Multiple-filled skutterudites: high thermoelectric figure of merit through separately optimizing electrical and thermal transports

Skutterudites CoSb(3) with multiple cofillers Ba, La, and Yb were synthesized and very high thermoelectric figure of merit ZT = 1.7 at 850 K was realized. X-ray diffraction of the densified multiple-filled bulk samples reveals all samples are phase pure. High-resolution scanning transmission electron microscopy (STEM) and energy dispersive X-ray spectroscopy (EDS) analysis confirm that multiple guest fillers occupy the nanoscale-cages in the skutterudites. The fillers are further shown to be uniformly distributed and the Co-Sb skutterudite framework is virtually unperturbed from atomic scale to a few micrometers. Our results firmly show that high power factors can be realized by adjusting the total filling fraction of fillers with different charge states to reach the optimum carrier density, at the same time, lattice thermal conductivity can also be significantly reduced, to values near the glass limit of these materials, through combining filler species of different rattling frequencies to achieve broad-frequency phonon scattering. Therefore, partially filled skutterudites with multiple fillers of different chemical nature render unique structural characteristics for optimizing electrical and thermal transports in a relatively independent way, leading to continually enhanced ZT values from single- to double-, and finally to multiple-filled skutterudites. The idea of combining multiple fillers with different charge states and rattling frequencies for performance optimization is also expected to be valid for other caged TE compounds.     

Vibrational solvatochromism and electrochromism of infrared probe molecules containing C≡O, C≡N, C=O, or C-F vibrational chromophore

Solvatochromic vibrational frequency shifts of a few different infrared (IR) probe molecules have been studied by carrying out quantum chemistry calculations for a number of their water clusters. We are particularly focused on the vibrational solvatochromic and electrochromic effects on the CO, CN, and CF stretch modes in carbon monoxide, acetone, 4-cyanopyridine, p-tolunitrile, fluorobenzene, and 3-fluoropyridine. Using multiple interaction site antenna model, we show that their solvatochromic vibrational frequency shifts can be successfully described by considering spatially nonuniform electrostatic potential generated by the surrounding water molecules. It turns out that the CO and CF stretch mode frequencies are approximately proportional to the solvent electric field projected onto the bond axes, whereas the vibrational frequencies of the nitrile stretch mode in 4-cyanopyridine and p-tolunitrile are not. Consequently, it is confirmed that the vibrational Stark tuning rates of the CO and CF stretching modes can be directly used to describe their solvatochromic frequency shifts in condensed phases. However, the nitrile stretch mode frequency shift induced by solvent electrostatic potential appears to be more complicated than its electrochromic phenomenon. To examine the validity of the distributed interaction site model for solvatochromic frequency shifts of these vibrational chromophores, we thus calculated the vibrational Stark tuning rates of the CO, CN, and CF stretch modes and found that they are in good agreement with the experimental results found in literatures. This confirms that a collection of properly chosen distributed interaction sites can be an excellent electric antenna sensing local electrostatics that affects on vibrational frequencies of IR probe modes.     

Formation of amorphous zinc citrate spheres and their conversion to crystalline ZnO nanostructures

We report a method for synthesizing zinc citrate spheres at a low temperature (90 °C) under normal atmospheric pressure. The spherical structures were amorphous and had an average diameter of ～1.7 μm. The amorphous zinc citrate spheres could be converted into crystalline ZnO nanostructures in aqueous solutions by heating at 90 °C for 1 h. By local dissolution of the zinc citrate spheres, nucleation and growth of ZnO occurred on the surfaces of the amorphous zinc citrate spheres. The morphologies and exposed crystal faces of the crystalline ZnO nanostructures (structure I: oblate spheroid; structure II: prolate spheroid; structure III: hexagonal disk; structure IV: sphere) could be controlled simply by varying the solution composition (solutions I, II, III, or IV) in which the as-prepared amorphous zinc citrate spheres were converted. The concentration of citrate anions and solution pH played a decisive role in determining the morphologies and exposed crystal faces of the crystalline ZnO nanostructures. On the basis of experimental results, we propose a plausible mechanism for the conversion of amorphous zinc citrate spheres into the variety of observed ZnO structures.     

A multistage pathway for human prion protein aggregation in vitro: from multimeric seeds to β-oligomers and nonfibrillar structures

Aberrant protein aggregation causes numerous neurological diseases including Creutzfeldt-Jakob disease (CJD), but the aggregation mechanisms remain poorly understood. Here, we report AFM results on the formation pathways of β-oligomers and nonfibrillar aggregates from wild-type full-length recombinant human prion protein (WT) and an insertion mutant (10OR) with five additional octapeptide repeats linked to familial CJD. Upon partial denaturing, seeds consisting of 3-4 monomers quickly appeared. Oligomers of ~11-22 monomers then formed through direct interaction of seeds, rather than by subsequent monomer attachment. All larger aggregates formed through association of these β-oligomers. Although both WT and 10OR exhibited identical aggregation mechanisms, the latter oligomerized faster due to lower solubility and, hence, thermodynamic stability. This novel aggregation pathway has implications for prion diseases as well as others caused by protein aggregation.     

