Single molecule detection from a large-scale SERS-active Au79Ag21 substrate

Detecting and identifying single molecules are the ultimate goal of analytic sensitivity. Single molecule detection by surface-enhanced Raman scattering (SM-SERS) depends predominantly on SERS-active metal substrates that are usually colloidal silver fractal clusters. However, the high chemical reactivity of silver and the low reproducibility of its complicated synthesis with fractal clusters have been serious obstacles to practical applications of SERS, particularly for probing single biomolecules in extensive physiological environments. Here we report a large-scale, free standing and chemically stable SERS substrate for both resonant and nonresonant single molecule detection. Our robust substrate is made from wrinkled nanoporous Au79Ag21 films that contain a high number of electromagnetic “hot spots” with a local SERS enhancement larger than 109. This biocompatible gold-based SERS substrate with superior reproducibility, excellent chemical stability and facile synthesis promises to be an ideal candidate for a wide range of applications in life science and environment protection

Black manganese-rich crusts on a Gothic cathedral

Black manganese-rich crusts are found worldwide on the façades of historical buildings. In this study, they were studied exemplarily on the façade of the Freiburger Münster (Freiburg Minster), Germany, and measured in-situ by portable X-ray fluorescence (XRF). The XRF was calibrated to allow the conversion from apparent mass fractions to Mn surface density (Mn mass per area), to compensate for the fact that portable XRF mass fraction measurements from thin layers violate the assumption of a homogeneous measurement volume. Additionally, 200-nm femtosecond laser ablation-inductively coupled plasma-mass spectrometry (fs LA-ICP-MS) measurements, scanning transmission X-ray microscopy-near edge X-ray absorption fine structure spectroscopy (STXM-NEXAFS), Raman spectroscopy, and imaging by light microscopy were conducted to obtain further insight into the crust material, such as potential biogenic contributions, element distributions, trace element compositions, and organic functional groups. While black crusts of various types are present at many places on the minster's facade, crusts rich in Mn (with a Mn surface density >150 μg cm−2) are restricted to a maximum height of about 7 m. The only exceptions are those developed on the Renaissance-Vorhalle (Renaissance Portico) at a height of about 8 m. This part of the façade had been cleaned and treated with a silicon resin as recently as 2003. These crusts thus accumulated over a period of only 12 years. Yet, they are exceptionally Mn-rich with a surface density of 1200 μg cm−2, and therefore require an accumulation rate of about 100 μg cm−2 Mn per year. Trace element analyses support the theory that vehicle emissions are responsible for most of the Mn supply. Lead, barium, and zinc correlate with manganese, indicating that tire material, brake pads, and resuspended road dust are likely to be the element sources. Microscopic investigations show no organisms on or in the Mn-rich crusts. In contrast, Mn-free black crusts sampled at greater heights (>8 m) exhibited fungal and cyanobacterial encrustation. Carbon-rich spots were found by STXM-NEXAFS underneath one of the Mn-rich crusts. However, these carbon occurrences originate from soot and polycyclic aromatic hydrocarbons (PAHs) deposited on top of the crust, rather than from organisms responsible for the crust's formation, as shown by STXM-NEXAFS and Raman spectroscopic measurements. Our results suggest that the crusts develop abiogenically, with vehicle emissions as dominant element sources

Catalytic processes monitored at the nanoscale with tip-enhanced Raman spectroscopy

Heterogeneous catalysts play a pivotal role in the chemical industry, but acquiring molecular insights into functioning catalysts remains a significant challenge1, 2, 3, 4. Recent advances in micro-spectroscopic approaches have allowed spatiotemporal information to be obtained on the dynamics of single active sites and the diffusion of single molecules5, 6. However, these methods lack nanometre-scale spatial resolution and/or require the use of fluorescent labels. Here, we show that time-resolved tip-enhanced Raman spectroscopy can monitor photocatalytic reactions at the nanoscale. We use a silver-coated atomic force microscope tip to both enhance the Raman signal and to act as the catalyst. The tip is placed in contact with a self-assembled monolayer of p-nitrothiophenol molecules adsorbed on gold nanoplates. A photocatalytic reduction process is induced at the apex of the tip with green laser light, while red laser light is used to monitor the transformation process during the reaction. This dual-wavelength approach can also be used to observe other molecular effects such as monolayer diffusion

Excretion of Eimeria spp. Oocysts in young lambs following iron supplementation

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