Nanostructured PtVFe catalysts: Electrocatalytic performance in proton exchange membrane fuel cells

This paper reports new findings of an investigation of the electrocatalytic performance of nanostructured PtVFe catalysts in proton exchange membrane fuel cells (PEMFC). The membrane electrode assembly was prepared using nano-engineered PtVFe nanoparticles with controlled composition and size supported on carbon as the cathode electrocatalysts. The results reveal that the PtVFe/C catalysts exhibited excellent fuel cell performance, better than that using the commercial Pt/C catalyst. This finding provides the first example demonstrating the viability of the PEMFC application of the nanostructured trimetallic catalysts.     

Role of support-nanoalloy interactions in the atomic-scale structural and chemical ordering for tuning catalytic sites

The understanding of the atomic-scale structural and chemical ordering in supported nanosized alloy particles is fundamental for achieving active catalysts by design. This report shows how such knowledge can be obtained by a combination of techniques including X-ray photoelectron spectroscopy and synchrotron radiation based X-ray fine structure absorption spectroscopy and high-energy X-ray diffraction coupled to atomic pair distribution function analysis, and how the support-nanoalloy interaction influences the catalytic activity of ternary nanoalloy (platinum-nickel-cobalt) particles on three different supports: carbon, silica, and titania. The reaction of carbon monoxide with oxygen is employed as a probe to the catalytic activity. The thermochemical processing of this ternary composition, in combination with the different support materials, is demonstrated to be capable of fine-tuning the catalytic activity and stability. The support-nanoalloy interaction is shown to influence structural and chemical ordering in the nanoparticles, leading to support-tunable active sites on the nanoalloys for oxygen activation in the catalytic oxidation of carbon monoxide. A nickel/cobalt-tuned catalytic site on the surface of nanoalloy is revealed for oxygen activation, which differs from the traditional oxygen-activation sites known for oxide-supported noble metal catalysts. The discovery of such support-nanoalloy interaction-enabled oxygen-activation sites introduces a very promising strategy for designing active catalysts in heterogeneous catalysis.     

Correlation between atomic coordination structure and enhanced electrocatalytic activity for trimetallic alloy catalysts

This Article describes findings of the correlation between the atomic scale structure and the electrocatalytic performance of nanoengineered PtNiFe/C catalysts treated at different temperatures for oxygen reduction reaction, aiming at providing a new fundamental insight into the role of the detailed atomic alloying and interaction structures of the catalysts in fuel cell reactions. Both mass and specific activities of the catalysts were determined using rotating disk electrode and proton exchange membrane fuel cell. The mass activities extracted from the kinetic regions in both measurements revealed a consistent trend of decreasing activity with increasing temperature. However, the specific activity data from RDE revealed an opposite trend, that is, increasing activity with increasing temperature. In addition to TEM, XRD, and XPS characterizations, a detailed XAFS analysis of the atomic scale coordination structures was carried out, revealing increased heteroatomic coordination with improved alloying structures for the catalyst treated at the elevated temperatures. XPS analysis has further revealed a reduced surface concentration of Pt for the catalyst for the high temperature treated catalyst. The higher mass activity for the lower temperature treated catalyst is due to Pt surface enrichment on the surface sites, whereas the higher specific activity for the higher temperature treated catalyst reflects an enhanced Pt-alloying surface sites. These findings have thus provided a new insight for assessing the structural correlation of the electrocatalytic activity with the fcc-type lattice change and the atomic scale alloying characteristics. Implications of these findings to the design of highly active alloy electrocatalysts are discussed, along with their enhanced electrocatalytic performance in the fuel cell.     

Cationic recognition by tert-butylcalix[4]arene-functionalized nanoprobes

A nanoparticle-based strategy has been demonstrated using structurally-tailored tert-butylcalixarenes immobilized on gold nanoparticles to tune the guest access to the calixarene cone cavity for cationic recognition. This strategy exploits the interparticle charge-induced aggregation upon selective capture of metal cations into the nanoparticle-immobilized tert-butylcalixarenes, which produces calorimetric changes for the detection. A possible pathway for the binding of M(n+) into the t-BCA structure and the interparticle interaction is proposed for the formation of an electric double layer inducing the interparticle association responsible for the red-shifted surface plasmon resonance band of the nanoparticles. The value of this class of calorimetric nanoprobes will be in the area of designing advanced host-guest probes using a variety of calixarene ligands for ionic recognition in a simplistic detection format.     

