Rapid Raman mapping for chocolate analysis

Raman microspectroscopy mapping capabilities have advanced significantly and have been applied to cell and pharmaceutical tablet formulation analysis. Bulk Raman investigations of food and their constituents have been carried out but little work exists on the application of Raman mapping capabilities to food. Here, we assess the applicability of Raman microspectroscopy mapping to the analysis of chocolate and examine both white and milk chocolate samples. It was found that the sucrose, lactose and fat constituents of white chocolate could be extracted and spatially resolved, indicating that the sucrose and lactose formed particles within a matrix of 'fats'. Fluorescence from cocoa solids present in milk chocolate prevented chemical mapping with the instrumentation used. Raman mapping should provide a powerful analytical technique for the analysis and development of food products

Ultrasensitive Dual ELONA/SERS-RPA Multiplex Diagnosis of Antimicrobial Resistance

\ua9 2024 The Authors. Published by American Chemical Society.Antimicrobial resistance (AMR) is a significant global health threat concern, necessitating healthcare practitioners to accurately prescribe the most effective antimicrobial agents with correct doses to combat resistant infections. This is necessary to improve the therapeutic outcomes for patients and prevent further increase in AMR. Consequently, there is an urgent need to implement rapid and sensitive clinical diagnostic methods to identify resistant pathogenic strains and monitor the efficacy of antimicrobials. In this study, we report a novel proof-of-concept magnetic scaffold-recombinase polymerase amplification (RPA) technique, coupled with an enzyme-linked oligonucleotide assay (ELONA) and surface-enhanced Raman scattering (SERS) detection, aimed at selectively amplifying and detecting the DNA signature of three resistant carbapenemase genes, VIM, KPC, and IMP. To achieve this, streptavidin-coated magnetic beads were functionalized with biotin-modified forward primers. RPA was conducted on the surface of the beads, resulting in an immobilized duplex amplicon featuring a single overhang tail specific to each gene. These tails were subsequently hybridized with recognition HRP probes conjugated to a complementary single-stranded oligonucleotide and detected colorimetrically. Additionally, they underwent hybridization with similar selective SERS probes and were measured using a handheld Raman spectrometer. The resulting quantification limits were at subpicomolar level for both assays, allowing the potential for early diagnosis. Moreover, we demonstrated the platform capability to conduct a multiplex RPA-SERS detection of the three genes in a single tube. Compared to similar approaches like PCR, RPA offers advantages of speed, affordability, and isothermal operation at 37 \ub0C, eliminating the need for a thermal cycler. The whole assay was completed within <2 h. Therefore, this novel magnetic scaffold ELONA/SERS-RPA platform, for DNA detection, demonstrated excellent capability for the rapid monitoring of AMR in point-of-care applications, in terms of sensitivity, portability, and speed of analysis

Silver colloids as plasmonic substrates for direct label-free surface-enhanced Raman scattering analysis of DNA

Ultrasensitive direct SERS analysis offers a powerful analytical tool for the structural characterization and classification of nucleic acids. However, acquisition of reliable spectral fingerprints of such complex biomolecules poses important challenges. In recent years, many efforts have been devoted to overcome these limitations, mainly implementing silver colloids as plasmonic substrates. However, a reliable cross-comparison of results reported in the recent literature is extremely hard to achieve, mostly due to the broad set of different surface properties of the plasmonic nanoparticles. Herein, we perform a thorough investigation of the role played by the metal/liquid interface composition of silver colloids in the direct label-free SERS analysis of DNA. Target molecules of increasing complexity, from short homopolymeric strands to long genomic duplexes, were used as probes. We demonstrate how apparently subtle changes in the colloidal surface chemistry can dramatically modify the affinity and the final SERS spectral profile of DNA. This has significant implications for the future design of new analytical strategies for the detection of DNA using SERS without labels

Introducing 12 new dyes for use with oligonucleotide functionalised silver nanoparticles for DNA detection with SERS

Oligonucleotide functionalised metallic nanoparticles (MNPs) have been shown to be an effective tool in the detection of disease-specific DNA and have been employed in a number of diagnostic assays. The MNPs are also capable of facilitating surface enhanced Raman scattering (SERS) enabling detection to become highly sensitive. Herein we demonstrate the expansion of the range of specific SERS-active oligonucleotide MNPs through the use of 12 new Raman-active monomethine and trimethine chalcogenopyrylium and benzochalcogenopyrylium derivatives. This has resulted in an increased ability to carry out multiplexed analysis beyond the current small pool of resonant and non-resonant Raman active molecules, that have been used with oligonucleotide functionalised nanoparticles. Each dye examined here contains a variation of sulphur and selenium atoms in the heterocyclic core, together with phenyl, 2-thienyl, or 2-selenophenyl substituents on the 2,2’,6, and 6’ positions of the chalcogenopyrylium dyes and 2 and 2’ positions of the benzochalcogenopyrylium dyes. The intensity of SERS obtained from each dye upon conjugate hybridisation with a complementary single stranded piece of DNA was explored. Differing concentrations of each dye (1000, 3000, 5000 and 7000 equivalents per NP-DNA conjugate) were used to understand the effects of Raman reporter coating on the overall Raman intensity. It was discovered that dye concentration did not affect the target/control ratio, which remained relatively constant throughout and that a lower concentration of Raman reporter was favourable in order to avoid NP instability. A relationship between the dye structure and SERS intensity was discovered, leaving scope for future development of specific dyes containing substituents favourable for discrimination in a multiplex by SERS. Methine dyes containing S and Se in the backbone and at least 2 phenyls as substituents give the highest SERS signal following DNA-induced aggregation. Principal component analysis (PCA) was performed on the data to show differentiation between the dye classes and highlight possible future multiplexing capabilities of the 12 investigated dyes

