Platinum nanoparticle-catalyzed lucigenin–hydrazine chemiluminescence

It was found that lucigenin alkaline solution could react with hydrazine in the presence of Pt nanoparticles to generate strong chemiluminescence (CL) centered at 480 nm. In order to explore the CL mechanism, UV–visible spectra, X-ray photoelectron spectra studies before and after the CL reaction were carried out. The effects of O₂ and superoxide dismutase (SOD) on the CL reaction were examined. The catalytic effect of Pt NPs on the hydrazine–O₂ reaction was studied. A possible mechanism is proposed to be due to that Pt NPs catalyzed the reaction between hydrazine and the dissolved oxygen under alkaline conditions to yield hydroperoxide species and superoxide radical anion, which further oxidized lucigenin to produce CL emission. Moreover, the effects of some organic compounds containing hydroxyl (OH), carboxyl (COOH), carbonyl (CO), amino (NH₂), or sulfur groups on the lucigenin–hydrazine–Pt NPs CL system were tested. Thiol-containing compounds such as cysteine (Cys), glutathione (GSH), homocysteine (Hcy), and 6-mercaptopurine (6-MP) were observed to greatly enhance the CL intensity. It is suggested that the CL enhancement might be due to the fact that thiol-containing compounds could facilitate the electron transfer process under the catalysis of Pt nanoparticles and accelerate the generation of OH and O₂^? radicals, leading to the strong CL.     

Cycling performance of LiNi<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript>Mn<Subscript>2 − <Emphasis Type="Italic">y</Emphasis></Subscript>O<Subscript>4</Subscript> prepared by the solid-state reaction

In order to improve the cycling performance of LiMn₂O₄, a part of Mn in LiMn₂O₄ was replaced by Ni. LiNi _y Mn_{2 − y} O₄ (y = 0.02, 0.05, 0.10, 0.15, and 0.20) were synthesized by preheating a mixture of LiOH, MnO₂ (CMD), and NiO at 400°C for 10 h and then calcining at 850°C for 48 h in air with intermediate grinding. The voltage vs. discharge capacity curves at a current density of 300 μA/cm² between 3.5 and 4.3 V showed two plateaus, but the plateaus became unclear as the value of y increased. The sample with y = 0.02 had the largest first discharge capacity of 118.1 mA h/g. The LiNi_0.10Mn_1.90O₄ sample had a relatively large first discharge capacity of 95.0 mA h/g and snowed an excellent cycling performance.     

Effects of metal oxides on intumescent flame‐retardant polypropylene

Variable amounts of transition metal oxides (MO), such as MnO₂, ZnO, Ni₂O₃, etc., were incorporated into blends of polypropylene (PP)/ammonium polyphosphate (APP)/dipentaerythritol (DPER) with the aim of studying and comparing their effects with main‐group MO on intumescent flame retardance (IFR). The PP/IFR/MO composites were prepared using a twin‐screw extruder, and the IFR behavior was evaluated through oxygen index and vertical burning tests. The progressive enhancement of flame retardancy has proved to be strongly associated with the interaction between APP and MO. With the aid of thermogravimetry (TG) analysis, Fourier transform infrared (FTIR) spectra and scanning electron microscopy, Ni₂O₃ has been shown to be the most effective among the aforementioned three MO. The flame‐retardant mechanism of the IFR system is also discussed in terms of catalytic charring, which relates to complex formation through the d‐orbitals of the transition metal elements. It is considered that the melt viscosity of a PP/APP/DPER blend containing Ni₂O₃ corresponds well to the gas release with increasing temperature. Copyright © 2009 John Wiley & Sons, Ltd.     

Morphological investigations of block sulfonated poly(arylene ether ketone) copolymers as potential proton exchange membranes

A series of block sulfonated poly(arylene ether ketone) (SPAEK) copolymers with different block lengths and ionic contents were synthesized by a two‐stage process. The morphology of these block SPAEK copolymers was investigated by various methods, such as differential scanning calorimetry (DSC), transmission electron microscope (TEM), and small angle X‐ray scattering (SAXS). Dark colored ionic domains of hundreds of nanometers spreading as a cloud‐like belt were observed in TEM images. The sizes of the ionic domains as a function of block copolymer composition were determined from SAXS curves. The results for the evolution of ionic domains revealed that the block copolymers exhibited more clearly phase‐separated microstructure with increasing ionic contents and hydrophobic sequence lengths. Proton conductivity is closely related to the microstructure, especially the presence of large interconnected ionic domains or ionic channels. Block SPAEK membranes have interconnected ionic clusters to provide continuous hydrophilic channels, resulting in higher proton conductivity. Copyright © 2010 John Wiley & Sons, Ltd.     

