Finding the Way to Solar Fuels with Dye-Sensitized Photoelectrosynthesis Cells.

The dye-sensitized photoelectrosynthesis cell (DSPEC) integrates high bandgap, nanoparticle oxide semiconductors with the light-absorbing and catalytic properties of designed chromophore-catalyst assemblies. The goals are photoelectrochemical water splitting into hydrogen and oxygen and reduction of CO2 by water to give oxygen and carbon-based fuels. Solar-driven water oxidation occurs at a photoanode and water or CO2 reduction at a cathode or photocathode initiated by molecular-level light absorption. Light absorption is followed by electron or hole injection, catalyst activation, and catalytic water oxidation or water/CO2 reduction. The DSPEC is of recent origin but significant progress has been made. It has the potential to play an important role in our energy future.

Polyethylenimine-enhanced electrocatalytic reduction of CO2 to formate at nitrogen-doped carbon nanomaterials.

Nitrogen-doped carbon nanotubes are selective and robust electrocatalysts for CO2 reduction to formate in aqueous media without the use of a metal catalyst. Polyethylenimine (PEI) functions as a co-catalyst by significantly reducing catalytic overpotential and increasing current density and efficiency. The co-catalysis appears to help in stabilizing the singly reduced intermediate CO2(•-) and concentrating CO2 in the PEI overlayer.

Pump-probe microscopy: spatially resolved carrier dynamics in ZnO rods and the influence of optical cavity resonator modes.

Femtosecond pump-probe microscopy is used to investigate the charge recombination dynamics at different points within a single needle-shaped ZnO rod. Recombination in the tips of the rod occurs through an excitonic or electron-hole plasma state, taking place on a picosecond time scale. Photoexcitation in the larger diameter sections of the interior exhibit dramatically slower recombination that occurs primarily through defects sites, i.e., trap mediated recombination. Transient absorption imaging shows that the spatial variation in the dynamics is also influenced by the cavity resonances supported within the hexagonal cross section of the rod. Finite element simulations suggest that these optical resonator modes produce qualitatively different intensity patterns in the two different locations. Near the end of the rod, the intensity pattern has significant standing-wave character, which leads to the creation of photoexcited carriers in the core of the structure. The larger diameter regions, on the other hand, exhibit intensity distributions in which the whispering gallery (WG) mode character dominates. At these locations, the photoexcited carriers are produced in subsurface depletion zone, where the internal fields separate the electrons and holes and lead to a greater degree of trap recombination on longer time scales.

Trans-10, cis-12-conjugated linoleic acid alters hepatic gene expression in a polygenic obese line of mice displaying hepatic lipidosis.

The trans-10, cis-12 isomer of conjugated linoleic acid (CLA) causes a rapid reduction of body and adipose mass in mice. In addition to changes in adipose tissue, numerous studies have reported alterations in hepatic lipid metabolism. Livers of CLA-fed mice gain mass, partly due to lipid accumulation; however, the precise molecular mechanisms are unknown. To elucidate these mechanisms, we examined fatty acid composition and gene expression profiles of livers from a polygenic obese line of mice fed 1% trans-10, cis-12-CLA for 14 days. Analysis of gene expression data led to the identification of 1393 genes differentially expressed in the liver of CLA-fed male mice at a nominal P value of .01, and 775 were considered significant using a false discovery rate (FDR) threshold of .05. While surprisingly few genes in lipid metabolism were impacted, pathway analysis found that protein kinase A (PKA) and cyclic adenosine monophosphate (cAMP) pathways signaling pathways were affected by CLA treatment and 98 of the 775 genes were found to be regulated by hepatocyte nuclear factor 4alpha, a transcription factor important in controlling liver metabolic status.

Direct imaging of optical cavity modes in ZnO rods using second harmonic generation microscopy.

Images of second harmonic generation (SHG) in needle-shaped ZnO rods obtained from individual structures show areas of enhanced second harmonic intensity along the longitudinal axis of the rod that are periodically distributed and symmetrically situated relative to the rod midpoint. The spatial modulation is a direct consequence of the fundamental optical field coupling into standing wave resonator modes of the ZnO structure, leading to an enhanced backscattered second harmonic condition that cannot be achieved in bulk ZnO. A more complicated second harmonic image is observed when excitation is below the band gap, which is attributed to whispering gallery modes. This physical phenomenon, which extends beyond just ZnO to many other optical materials, could pave the way to new applications that exploit the nonlinear optical properties of individual structures.

Functional genomic characterization of delipidation elicited by trans-10, cis-12-conjugated linoleic acid (t10c12-CLA) in a polygenic obese line of mice.

Gene expression was measured during t10c12-CLA-induced body fat reduction in a polygenic obese line of mice. Adult mice (n = 185) were allotted to a 2 x 2 factorial experiment consisting of either nonobese (ICR-control) or obese (M16-selected) mice fed a 7% fat, purified diet containing either 1% linoleic acid (LA) or 1% t10c12-CLA. Body weight (BW) by day 14 was 12% lower in CLA- compared with LA-fed mice (P < 0.0001). By day 14, t10c12-CLA reduced weights of epididymal, mesenteric, and brown adipose tissues, as a percentage of BW, in both lines by 30, 27, and 58%, respectively, and increased liver weight/BW by 34% (P < 0.0001). Total RNA was isolated and pooled (4 pools per tissue per day) from epididymal adipose (days 5 and 14) of the obese mice to analyze gene expression profiles using Agilent mouse oligo microarray slides representing > 20,000 genes. Numbers of genes differentially expressed by greater than or equal to twofold in epididymal adipose (days 5 and 14) were 29 and 125, respectively. It was concluded that, in adipose tissue, CLA increased expression of uncoupling proteins (1 and 2), carnitine palmitoyltransferase system, tumor necrosis factor-alpha (P < 0.05), and caspase-3 but decreased expression of peroxisome proliferator-activated receptor-gamma, glucose transporter-4, perilipin, caveolin-1, adiponectin, resistin, and Bcl-2 (P < 0.01). In conclusion, this experiment has revealed candidate genes that will be useful in elucidating mechanisms of adipose delipidation.