Paper/GO/e-Au flexible SERS sensors for in situ detection of tricyclazole in orange juice and on cucumber skin at the sub-ppb level: machine learning-assisted data analysis.

Despite being an excellent surface enhanced Raman scattering (SERS) active material, gold nanoparticles were difficult to be loaded onto the surface of filter paper to fabricate flexible SERS substrates. In this study, electrochemically synthesized gold nanoparticles (e-AuNPs) were deposited on graphene oxide (GO) nanosheets in solution by ultrasonication, resulting in the formation of a GO/Au hybrid material. Thanks to the support of GO, the hybrid material could adhere onto the surface of filter paper, which was immersed into a GO/Au solution for 24 h and dried naturally at room temperature. The paper-based materials were then employed as substrates for a surface enhanced Raman scattering (SERS) sensing platform to detect tricyclazole (TCZ), a widely used pesticide, resulting in better sensitivity compared to the use of paper/Au SERS sensors. With the most optimal GO content of 4%, paper/GO/Au SERS sensors could achieve a limit of detection of 1.32 × 10-10 M in standard solutions. Furthermore, the filter paper-based SERS sensors also exhibited significant advantages in sample collection in real samples. On one hand, the sensors were dipped into orange juice, allowing TCZ molecules in this real sample to be adsorbed onto their SERS active surface. On the other hand, they were pasted onto cucumber skin to collect the analytes. As a result, the paper/GO/Au SERS sensors could sense TCZ in orange juice and on cucumber skin at concentrations as low as 10-9 M (∼2 ppb). In addition, a machine learning model was designed and developed, allowing the sensing system to discriminate TCZ from nine other organic compounds and predict the presence of TCZ on cucumber skin at concentrations down to 10-9 M.

Surface ligand modified silver nanoparticles-based SERS sensing platform for ultrasensitive detection of the pesticide thiram in green tea leaves: roles of coating agents in sensing performance.

Silver nanoparticles (AgNPs) have been regarded as a highly promising substrate for surface-enhanced Raman scattering (SERS) sensors. In this study, we focused on the electrochemical synthesis method by developing three kinds of AgNPs using three different electrolytes: citrate (e-Ag-C), oleic acid (e-Ag-O) and fish mint (Houttuynia cordata Thunb.) extract (e-Ag-bio). The as-prepared AgNPs were characterized and then employed as SERS substrates to detect the pesticide thiram. The obtained results show that e-Ag-O exhibits the best SERS performance. The effect of the coating agent was explained by chemical and electromagnetic enhancements (CM and EM). Although thiram could absorb onto e-Ag-C at the highest level, allowing its Raman signal to be best enhanced via the CM, the smallest interparticle distance of e-Ag-O could have resulted in the largest improvement in the EM. Using e-Ag-O to develop SERS-based sensors for thiram, we obtain the impressive detection limit of 1.04 × 10-10 M in standard samples and 10-9 M in tea leaves. The linear ranges are from 10-4 M to 10-7 M and from 10-7 M to 10-9 M, covering the maximum residue levels for plant commodities established by the United States Environment Protection Agency and European Food Safety Authority (2-13 ppm ∼7.7 × 10-6 M to 5 × 10-5 M).

Overpromoted and underregulated: National binding legal measures related to commercially produced complementary foods in seven Southeast Asian countries are not fully aligned with available guidance.

The market for commercially produced complementary foods (CPCF) is rapidly expanding in Southeast Asia; however, the existence and content of mandatory national policies, standards and legislation (binding legal measures) for CPCF in the region is unclear. To assess the status of national binding legal measures for CPCF in Southeast Asia, a legal and policy desk review was conducted in seven countries (Cambodia, Laos People's Democratic Republic, Indonesia, Malaysia, Philippines, Thailand and Viet Nam). The alignment of the national binding legal measures relevant to CPCF was assessed against guidance on CPCF nutrient composition and labelling requirements provided by Codex Alimentarius and the World Health Organization (WHO). Each of the seven countries had at least two national binding legal measures related to the nutrient composition or labelling of CPCF; however, there was limited alignment with the guidance from Codex and WHO. No country was fully aligned with the three CPCF-specific Codex standards/guidelines and only one country was in full alignment with the recommendations related to the protection of breastfeeding from the 'WHO Guidance on ending the inappropriate promotion of foods for infants and young children'. The findings of the review indicate that the existing national binding legal measures are insufficient to ensure that the CPCF sold as suitable for older infants and young children are nutritionally adequate and labelled in a responsible manner that does not mislead caregivers. Improved and enforced national binding legal measures for CPCF, in alignment with global guidance, are required to ensure that countries protect, promote and support optimal nutrition for children 6-36 months of age.

Enhanced sensing performance of carbaryl pesticide by employing a MnO2/GO/e-Ag-based nanoplatform: role of graphene oxide as an adsorbing agent in the SERS analytical performance.