Computational identification and experimental characterization of substrate binding determinants of nucleotide pyrophosphatase/phosphodiesterase 7

Background

Elevated numbers of regulatory T cells (T_regs) have been implicated in certain cancers. Depletion of T_regs has been shown to increase anti-tumor immunity. T_regs also play a critical role in the suppression of autoimmune responses. The study of T_regs has been hampered by a lack of adequate surface markers. Leucine Rich Repeat Containing 32 (LRRC32), also known as Glycoprotein A Repetitions Predominant (GARP), has been postulated as a novel surface marker of activated T_regs. However, there is limited information regarding the processing of LRRC32 or the regulatory phenotype and functional activity of T_regs expressing LRRC32.

Results

Using naturally-occurring freshly isolated T_regs, we demonstrate that low levels of LRRC32 are present intracellularly prior to activation and that freshly isolated LRRC32⁺ T_regs are distinct from LRRC32^- T_regs with respect to the expression of surface CD62L. Using LRRC32 transfectants of HEK cells, we demonstrate that the N-terminus of LRRC32 is cleaved prior to expression of the protein at the cell surface. Furthermore, we demonstrate using a construct containing a deleted putative signal peptide region that the presence of a signal peptide region is critical to cell surface expression of LRRC32. Finally, mixed lymphocyte assays demonstrate that LRRC32⁺ T_regs are more potent suppressors than LRRC32^- T_regs.

Conclusions

A cleaved signal peptide site in LRRC32 is necessary for surface localization of native LRRC32 following activation of naturally-occurring freshly-isolated regulatory T cells. LRRC32 expression appears to alter the surface expression of activation markers of T cells such as CD62L. LRRC32 surface expression may be useful as a marker that selects for more potent T_reg populations. In summary, understanding the processing and expression of LRRC32 may provide insight into the mechanism of action of T_regs and the refinement of immunotherapeutic strategies aimed at targeting these cells.     

Harnessing molecule-solid duality of nanoclusters/nanoparticles for nanoscale control of size, shape and alloying

This report demonstrates a molecule-solid duality concept for nanoscale control of size, shape and alloying by showing novel evolution of binary copper and gold nanoclusters or nanoparticles towards alloy nanocubes, as evidenced by in situ real time synchrotron X-ray diffraction characterization.     

Isoflavone glycosides from the root wood of Erythrina latissima

The molecular structures of 3 isoflavone glycosides isolated from the root wood of Erythrina latissima were established as 4'-hydroxyisoflavone-7-O-beta-D-glucopyranoside (compound 1); 4'-hydroxyisoflavone-7-O-alpha-L-rhamnosyl (1-->6)-beta-D-glucopyranoside (compound 2); and a new compound 4', 8-dimethoxy isoflavone-7-O-alpha-L-rhamnosyl (1-->6) glucopyranoside (8-O-methylretusin-7-O-alpha-L-rhamnosyl (1-6)-beta-D-glucopyranoside) (compound 3).     

Core-shell-structured magnetic ternary nanocubes

We report a novel core-shell-structured ternary nanocube of MnZn ferrite synthesized by controlling the reaction temperature and composition in the absence of conventionally used reducing agents. The highly monodispersed core-shell structure consists of an Fe(3)O(4) core and an MnZn Ferrite shell. The observation of a Moire? pattern indicates that the core and the shell are two highly crystalline materials with slightly different lattice constants that are rotated relative to each other by a small angle. The ternary core-shell nanocubes display magnetic properties regulated by a combination of the core-shell composition and exhibit an increased coercivity and field-cooled/zero-field-cooled characteristics drastically different from those of regular MnZn ferrite nanoparticles. The ability to engineer the spatial nanostructures of ternary magnetic nanoparticles in terms of shape and composition offers atomic-level versatility in fine-tuning the nanoscale magnetic properties.     

Targeting of cancer cells with ferrimagnetic ferritin cage nanoparticles

Protein cage architectures such as virus capsids and ferritins are versatile nanoscale platforms amenable to both genetic and chemical modification. Incorporation of multiple functionalities within these nanometer-sized protein architectures demonstrate their potential to serve as functional nanomaterials with applications in medical imaging and therapy. In the present study, we synthesized an iron oxide (magnetite) nanoparticle within the interior cavity of a genetically engineered human H-chain ferritin (HFn). A cell-specific targeting peptide, RGD-4C which binds alphavbeta3 integrins upregulated on tumor vasculature, was genetically incorporated on the exterior surface of HFn. Both magnetite-containing and fluorescently labeled RGD4C-Fn cages bound C32 melanoma cells in vitro. Together these results demonstrate the capability of a genetically modified protein cage architecture to serve as a multifunctional nanoscale container for simultaneous iron oxide loading and cell-specific targeting.     

Selective attachment and release of a chemotherapeutic agent from the interior of a protein cage architecture

The antitumor agent doxorubicin was covalently bound and selectively released in a pH dependent manner from the interior surface of a genetically modified small heat shock protein (Hsp) cage.