Microsphere packages of carotenoids: intact sea urchin eggs tracked by Raman spectroscopy tools.

Although natural exposure to ambient UV radiation in oligotrophic seawater at small depths can reach the levels responsible for cellular damage, the sea urchin Paracentrotus lividus is frequently in such sites, particularly on the southern Adriatic Sea shore. Spawning their eggs and spending their early life stage in rocky shores at depths of 0.5-2 m are the results of their successful adaptation strategies, although adults may dwell at greater depths. Surprisingly, there is a paucity of reports regarding the carotenoid content in sea urchin eggs. Beyond their important role in photoprotection against high UV exposure, cell division and early development, the content and distribution of carotenoids contribute to the successful survival of sea urchins and also determine the color of their gonads (roe), which is of commercial importance as a delicacy. Herein, for the first time, we have described the carotenoid content and distribution in intact, freshly released eggs of P. lividus species, non-destructively employing resonance Raman spectroscopy and imaging; near-infrared Raman spectroscopy revealed additional molecular carotenoid content. Echinenone and ß-carotene resonance Raman signals were the most intense, and they were identified as the principal carotenoids that are preferentially accumulated in eggs rather than in gonads. Raman imaging in confocal mode revealed the uniform distribution of the carotenoid signal over the whole eggs, while the distribution of proteins appeared spotted. Egg carotenoids generally maintained their identity after 2 months of dry storage, with slight signs of C[double bond, length as m-dash]C bond oxidation. The potential utilization of P. lividus sea urchin eggs as valuable microsphere packages of native carotenoids is discussed.

Lipophilic marine biotoxins SERS sensing in solutions and in mussel tissue.

To detect and recognise three structurally related marine biotoxins responsible for the diarrheic shellfish poisoning (DSP) symptom, namely okadaic acid (OA), dinophysistoxin-1 (DTX-1) and dinophysistoxin-2 (DTX-2) respectively, as well as the structurally different yessotoxin (YTX), we developed a novel surface-enhanced micro-Raman scattering (micro-SERS) approach to investigate for the first time their micro-SERS signalling in solution and jointly analysed them in conjunction with the normal and toxic mussel tissue. YTX provided the main SERS feature surprisingly similar to DTX-1 and DTX-2, suggesting similar molecular adsorption mechanism with respect to the AgNPs. A fingerprint SERS band at 1017 cm-1 characteristic for the C-CH3 stretching in DTX-1 and DTX-2 and absent in OA SERS signal, allowed direct SERS discrimination of DTX-1,2 from OA. In acid form or as dissolved potassium salt, OA showed reproducible SERS feature for 0.81 µM to 84.6 nM concentrations respectively, while its ammonium salt slightly changed the overall SERS signature. The inherently strong fluorescence of the shellfish tissue, which hampers Raman spectroscopy analysis, further increases when toxins are present in tissue. Through SERS, tissue fluorescence is partially quenched. Artificially intoxicated mussel tissue with DSP toxins and incubated with AgNPs allowed direct SERS evidence of the toxin presence, opening a novel avenue for the in situ shellfish tracking and warning via micro-SERS. Natural toxic tissue containing 57.91 µg kg-1 YTX (LC-MS confirmed) was micro-SERS assessed to validate the new algorithm for toxins detection. We showed that a portable Raman system was able to reproduce the lab-based SERS results, being suitable for in situ raw seafood screening. The new approach provides an attractive, faster, effective and low-cost alternative for seafood screening, with economic, touristic and sustainable impact in aquaculture, fisheries, seafood industry and consumer trust.

Detection of thiabendazole applied on citrus fruits and bananas using surface enhanced Raman scattering.

Thiabendazole (TBZ) is a chemical fungicide and parasiticide largely used in food industry against mold and blight in vegetables and fruits during transportation and long term deposit. We investigated the possibility to detect and monitor the TBZ from the chemically treated bananas and citrus fruits available on Romanian market, using surface enhanced Raman spectroscopy (SERS) with a compact, portable, mini-Raman spectrometer. To assess the potential of the technique for fast, cheap and sensitive detection, we report the first complete vibrational characterization of the TBZ in a large pH and concentration range in conjunction with the density functional theory (DFT) calculations. From the relative intensity of the specific SERS bands as a function of concentration, we estimated a total amount of TZB as 78 mg/kg in citrus fruits, 13 times higher than the maximum allowed by current regulations, whereas in banana fruit the value was in the allowed limit.

Amnesic shellfish poisoning biotoxin detection in seawater using pure or amino-functionalized Ag nanoparticles and SERS.

Domoic acid (DA) biotoxin responsible for the amnesic shellfish poisoning (ASP) has been unambiguously detected in seawater in a broad range of concentration, with both pure and amino-functionalized Ag nanoparticles employed for surface enhanced Raman scattering (SERS). To achieve this, a comprehensive SERS study on DA dissolved in distilled water has been conducted. SERS of DA dissolved in seawater in concentrations ranging from 3.3 × 10(-4) to 3.3 × 10(-8) mol l(-1) exhibited specific signal, completely different to those of the corresponding DA aqueous solutions, due to the seawater interference in the overall SERS effect. In order to assess the capability of the technique as a cheaper alternative for rapid and unambiguous detection of the DA biotoxin in seawater, three detection schemes have been proposed. DA was detectable at 0.33 nmoll(-1) concentration (0.33) dissolved in distilled water and 0.033 nmol l(-1) (0.033 ppb) in seawater respectively, much lower than the admitted level by the current regulation. A solvent specific interaction of DA with the NPs was concluded, since DA aqueous solution added to Ag nanoparticles provided different SERS signal compared to that of DA directly dissolved in seawater. Employing amino-functionalized Ag nanoparticles with 4-aminothiophenol as SERS tag, SERS signal of DA on amino-AgNPs revealed significant specificity associated with the aromatic primary amine interaction of the SERS tag with DA, thus allowing DA detection in seawater at 4.16 × 10(-4) mol l(-1) concentration, much higher than in the case of pure NPs. To highlight the findings, a brief literature review to date on the DA biotoxin detection was also provided.