Oxygen Carrier Based on Hemoglobin/Poly(L-lysine)-block-poly(L-phenylalanine) Vesicles

An oxygen carrier was prepared by encapsulating carbonylated hemoglobin (CO-Hb) molecules into polypeptide vesicles made from poly(L-lysine)-block-poly(L-phenylalanine) (PLL-b-PPA) diblock copolymers in aqueous medium at pH 5.8. The encapsulation was confirmed by confocal laser scanning microscopy (CLSM). The morphology and size of the Vesicles were studied by field-emission scanning electron microscopy (ESEM). They had a spherical shape with it mean diameter of about 4 to 5 mu m. The encapsulation efficiency of hemoglobin was 40 wt %, and the hemoglobin content in the vesicles was 32 wt %. The CO-Hb encapsulated in the PLL-b-PPA vesicles was more stable than free CO-Hb under ambient conditions, In the presence of a O-2 atmosphere, the CO-Hb in the vesicle could be converted into oxygen-binding hemoglobin (O-2-Hb) under irradiation of visible light for 2 h. Therefore, the CO-Hb/PLL-b-PPA vesicles are expected to be used its red blood cell substitutes.

Electrochemical designing of Au/Pt core shell nanoparticles as nanostructured catalyst with tunable activity for oxygen reduction

Au/Pt core shell nanoparticles (NPs) have been prepared via a layer-by-layer growth of Pt layers on An NPs using underpotential deposition (UPD) redox replacement technique. A single UPD Cu monolayer replacement with Pt(11) yielded a uniform Pt film on Au NPs, and the shell thickness can be tuned by controlling the number of UPD redox replacement cycles. Oxygen reduction reaction (ORR) in air-saturated 0.1 M H2SO4 was used to investigate the electrocatalytic behavior of the as-prepared core shell NPs. Cyclic voltammograms of ORR show that the peak potentials shift positively from 0.32 V to 0.48 V with the number of Pt layers increasing from one to five, suggesting the electrocatalytic activity increases with increasing the thickness of Pt shell. The increase in electrocatalytic activity may originate mostly from the large decrease of electronic influence of Au cores on surface Pt atoms. Rotating ring-disk electrode voltammetry and rotating disk electrode voltammetry demonstrate that ORR is mainly a four-electron reduction on the as-prepared modified electrode with 5 Pt layers and first charge transfer is the rate-determining step.

The real role of carbon in Pt/C catalysts for oxygen reduction reaction

A new electrocatalysis of carbon materials for oxygen reduction reaction (ORR) on Pt/C catalysts was discovered. It was found that there exist two kinds of electroactive sites on these supports of carbon materials, which can effectively electrocatalyze the reduction of peroxide intermediated from oxygen reduction on Pt, as this provides continuous driving force to move the equilibrium toward the production of peroxide from ORR.

Hydrothermal synthesis, structure characterization of a new mixed Mo/V metal-oxygen cluster compound: [Co(phen)(3)](2)[HPMo4V (Mo4V6IV)-V-VI M2O44]center dot 4H(2)O, (M=0.78Mo(V)+0.22V(IV))

A new polyoxometalate [Co(phen)(3)](2)[HPMo4V Mo-4(VI) V-6(IV) M2O44]center dot 4H(2)O (M = 0.78Mo(V)+ 0.22V(IV)) 1 was hydrothermally synthesized and characterized by IR, elemental analyses, X-ray photoelectron spectrum, ESR and single crystal X-ray diffraction. The title compound is in the triclinic space group P (1) over bar with a = 12.0953(7) angstrom, b = 14.0182(6) angstrom, c = 14.6468(7) angstrom, V=2402.55(18) angstrom(3), alpha = 105.134(2), beta = 91.841(3), gamma = 91.401(2), Z = 1, and R-1 (wR(2)) = 0.0617 (0.1701). The compound was prepared from tetra-capped pseudo-Kepin with phosphorus-centered polyoxoanions [PMo8V6M2O44](5-) , [Co(phen)(3)](2+) cations and linked through hydrogen bonds and pi-pi stacking interaction into three-dimensional supramolecular framework. Astudy of the magnetic properties of 1 demonstrates that it exhibits antiferromagnetic coupling interactions.

