Electrochemical studies of capped metalloporphyrous

Issued as Progress report summary, and Application for continuation grant, Project no. G-33-695 (continues G-33-617; continued by G-33-679

Peeling of Long, Straight Carbon Nanotubes from Surfaces

The adhesion of long, straight, single-walled carbon nanotubes to surfaces is examined usingmultidimensional force spectroscopy. We observed characteristic signatures in the deflection and frequency response of the cantilever indicative of nanotube buckling and slip-stickmotion as a result of compression and subsequent adhesion and peeling of the nanotube fromthe surface.The spring constant and the elastic modulus of the SWNT were estimated from the frequency shifts under tension. Using elastica modeling for postbuckled columns, we have determined the static coefficient of friction for the SWNT on alkanethiol-modified gold surfaces and showed that it varies with the identity of the monolayer terminal group.Fil: Barker, Kane M.. Georgia Institute of Technology. School of Chemistry and Biochemistry; Estados UnidosFil: Poggi, Mark A.. Georgia Institute of Technology. School of Chemistry and Biochemistry; Estados UnidosFil: Lizarraga, Leonardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Centro de Investigaciones en Bionanociencias "Elizabeth Jares Erijman"; Argentina. Georgia Institute of Technology. School of Chemistry and Biochemistry; Estados UnidosFil: Lillehei, Peter T.. NASA Langley Research Center. Advanced Materials and Processing Branch; Estados UnidosFil: Ferri, Aldo. Georgia Institute of Technology. George W. Woodruff School of Mechanical Engineering; Estados UnidosFil: Bottomley, Lawrence A.. Georgia Institute of Technology. School of Chemistry and Biochemistry; Estados Unido

The REFOLD database: a tool for the optimization of protein expression and refolding

A large proportion of proteins expressed in Escherichia coli form inclusion bodies and thus require renaturation to attain a functional conformation for analysis. In this process, identifying and optimizing the refolding conditions and methodology is often rate limiting. In order to address this problem, we have developed REFOLD, a web-accessible relational database containing the published methods employed in the refolding of recombinant proteins. Currently, REFOLD contains >300 entries, which are heavily annotated such that the database can be searched via multiple parameters. We anticipate that REFOLD will continue to grow and eventually become a powerful tool for the optimization of protein renaturation. REFOLD is freely available at

Well-organized raspberry-like Ag@Cu bimetal nanoparticles for highly reliable and reproducible surface-enhanced Raman scattering

Surface-enhanced Raman scattering (SERS) is ideally suited for probing and mapping surface species and incipient phases on fuel cell electrodes because of its high sensitivity and surface-selectivity, potentially offering insights into the mechanisms of chemical and energy transformation processes. In particular, bimetal nanostructures of coinage metals (Au, Ag, and Cu) have attracted much attention as SERS-active agents due to their distinctive electromagnetic field enhancements originated from surface plasmon resonance. Here we report excellent SERS-active, raspberry-like nanostructures composed of a silver (Ag) nanoparticle core decorated with smaller copper (Cu) nanoparticles, which displayed enhanced and broadened UV-Vis absorption spectra. These unique Ag@Cu raspberry nanostructures enable us to use blue, green, and red light as the excitation laser source for surface-enhanced Raman spectroscopy (SERS) with a large enhancement factor (EF). A highly reliable SERS effect was demonstrated using Rhodamine 6G (R6G) molecules and a thin film of gadolinium doped ceria.close3

Embracing ligands. Synthesis, characterisation and the correlation between 59Co NMR and ligand field parameters of Co(III) complexes with a new class of nitrogen-thioether multidentate ligand