Barrier effect and coupled transport in the electrodialysis of metal complexonate solutions

The electrodialysis of an aqueous solution of an alkaline earth complex with ethylenediaminetetraacetic acid (EDTA) was studied in a wide range of current densities. The curve of the complexonate flow across an anionite membrane versus current density has three characteristic sections. The first section corresponds to a linear increase in the flow as a function of current density, the second to a decrease in the flow and decomposition of the complex (barrier effect), and the third to an increase in the complexonate flow due to the transport coupled with the flow of hydroxyl ions formed in the dissociation of water molecules at the interface of the solution and the anionite membrane. Conditions for complete separation of the singly and doubly charged cations were found.     

Structure and wettability relationship of coelectrospun poly (L‐lactic acid)/gelatin composite fibrous mats

Coelectrospun polylactide(PLA)/gelatin (GE) composite fibrous matrixes have been identified to exhibit much improved performances compared to the respective components; however, the reasons for their water contact angles decreasing to zero at proper PLA/GE ratios remain unclear. To get a deep understanding of the phenomenon, PLA and GE were coelectrospun with different PLA/GE ratios in this study. Although the resulting composite fibers were homogeneous in appearance, they were detected different microscopic structures by transmission electron mircroscope (TEM) and via morphological observations after selective removal of either PLA or GE component. Together with the results of degradation study in phosphate buffered solution, a kind of cocontinuous phase separation microstructure could be identified for the PLA(50 wt%)/GE(50 wt%) composite fibers, which also showed the water contact angle of 0°. This value was far lower than those of electrospun PLA (～123°) and GE (～42°) fibrous matrixes. The X‐ray photoelectron spectrometry (XPS) data revealed that the polar side groups of protein macromolecules have moved toward composite fiber surface with solvent evaporation during electrospinning, due to the hydrophobic interaction between PLA and GE. Then the excellent hydrophilicity of PLA(50 wt%)/GE(50 wt%) composite fibers could be suggested as the consequence of: (1) the cocontinuous phase separation structure could provide more interface and void for water molecules penetrating; and (2) the accumulation of polar groups on composite fiber surface significantly increased the surface wettability. Copyright © 2010 John Wiley & Sons, Ltd.     

Three-dimensionally crossing manifold micro-mixer for fast mixing in a short channel length

In this study, we report a neo-conceptive three-dimensionally (3D) crossing manifold micromixer (CMM) embedded in microchannel. Fabricated by sequential processes of photolithography and two photon absorption stereolithography, this leads to a microfluidic system with a built-in micromixer in a site controlled manner. The effectiveness of CMM is investigated numerically and experimentally. Through the numerical simulation, it is estimated that a high mixing ratio of 90% can be obtained even in a channel length shorter than five times the channel width. This compares well with the conventional passive type of micromixers that have a gradual increase in mixing efficiency with the length of the channel. Furthermore, the mixing performance of the realized CMM built-in microchannel is observed by confocal microscopy.     

pH-responsive self-duplex of (Py)A-substituted oligodeoxyadenylate in graphene oxide solution as a molecular switch

In this paper, we demonstrated a highly discriminated and reliable molecular switch based on the interaction between the self-duplex of (Py)A-substituted oligodeoxyadenylate and graphene oxide in aqueous solution. This system showed a clear on/off state through the association and dissociation of (Py)A-modified oligodeoxynucleotide with graphene oxide in manipulated pH conditions, high amplitude efficiency for at least 50 cycles, and rapid response within seconds. Our molecular switch system has high reproducibility and simple operation by using pH stimulus.     

Cationic nucleolipids as efficient siRNA carriers

We synthesized five novel uridine-based cationic nucleolipids, introducing basic amino acid residues at the 5' position of uridine, through 1,3-dipolar cycloaddition, and hydrophobic alkyl moieties at the 2' and 3' positions, through carbamate linkages. Their lipoplexes delivered siRNAs efficiently to cells, in vitro, without any severe toxicity.     

Cadmium(II) N-acetylcysteine complex formation in aqueous solution

The complex formation between Cd(II) ions and N-acetylcysteine (H(2)NAC) in aqueous solution was investigated using Cd K- and L(3)-edge X-ray absorption and (113)Cd NMR spectroscopic techniques. Two series of 0.1 M Cd(II) solutions with the total N-acetylcysteine concentration c(H2NAC) varied between 0.2-2 M were studied at pH 7.5 and 11.0, respectively. At pH = 11 a novel mononuclear [Cd(NAC)(4)](6-) complex with the average Cd-S distance 2.53(2) ? and the chemical shift δ((113)Cd) = 677 ppm was found to dominate at a concentration of the free deprotonated ligand [NAC(2-)] > 0.1 M, consistent with our previous reports on cadmium tetrathiolate complex formation with cysteine and glutathione. At pH 7.5 much higher ligand excess ([HNAC(-)] > 0.6 M) is required to make this tetrathiolate complex the major species. The (113)Cd NMR spectrum of a solution containing c(Cd(II)) = 0.5 M and c(H2NAC) = 1.0 M measured at 288 K showed three broad signals at 421, 583 and 642 ppm, which can be attributed to CdS(3)O(3), CdS(3)O and CdS(4) coordination sites, respectively, in oligomeric Cd(II)-NAC species with single thiolate bridges between the cadmium ions.