Mechanistic studies of pyridinium electrochemistry: alternative chemical pathways in the presence of CO2.

Protonated heterocyclic amines, such as pyridinium, have been utilized as catalysts in the electrocatalytic reduction of carbon dioxide. While these represent a new and exciting class of electrocatalysts, the details of the mechanism and faradaic processes occurring in solution are unclear. We report a series of cyclic voltammetry experiments involving Pt, Ag, Au, and Cu electrodes, under both aqueous and nonaqueous conditions, directed towards gaining an improved mechanistic understanding of pyridinium electrochemistry. Surface-enhanced Raman (SER) spectroelectrochemistry was also performed on Cu film-over-nanosphere electrodes in order to identify adsorbed species. It was found that the reduction potential of pyridinium (-0.58 V vs. SCE) and its electrochemical reversibility are unique features of platinum electrodes. In contrast, the reduction potentials on Ag, Au, and Cu electrodes are ∼400 mV more negative than Pt in both the presence and the absence of CO2. SER spectroelectrochemistry of pyridinium solutions shows no evidence for a pyridinium radical or a pyridinium ion. Increased cathodic current in the presence of CO2 is only detected at scan rates less than 10 mV s(-1) in aqueous solutions. The addition of CO2 resulted in a shift in the potential for the hydrogen evolution reaction. Pyridinium electrochemistry was observed under nonaqueous conditions; however no increase in cathodic current was observed when CO2 was added to the solution. Based on this set of results it is concluded that the reduction potential of pyridinium is surface dependent, CO2 acts as a pseudo-reserve of H(+), and pyridinium and CO2 create an alternative mechanism for hydrogen evolution.

Observation of multiple vibrational modes in ultrahigh vacuum tip-enhanced Raman spectroscopy combined with molecular-resolution scanning tunneling microscopy.

Multiple vibrational modes have been observed for copper phthalocyanine (CuPc) adlayers on Ag(111) using ultrahigh vacuum (UHV) tip-enhanced Raman spectroscopy (TERS). Several important new experimental features are introduced in this work that significantly advance the state-of-the-art in UHV-TERS. These include (1) concurrent sub-nm molecular resolution STM imaging using Ag tips with laser illumination of the tip-sample junction, (2) laser focusing and Raman collection optics that are external to the UHV-STM that has two cryoshrouds for future low temperature experiments, and (3) all sample preparation steps are carried out in UHV to minimize contamination and maximize spatial resolution. Using this apparatus we have been able to demonstrate a TERS enhancement factor of 7.1 × 10(5). Further, density-functional theory calculations have been carried out that allow quantitative identification of eight different vibrational modes in the TER spectra. The combination of molecular-resolution UHV-STM imaging with the detailed chemical information content of UHV-TERS allows the interactions between large polyatomic molecular adsorbates and specific binding sites on solid surfaces to be probed with unprecedented spatial and spectroscopic resolution.

Wulff construction for alloy nanoparticles.

The Wulff construction is an invaluable tool to understand and predict the shape of nanoparticles. We demonstrate here that this venerable model, which gives a size-independent thermodynamic shape, becomes size dependent in the nanoscale regime for an alloy and that the infinite reservoir approximation breaks down. The improvements in structure and energetic modeling have wide-ranging implications both in areas where energetics govern (e.g., nucleation and growth) and where the surface composition is important (e.g., heterogeneous catalysis).

A method to correlate optical properties and structures of metallic nanoparticles.

The optical response of individual nanoparticles is strongly influenced by their structures. In this report, we present a quick and simple pattern-matching based approach in which optical images of nanoparticles from localized surface plasmon resonance and single-molecule surface-enhanced Raman spectroscopy were used in conjunction with transmission electron microscopy for correlation of optical responses and the nanostructures of exactly the same nanoparticles or clusters of nanoparticles.

Functional consequences of cyclin D1/BRCA1 interaction in breast cancer cells.

The inheritance of one defective BRCA1 or BRCA2 allele predisposes an individual to developing breast and ovarian cancers. BRCA1 is a multifunctional tumor suppressor protein, which through interaction with a vast array of proteins has implications in processes such as cell cycle, transcription, DNA damage response and chromatin remodeling. Conversely, the oncogene, cyclin D1 is overexpressed in about 35% of all breast cancer cases. In this study, we provide detailed analyses on the phosphorylation state of BRCA1 by cyclin D1/cdk4 complexes. In particular, we have identified Ser 632 of BRCA1 as a cyclin D1/cdk4 phosphorylation site in vitro. Using chromatin immunoprecipitation assays, we observed that the inhibition of cyclin D1/cdk4 activity resulted in increased BRCA1 DNA binding at particular promoters in vivo. In addition, we identified multiple novel genes that are bound by BRCA1 in vivo. Collectively, these results indicate that cyclin D1/cdk4-mediated phosphorylation of BRCA1 inhibits the ability of BRCA1 to be recruited to particular promoters in vivo. Therefore, cyclin D1/Cdk4 phosphorylation of BRCA1 could provide a mechanism to interfere with the DNA-dependent activities of BRCA1.

Biological applications of localised surface plasmonic phenomenae.

