No abstract

We present here an ultrasensitive electrochemical biosensor based on a lectin biorecognition capable to detect concentrations of glycoproteins down to attomolar (aM) level by investigation of changes in the charge transfer resistance (Rct) using electrochemical impedance spectroscopy (EIS). On polycrystalline gold modified by an aminoalkanethiol linker layer, gold nanoparticles were attached. A Sambucus nigra agglutinin was covalently immobilised on a mixed self-assembled monolayer formed on gold nanoparticles and finally, the biosensor surface was blocked by poly(vinyl alcohol). The lectin biosensor was applied for detection of sialic acid containing glycoproteins fetuin and asialofetuin. Building of a biosensing interface was carefully characterised by a broad range of techniques such as electrochemistry, EIS, atomic force microscopy, scanning electron microscopy and surface plasmon resonance with the best performance of the biosensor achieved by application of HS-(CH2)11-NH2 linker and gold nanoparticles with a diameter of 20 nm. The lectin biosensor responded to an addition of fetuin (8.7% of sialic acid) with sensitivity of (338 ± 11) Ω decade(-1) and to asialofetuin (≤ 0.5% of sialic acid) with sensitivity of (109 ± 10) Ω decade(-1) with a blank experiment with oxidised asialofetuin (without recognisable sialic acid) revealing sensitivity of detection of (79 ± 13) Ω decade(-1). These results suggest the lectin biosensor responded to changes in the glycan amount in a quantitative way with a successful validation by a lectin microarray. Such a biosensor device has a great potential to be employed in early biomedical diagnostics of diseases such as arthritis or cancer, which are connected to aberrant glycosylation of protein biomarkers in biological fluids.

We report the first finding of diamond and moissanite in metasedimentary crustal rocks of Pohorje Mountains (Slovenia) in the Austroalpine ultrahigh‐pressure (UHP) metamorphic terrane of the Eastern Alps. Microscopic observations and Raman spectroscopy show that diamond occurs in situ as inclusions in garnet, being heterogeneously distributed. Under the optical microscope, diamond‐bearing inclusions are of cuboidal to rounded shape and of pinkish, yellow to brownish colour. The Raman spectra of the investigated diamond show a sharp, first order peak of sp3‐bonded carbon, in most cases centred between 1332 and 1330 cm−1, with a full width at half maximum between 3 and 5 cm−1. Several spectra show Raman bands typical for disordered graphitic (sp2‐bonded) carbon. Detailed observations show that diamond occurs either as a monomineralic, single‐crystal inclusion or it is associated with SiC (moissanite), CO2 and CH4 in polyphase inclusions. This rare record of diamond occurring with moissanite as fluid‐inclusion daughter minerals implies the crystallization of diamond and moissanite from a supercritical fluid at reducing conditions. Thermodynamic modelling suggests that diamond‐bearing gneisses attained P–T conditions of ≥3.5 GPa and 800–850 °C, similar to eclogites and garnet peridotites. We argue that diamond formed when carbonaceous sediment underwent UHP metamorphism at mantle depth exceeding 100 km during continental subduction in the Late Cretaceous (c. 95–92 Ma). The finding of diamond confirms UHP metamorphism in the Pohorje Mountains, the most deeply subducted part of Austroalpine units.