Preparation of hybrid thin film modified carbon nanotubes on glassy carbon electrode and its electrocatalysis for oxygen reduction

A hybrid thin film containing Pt nanoparticles and [tetrakis(N-methylpyridyl)porphyrinato] cobalt (CoTMPyP) modified multi-walled carbon nanotubes (MWNTs) on a glassy carbon (GC) electrode surface was fabricated. This hybrid film electrode exhibited remarkable electrocatalytic activity for oxygen reduction and high stability with promising applications in fuel cells.

Electrochemical design of ultrathin platinum-coated gold nanoparticle monolayer films as a novel nanostructured electrocatalyst for oxygen reduction

The deliberate tailoring of nanostructured metallic catalysts at the monolayer-level is an ongoing challenge and could lead to new electronic and catalytic properties, since surface-catalyzed reactions are extremely sensitive to the atomic-level details of the catalytic surface. In this article, we present a novel electrochemical strategy to nanoparticle-based catalyst design using the recently developed underpotential deposition (UPD) redox replacement technique. A single UPD Cu replacement with Pt2+ yielded a uniform Pt layer on colloid gold surfaces. The ultrathin (nominally monolayer-level) Pt coating of the novel nanostructured particles was confirmed by cyclic voltammetry and X-ray photoelectron spectra (XPS). The present results demonstrate that ultrathin Pt coating effects efficiently and behaves as the nanostructured monometallic Pt for electrocatalytic oxygen reduction, and also shows size-dependent, tunable electrocatalytic ability. The as-prepared ultrathin Pt-coated Au nanoparticle monolayer electrodes reduce O-2 predominantly by four electrons to H2O, as confirmed by the rotating ring-disk electrode (RRDE) technique.

Electrocatalytic reduction of oxygen at multi-walled carbon nanotubes and cobalt porphyrin modified glassy carbon electrode

The multi-walled carbon nanotubes (MWNTs) modified glassy carbon electrode exhibited electrocatalytic activity to the reduction of oxygen in 0.1 M HAc-NaAc (pH 3.8) buffer solution. Further modification with cobalt porphyrin film on the MWNTs by adsorption, the resulted modified electrode showed more efficient catalytic activity to O-2 reduction. The reduction peak potential of O-2 is shifted much more positively to 0.12 V (vs. Ag/AgCl), and the peak current is increased greatly. Cyclic voltammetry (CV), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM), were used to characterize the material and the modified film on electrode surface. Electrochemical experiments gave the total number of electron transfer for oxygen reduction as about 3, which indicated a co-exist process of 2 electrons and 4 electrons for reduction of oxygen at this modified electrode. Meanwhile, the catalytic activities of the multilayer film (MVVNTs/CoTMPyP)(n) prepared by layer-by-layer method were investigated, and the results showed that the peak current of O-2 reduction increased and the peak potential shifted to a positive direction with the increase of layer numbers.

Study on the structure change and oxygen vacation shift for Ce1-xSmxO2-y solid solution

A series of solid electrolytes Ce1-xSmxO2-y (x=0similar to0.6) were prepared by sol-gel method. XRD measurement showed that single-phase solid solution was formed in all investigated ranges at 160 degreesC, which is a significantly lower synthesis temperature compared to traditional solid state reaction. High temperature X-ray, ESR, and Raman scattering were used to characterize the samples. ESR measurement showed that ESR with sample irradiated by high-energy particle is an effective way to study the defect structure. These changes in the Raman spectrum are attributed to O vacancies, which are introduced into the lattice when tetravalent Ce4+ is substituted by trivalent Sm3+.

Methanol tolerant FeTPP-Pt/C Co-catalysts for the electroreduction of oxygen

It was found for the first time that iron tetraphenylporphyrin (FeTPP)-Pt/C showed the good activity for the electroreduction of oxygen and methanol tolerant ability. Their performances were related to the heat-treatment temperature.