Researchers and industrialists have taken advantage of the unusual optical, magnetic, electronic, catalytic, and mechanical properties of nanomaterials. Nanoparticles and nanoscale materials have proven to be useful for biological uses. Nanoscale materials hold a particular interest to those in the biological sciences because they are on the same size scale as biological macromolecules, proteins and nucleic acids. The interactions between biomolecules and nanomaterials have formed the basis for a number of applications including detection, biosensing, cellular and in situ hybridisation labelling, cell tagging and sorting, point-of-care diagnostics, kinetic and binding studies, imaging enhancers, and even as potential therapeutic agents. Noble metal nanoparticles are especially interesting because of their unusual optical properties which arise from their ability to support surface plasmons. In this review the authors focus on biological applications and technologies that utilise two types of related plasmonic phenomonae: localised surface plasmon resonance (LSPR) spectroscopy and surface-enhanced Raman spectroscopy (SERS). The background necessary to understand the application of LSPR and SERS to biological problems is presented and illustrative examples of resonant Rayleigh scattering, refractive index sensing, and SERS-based detection and labelling are discussed.

Surface-enhanced Raman spectroscopy biosensors: excitation spectroscopy for optimisation of substrates fabricated by nanosphere lithography.

In the 28 years since its discovery, surface-enhanced Raman scattering (SERS) has progressed from model system studies of pyridine on a roughened silver electrode to state-of-the-art surface science studies and real-world sensing applications. Each year, the number of SERS publications increases as nanoscale material design techniques advance and the importance of trace analyte detection increases. To achieve the lowest limits of detection, both the relationship between surface nanostructure and laser excitation wavelength and the analyte-surface binding chemistry must be carefully optimised. This work exploits the highly tunable nature of nanoparticle optical properties to establish the optimisation conditions. Two methods are used to study the optimised conditions of the SERS substrate: plasmon-sampled and wavelength-scanned surfaced Raman excitation spectroscopy (SERES). The SERS enhancement condition is optimised when the energy of the localised surface plasmon resonance of the nanostructures lies between the energy of the excitation wavelength and the energy of the vibration band of interest. These optimised conditions enabled the development of SERS-based sensors for the detection of a Bacillus anthracis biomarker and glucose in a serum-protein matrix.

Low-loss liquid-core optical fiber for low-refractive-index liquids: fabrication, characterization, and application in Raman spectroscopy.

We describe a liquid-core optical fiber based on capillary tubing of Teflon AF 2400, which is a clear, amorphous fluoropolymer having a refractive index of 1.29. When filled with virtually any transparent liquid, the fiber is capable of transmitting light by total internal reflection. Loss below 3 dB/microm is demonstrated throughout much of the visible region for a 250-microm-i.d. fiber filled with water. The utility of this device in enhancing the intensity of Raman spectra of core liquids is demonstrated.

Evidence for retention of biological activity of a non-heme iron enzyme adsorbed on a silver colloid: a surface-enhanced resonance Raman scattering study.

The structure and catalytic properties of the enzyme (E) chlorocatechol dioxygenase (CCD) adsorbed on a citrate-reduced silver colloid are analyzed by surface-enhanced resonance Raman spectroscopy (SERRS). This is the first SERRS study of a non-heme metalloenzyme. It is demonstrated that the native conformation of CCD is retained in the adsorbed state by comparison of resonance Raman scattering (RRS) from CCD in solution with SERRS from CCD adsorbed on the silver colloid. Both spectra show clear evidence of vibrational bands typical of iron-tyrosinate proteins. Furthermore, it is demonstrated that adsorbed CCD retains 60-85% of its enzymatic activity in the reaction of catechol substrate (S) with O2 to give the dioxygenated product (P) cis,cis-muconate. This is accomplished by enzyme assays of Ag-adsorbed CCD and comparison of the SERRS of Ag-adsorbed enzyme-substrate (ES) complex under anaerobic conditions with that of Ag-adsorbed ES in the presence of dioxygen. The SERRS difference spectrum, ES(aerobic)--ES(anaerobic), shows clear evidence for the appearance of the vibrational modes of adsorbed product. The analogous SERR difference spectroscopy experiment is also carried out for the enzyme-inhibitor (EI) complex of CCD with tetrachlorocatechol (TCC). Slow turnover of CCD-TCC is observed by SERRS on exposure to dioxygen which is consistent with the slow rate of turnover of TCC by CCD in solution.

A new "cool" lens capsulotomy laser.

A new infrared "cool" laser has been developed to facilitate extracapsular cataract extraction. It has been used to produce clinically and histologically safe, effective anterior and posterior capsulotomies in animal studies. This newly developed ophthalmic laser system operates at a wavelength of 1220 nm, and has a maximal retinal absorption of only 0.1%. This is 100 times less than the retinal absorption at the wavelength of the neodymium-YAG laser. Retinal safety is not dependent on the creation of a plasma shield or on mechanical safety devices, as it is for the neodymium-YAG laser. The 1220 nm wavelength also enhances the "cool laser" effect, so that only 1/100 of the power intensity of the modelocked neodymium-YAG laser is required. In addition to lowering the required ocular exposure this may reduce the likelihood of intraocular damage. To our knowledge this represents the first intraocular use of a laser at this wavelength region (1200 to 1290 nm). A second generation laser, using erbium yttrium lithium fluoride (YLF) as its lasing medium, is currently being developed.

Resonance Raman studies and structure of a sulfide complex of methemerythrin.

The complex of sulfide and methemerythrin has been characterized by resonance Raman spectroscopy. At pH 8.0 the complex contains two irons and one S2- at the active site. The resonance Raman spectrum of the sulfidomethemerythrin complex contains only one vibration, at 444 cm-1. This vibration is assigned to an iron-sulfide stretch. The possibility that sulfidomethemerythrin contains a mu-sulfido bridge. FeIII-S2-FeIII, analogous to the proposed mu-oxo bridge in azidomethemerythrin is discussed.