long-range electron transfer between the electrode and the AuNPs bound to MBs is not feasible. The high signal amplification and low background current enable the detection of 1 fM target DNA.     

Side-on bound dinitrogen complex of zirconium supported by a P2N2 macrocyclic ligand

Reduction of [P 2N 2]ZrCl 2 (where P 2N 2 = PhP(CH 2SiMe 2NSiMe 2CH 2) 2PPh) by KC 8 under N 2 generates the dinuclear dinitrogen complex ([P 2N 2]Zr) 2(mu-eta (2):eta (2)-N 2) and impurities in varying yields depending on the solvent and temperature. The toluene complex [P 2N 2]Zr(eta (6)-C 7H 8) along with a dinuclear species with bridging PC 6H 5 groups is observable. Also observable in the crude reaction mixtures is the mu-oxodiazenido derivative, ([P 2N 2]Zr) 2(mu-eta (2):eta (2)-N 2H 2)(mu-O), due to reaction with trace H 2O. This paper reports the full details of the preparation of ([P 2N 2]Zr) 2(mu-eta (2):eta (2)-N 2) including an improved method that involves reduction at low temperatures in a tetrahydrofuran solvent. Also reported is a reproducible synthesis of the oxodiazenido complex along with the X-ray structures of the dinitrogen complex and the oxodiazenido derivative.     

Preparation of an open-tubular capillary column with a monolithic layer of S-ketoprofen imprinted and 4-styrenesulfonic acid incorporated polymer and its enhanced chiral separation performance in capillary electrochromatography

Enhanced chiral separation performance has been observed for ketoprofen enantiomers in capillary electrochromatography (CEC) with an open-tubular (OT) column prepared with a specific molecule imprinted polymer (MIP) on the innerwall of 50mum ID capillary. The column was prepared by in situ thermal polymerization inside the pretreated and silanized fused silica capillary. A specific diluted monomer mixture composed of S-ketoprofen, methacrylic acid (MAA, functional monomer), ethylene glycol dimethacrylate (EDMA, cross-linker), and 4-styrenesulfonic acid (4-SSA) dissolved in 9/1 (v/v) acetonitrile/2-propanol was used to fabricate the OT-MIP layer. 4-SSA was added to form a MIP layer capable of stable and strong electro-osmotic flow (EOF) over the pH range of this study securing CEC elution of ketoprofen having partial negative charge near the optimized pH. Various parameters such as buffer pH, organic modifier composition, salt concentration, and applied potential have been optimized for CEC chiral separation of ketoprofen enantiomers. Very good separation selectivity and efficiency were observed, thus the chromatographic resolution of ketoprofen enantiomers was as high as 10.5, and the number of theoretical plates of R-ketoprofen, 156,000/m (40,000/m for S-ketoprofen), which proves that the OT-MIP-CEC type approach is a promising strategy in MIP study.     

On the difficulties of predicting the adsorption of volatile organic compounds at low pressures in microporous solid: the example of ethyl benzene

Adsorption isotherms of toluene and ethyl benzene, at 25 degrees C and 40 degrees C, were determined in two microporous activated carbons and one zeolite. Significant differences were found in the adsorption behavior, at low pressures, between the two vapors on the same adsorbent material. The quantities of adsorbed ethyl benzene at 25 degrees C, in the low-pressure region, were lower than what was observed at 40 degrees C in all the studied adsorbents, contrary to what was found for toluene. This fact was not related to kinetic effects at the two temperatures nor to vapor swelling of the adsorbents structure. Also, there was no molecular sieving since at high pressures the toluene and ethyl benzene occupied the same adsorption space. The differences found in the ethyl benzene adsorption at the two temperatures pose difficulties in the analysis of the adsorption data and, therefore, in the prediction of results. This is discussed in the analysis of the results with the application of the Dubinin-Astakhov equation and in the estimation of the isosteric heats of adsorption. The adsorption potentials of two possible ethyl benzene conformations were estimated for the adsorption in the pores of activated carbon from the Horvath and Kawazoe model, and the values compared with those found experimentally. The results were interpreted in terms of the ethyl benzene conformation effects when the molecule is confined in pores that are about the same size of one of the conformations.     

Impact of pinning of the triple contact line on electrowetting performance

Pinning of the triple contact line adversely affects electrowetting on dielectric. Electrowetting response of substrates with contact angle hysteresis ranging from 1° to 30° has been characterized, and the results are interpreted within the framework of electromechanics corrected for pinning. The relationship between contact angle hysteresis, threshold potential for liquid actuation, and electrowetting hysteresis is quantified. Our results demonstrate that a modified electrowetting equation, based on balance of forces (including the pinning forces) acting on the triple contact line and on the drop, describes the electrowetting response of substrates with significant contact angle hysteresis. Finally, the surface properties of PDMS Sylgard 184 were found to be influenced by the electric field.     

Molecular Orbital Controlling Donor Moiety for High‐Efficiency Thermally Activated Delayed Fluorescent Emitters

A new donor moiety, 7,7,13,13‐tetramethyl‐7,13‐dihydro‐5H‐indeno[1,2‐b]acridine (IAc), was developed to control the highest occupied molecular orbital (HOMO) dispersion of thermally activated delayed fluorescent (TADF) emitters. The IAc unit expanded the HOMO dispersion of the emitters and increased the quantum efficiency of the TADF devices up to 20.9 %.     

Development of novel synthetic method of carbon nanotubes from electrospun polystyrene fibers by using microwave heating

We have developed a novel synthetic method that enables us to easily synthesize metal‐capsulated carbon nanotubes (CNTs) in a laboratory by using a combined technology of electrospinning‐metallization and microwave heating. These techniques greatly shorten the time for the synthesis of the CNTs in comparison with the conventional methods. TEM analysis confirmed a successful formation of the CNTs, and the resulting CNTs were multi‐walled and found to be about 25–100 nm in diameters. The products prepared by heating at 600 and 900°C exhibited less‐developed and strongly curved CNTs, whereas the products prepared by heating at 700 and 800°C relatively well‐developed long CNTs. Copyright © 2010 John Wiley & Sons, Ltd.