Hydrodynamic fractionation of finite size gold nanoparticle clusters

We demonstrate a high-resolution in situ experimental method for performing simultaneous size classification and characterization of functional gold nanoparticle clusters (GNCs) based on asymmetric-flow field flow fractionation (AFFF). Field emission scanning electron microscopy, atomic force microscopy, multi-angle light scattering (MALS), and in situ ultraviolet-visible optical spectroscopy provide complementary data and imagery confirming the cluster state (e.g., dimer, trimer, tetramer), packing structure, and purity of fractionated populations. An orthogonal analysis of GNC size distributions is obtained using electrospray-differential mobility analysis (ES-DMA). We find a linear correlation between the normalized MALS intensity (measured during AFFF elution) and the corresponding number concentration (measured by ES-DMA), establishing the capacity for AFFF to quantify the absolute number concentration of GNCs. The results and corresponding methodology summarized here provide the proof of concept for general applications involving the formation, isolation, and in situ analysis of both functional and adventitious nanoparticle clusters of finite size.     

Synthesis and characterization of a thiazolo[5,4-d]thiazole-based copolymer for high performance polymer solar cells

A highly processable, new semiconducting polymer, PCDTTz, based on alternating thiazolothiazole and carbazole units was synthesized. The new polymer exhibited a field-effect carrier mobility of up to 3.8 × 10(-3) cm(2) V(-1) s(-1) and bulk heterojunction solar cells made from PCDTTz produced a power conversion efficiency of 4.88% under AM 1.5 G (100 mW cm(-2)) conditions.     

Association of Paraoxonase 1 (PON1) polymorphisms with osteoporotic fracture risk in postmenopausal Korean women

There is increasing evidence of a biochemical link between lipid oxidation and bone metabolism. Paraoxonase 1 (PON1) prevents the oxidation of low-density lipoprotein (LDL) and metabolizes biologically active phospholipids in oxidized LDLs. Here, we performed association analyses of genetic variation in PON1 to ascertain its contribution to osteoporotic fractures (OFs) and bone mineral density (BMD). We directly sequenced the PON1 gene in 24 Korean individuals and identified 26 sequence variants. A large population of Korean postmenopausal women (n=1,329) was then genotyped for eight selected PON1 polymorphisms. BMD at the lumbar spine and femoral neck was measured using dual-energy X-ray absorptiometry. Lateral thoracolumbar (T4-L4) radiographs were obtained for vertebral fracture assessment, and the occurrence of non-vertebral fractures (i.e., wrist, hip, forearm, humerus, rib, and pelvis) was examined using self-reported data. Multivariate analyses showed that none of the polymorphisms was associated with BMD at either site. However, +5989A>G and +26080T>C polymorphisms were significantly associated with non-vertebral and vertebral fractures, respectively, after adjustment for covariates. Specifically, the minor allele of +5989A>G exerted a highly protective effect against non-vertebral fractures (OR=0.59, P=0.036), whereas the minor allele of +26080T>C was associated with increased susceptibility to vertebral fractures (OR=1.73, P=0.020). When the risk for any OFs (i.e., vertebral or non-vertebral) was considered, the statistical significance of both polymorphisms persisted (P=0.002-0.010). These results suggest that PON1 polymorphisms could be one of useful genetic markers for OF risk in postmenopausal women.     

Alveolar macrophages modulate allergic inflammation in a murine model of asthma

The role of alveolar macrophages (AMs) in the pathogenesis of asthma is still unknown. The aim of the present study was to investigate the effects of AM in the murine model of asthma. AMs were selectively depleted by liposomes containing clodronate just before allergen challenges, and changes in inflammatory cells and cytokine concentrations in bronchoalveolar lavage (BAL) fluid were measured. AMs were then adoptively transferred to AM-depleted sensitized mice and changes were measured. Phenotypic changes in AMs were evaluated after in vitro allergen stimulation. AM-depletion after sensitization significantly increased the number of eosinophils and lymphocytes and the concentrations of IL-4, IL-5 and GM-CSF in BAL fluid. These changes were significantly ameliorated only by adoptive transfer of unsensitized AMs, not by sensitized AMs. In addition, in vitro allergen stimulation of AMs resulted in their gaining the ability to produce inflammatory cytokines, such as IL-1β, IL-6 and TNF-α, and losing the ability to suppress GM-CSF concentrations in BAL fluid. These findings suggested that AMs worked probably through GM-CSF-dependent mechanisms, although further confirmatory experiments are needed. Our results indicate that the role of AMs in the context of airway inflammation should be re-examined.