The Mount Perkins block, northwestern Arizona: An exposed cross section of an evolving, preextensional to synextensional magmatic system

This is the published version. Reuse is subject to Society of Exploration Geophysicists terms of use and conditions.The steeply tilted Mount Perkins block, northwestern Arizona, exposes a cross section of a magmatic system that evolved through the onset of regional extension. New 40Ar/39Ar ages of variably tilted (0–90°) volcanic strata bracket extension between 15.7 and 11.3 Ma. Preextensional intrusive activity included emplacement of a composite Miocene laccolith and stock, trachydacite dome complex, and east striking rhyolite dikes. Related volcanic activity produced an ∼18–16 Ma stratovolcano, cored by trachydacite domes and flanked by trachydacite-trachyandesite flows, and ∼16 Ma rhyolite flows. Similar compositions indicate a genetic link between the stratovolcano and granodioritic phase of the laccolith. Magmatic activity synchronous with early regional extension (15.7–14.5 Ma) generated a thick, felsic volcanic sequence, a swarm of northerly striking subvertical rhyolite dikes, and rhyolite domes. Field relations and compositions indicate that the dike swarm and felsic volcanic sequence are cogenetic. Modes of magma emplacement changed during the onset of extension from subhorizontal sheets, east striking dikes, and stocks to northerly striking, subvertical dike swarms, as the regional stress field shifted from nearly isotropic to decidedly anisotropic with an east-west trending, horizontal least principal stress. Preextensional trachydacitic and preextensional to synextensional rhyolitic magmas were part of an evolving system, which involved the ponding of mantle-derived basaltic magmas and ensuing crustal melting and assimilation at progressively shallower levels. Major extension halted this system by generating abundant pathways to the surface (fractures), which flushed out preexisting crustal melts and hybrid magmas. Remaining silicic melts were quenched by rapid, upper crustal cooling induced by tectonic denudation. These processes facilitated eruption of mafic magmas. Accordingly, silicic magmatism at Mount Perkins ended abruptly during peak extension ∼14.5 Ma and gave way to mafic magmatism, which continued until extension ceased

Surface science of soft scorpionates

The chemisorption of the soft scorpionate Li[PhTmMe] onto silver and gold surfaces is reported. Surface enhanced Raman spectroscopy in combination with the Raman analysis of suitable structural models, namely, [Cu(κ3-S,S,S-PhTmMe)(PCy3)], [Ag(κ3-S,S,S-PhTmMe)(PCy3)], [Ag(κ2-S,S-PhTmMe)(PEt3)], and [Au(κ1-S-PhTmMe)(PCy3)], are employed to identify the manner in which this potentially tridentate ligand binds to these surfaces. On colloidal silver surface-enhanced Raman spectroscopy (SERS) spectra are consistent with PhTmMe binding in a didentate fashion to the surface, holding the aryl group in close proximity to the surface. In contrast, on gold colloid, we observe that the species prefers a monodentate coordination in which the aryl group is not in close proximity to the surface

Quantitative surface-enhanced resonance Raman scattering of phthalocyanine-labelled oligonucleotides

The evaluation of phthalocyanine labels for the surface-enhanced resonance Raman scattering (SERRS) detection of oligonucleotides is reported. Three phthalocyanine-labelled oligonucleotides were assessed, each containing a different metal centre. Detection limits for each labelled oligonucleotide were determined using two excitation frequencies where possible. Limits of detection as low as 2.8 × 10−11 mol. dm−3 were obtained which are comparable to standard fluorescently labelled probes used in previous SERRS studies. The identification of two phthalocyanine-labelled oligonucleotides without separation was also demonstrated indicating their suitability for multiplexing. This study extends the range of labels suitable for quantitative surface-enhanced resonance Raman scattering with silver nanoparticles and offers more flexibility and choice when considering SERRS for quantitative DNA detection

Quantitative surface-enhanced resonance Raman scattering of phthalocyanine-labelled oligonucleotides

The evaluation of phthalocyanine labels for the surface-enhanced resonance Raman scattering (SERRS) detection of oligonucleotides is reported. Three phthalocyanine-labelled oligonucleotides were assessed, each containing a different metal centre. Detection limits for each labelled oligonucleotide were determined using two excitation frequencies where possible. Limits of detection as low as 2.8 × 10−11 mol. dm−3 were obtained which are comparable to standard fluorescently labelled probes used in previous SERRS studies. The identification of two phthalocyanine-labelled oligonucleotides without separation was also demonstrated indicating their suitability for multiplexing. This study extends the range of labels suitable for quantitative surface-enhanced resonance Raman scattering with silver nanoparticles and offers more flexibility and choice when considering SERRS for quantitative DNA detection