The syntheses of the hexadentate ligands 2,2,10,10-tetra(methyleneamine)-4,8-dithiaundecane (PrN(4)S(2)amp), 2,2,11,11-tetra(methyleneamine)-4,9-dithiadodecane (BuN(4)S(2)amp), and 1,2-bis(4,4-methyleneamine)-2-thiapentyl)benzene (XyN(4)S(2)amp) are reported and the complexes [Co(RN(4)S(2)amp)](3+) (R = Pr, Bu, Xy) characterised by single crystal X-ray study. The low-temperature (11 K) absorption spectra have been measured in Nafion films. From the observed positions of both spin-allowed (1)A(1g) --> T-1(1g) and (1)A(1g) --> T-1(2g) and spin forbidden (1)A(1g) --> T-3(1g) and (1)A(1g) --> T-3(2g) bands, octahedral ligand-field parameters (10D(q), B and C) have been determined. DFT calculations suggest that significant interaction between the d-d and CT excitations occurs for the complexes. The calculations offer an explanation for the observed deviations from linearity of the relationship between Co-59 magnetogyric ratio and beta(DeltaE)(-1) (beta = the nephelauxetic ratio; DeltaE the energy of the (1)A(1g) --> T-1(1g) transition) for a series of amine and mixed amine/thioether donor complexes

The structure of the bacterial oxidoreductase enzyme DsbA in complex with a peptide reveals a basis for substrate specificity in the catalytic cycle of DsbA enzymes

Oxidative protein folding in Gram-negative bacteria results in the formation of disulfide bonds between pairs of cysteine residues. This is a multistep process in which the dithiol-disulfide oxidoreductase enzyme, DsbA, plays a central role. The structure of DsbA comprises an all helical domain of unknown function and a thioredoxin domain, where active site cysteines shuttle between an oxidized, substrate-bound, reduced form and a DsbB-bound form, where DsbB is a membrane protein that reoxidizes DsbA. Most DsbA enzymes interact with a wide variety of reduced substrates and show little specificity. However, a number of DsbA enzymes have now been identified that have narrow substrate repertoires and appear to interact specifically with a smaller number of substrates. The transient nature of the DsbA-substrate complex has hampered our understanding of the factors that govern the interaction of DsbA enzymes with their substrates. Here we report the crystal structure of a complex between Escherichia coli DsbA and a peptide with a sequence derived from a substrate. The binding site identified in the DsbA-peptide complex was distinct from that observed for DsbB in the DsbA-DsbB complex. The structure revealed details of the DsbA-peptide interaction and suggested a mechanism by which DsbA can simultaneously show broad specificity for substrates yet exhibit specificity for DsbB. This mode of binding was supported by solution nuclear magnetic resonance data as well as functional data, which demonstrated that the substrate specificity of DsbA could be modified via changes at the binding interface identified in the structure of the comple

High-temperature surface enhanced Raman spectroscopy for in situ study of solid oxide fuel cell materials

In situ probing of surface species and incipient phases is vital to unraveling the mechanisms of chemical and energy transformation processes. Here we report Ag nanoparticles coated with a thin-film SiO2 shell that demonstrate excellent thermal robustness and chemical stability for surface enhanced Raman spectroscopy (SERS) study of solid oxide fuel cell materials under in situ conditions (at ???400 ??C).close3

Multiple novel prostate cancer susceptibility signals identified by fine-mapping of known risk loci among Europeans

Genome-wide association studies (GWAS) have identified numerous common prostate cancer (PrCa) susceptibility loci. We have fine-mapped 64 GWAS regions known at the conclusion of the iCOGS study using large-scale genotyping and imputation in 25 723 PrCa cases and 26 274 controls of European ancestry. We detected evidence for multiple independent signals at 16 regions, 12 of which contained additional newly identified significant associations. A single signal comprising a spectrum of correlated variation was observed at 39 regions; 35 of which are now described by a novel more significantly associated lead SNP, while the originally reported variant remained as the lead SNP only in 4 regions. We also confirmed two association signals in Europeans that had been previously reported only in East-Asian GWAS. Based on statistical evidence and linkage disequilibrium (LD) structure, we have curated and narrowed down the list of the most likely candidate causal variants for each region. Functional annotation using data from ENCODE filtered for PrCa cell lines and eQTL analysis demonstrated significant enrichment for overlap with bio-features within this set. By incorporating the novel risk variants identified here alongside the refined data for existing association signals, we estimate that these loci now explain ∼38.9% of the familial relative risk of PrCa, an 8.9% improvement over the previously reported GWAS tag SNPs. This suggests that a significant fraction of the heritability of PrCa may have been hidden during the discovery phase of GWAS, in particular due to the presence of multiple independent signals within the same regio

Design, fabrication, and testing of microDSC sensors

Issued as final reportSensor Tec