A functional ternary substrate was developed for surface-enhanced Raman scattering (SERS) sensing systems. MnO2 nanosheets were synthesized by a simple and controllable hydrothermal method, followed by the integration of graphene oxide (GO) nanosheets. Subsequently, MnO2/GO nanostructures were decorated with plasmonic Ag nanoparticles (e-AgNPs). The MnO2/GO/e-Ag substrate could enhance the SERS sensing signal for organic chemicals without the assistance of chemical bonds between those analytes and the semiconductor within the ternary substrate, which have been proven to promote charge transfer and elevate the SERS enhancement in previous studies. Instead, GO nanosheets acted as a carpet also supporting the MnO2 nanosheets and e-AgNPs to form a porous structure, allowing the analytes to be well-adsorbed onto the ternary substrate, which improved the sensing performance of the SERS platform, compared to pure e-AgNPs, MnO2/e-Ag, and GO/e-Ag alone. The GO content in the nanocomposite was also considered to optimize the SERS substrate. With the most optimal GO content of 0.1 wt%, MnO2/GO/e-Ag-based SERS sensors could detect carbaryl, a pesticide, at concentrations as low as 1.11 × 10-8 M in standard solutions and 10-7 M in real tap water and cucumber extract.

Ultrasensitive detection of crystal violet using a molybdenum sulfide-silver nanostructure-based sensing platform: roles of the adsorbing semiconductor in SERS signal enhancement.

Crystal violet (CV) is an organic dye that is stabilized by the extensive resonance delocalization of electrons over three electron-donating amine groups. This prevents the molecule from being linked to a metal surface, and therefore, reduces the sensitivity of surface-enhanced Raman scattering (SERS) sensors for this toxic dye. In this work, we improved the sensing performance of a silver-based SERS sensor for CV detection by modifying the active substrate. Molybdenum sulfide (MoS2) nanosheets were employed as a scaffold for anchoring electrochemically synthesized silver nanoparticles (e-AgNPs) through a single step of ultrasonication, leading to the formation of MoS2/Ag nanocomposites. As an excellent adsorbent, MoS2 promoted the adsorption of CV onto the surface of the substrate, allowing more CV molecules to be able to experience the SERS effect originating from the e-AgNPs. Hence, the SERS signal of CV was significantly enhanced. In addition, the effects of the MoS2 content of the nanocomposites on their SERS performance were also taken into account. Using MoS2/Ag with the most optimal MoS2 content of 10%, the SERS sensor exhibited the best enhancement of the SERS signal of CV with an impressive detection limit of 1.17 × 10-11 M in standard water and 10-9 M in tap water thanks to an enhancement factor of 2.9 × 106, which was 11.2 times higher than that using pure e-AgNPs.

Gold and Iron Oxide Nanoparticle Assemblies on Turnip Yellow Mosaic Virus for In-Solution Photothermal Experiments.

The ability to construct three-dimensional architectures via nanoscale engineering is important for emerging applications in sensors, catalysis, controlled drug delivery, microelectronics, and medical diagnostics nanotechnologies. Because of their well-defined and highly organized symmetric structures, viral plant capsids provide a 3D scaffold for the precise placement of functional inorganic particles yielding advanced hierarchical hybrid nanomaterials. In this study, we used turnip yellow mosaic virus (TYMV), grafting gold nanoparticles (AuNP) or iron oxide nanoparticles (IONP) onto its outer surface. It is the first time that such an assembly was obtained with IONP. After purification, the resulting nano-biohybrids were characterized by different technics (dynamic light scattering, transmission electron microcopy, X-ray photoelectron spectroscopy…), showing the robustness of the architectures and their colloidal stability in water. In-solution photothermal experiments were then successfully conducted on TYMV-AuNP and TYMV-IONP, the related nano-biohybrids, evidencing a net enhancement of the heating capability of these systems compared to their free NP counterparts. These results suggest that these virus-based materials could be used as photothermal therapeutic agents.

A manganese dioxide-silver nanostructure-based SERS nanoplatform for ultrasensitive tricyclazole detection in rice samples: effects of semiconductor morphology on charge transfer efficiency and SERS analytical performance.

Taking advantage of metal-semiconductor junctions, functional nanocomposites have been designed and developed as active substrates for surface-enhanced Raman scattering (SERS) sensing systems. In this work, we prepared three types of nanocomposites based on manganese oxide (MnO2) nanostructures and electrochemically synthesized silver nanoparticles (e-AgNPs), which differed according to the morphologies of MnO2. The SERS performance of MnO2 nanosheet/e-Ag (MnO2-s/e-Ag), MnO2 nanorod/e-Ag (MnO2-r/e-Ag), and MnO2 nanowire/e-Ag (MnO2-w/e-Ag) was then evaluated using tricyclazole (TCZ), a commonly used pesticide, as an analyte. Compared to the others, MnO2-s/e-Ag exhibited the most remarkable SERS enhancement. Thanks to its large surface area and ability to accept/donate the electrons of the semiconductor, MnO2-s acted as a bridge to improve the charge transfer efficiency from e-Ag to TCZ. In addition, the MnO2 content of the nanocomposites was also considered to optimize the SERS sensing performance. With the optimal MnO2 content of 25 wt%, MnO2-s/e-Ag could achieve the best SERS performance, allowing the detection of TCZ at concentrations down to 6 × 10-12 M in standard solutions and 10-11 M in real rice samples.

Assembly of gold nanoparticles using turnip yellow mosaic virus as an in-solution SERS sensor.

A common challenge in nanotechnology is the conception of materials with well-defined nanoscale structure. In recent years, virus capsids have been used as templates to create a network to organize 3D nano-objects, building thus new functional nanomaterials and then devices. In this work, we synthetized 3D gold nanoclusters and we used them as Surface Enhanced Raman Scattering (SERS) sensor substrates in solution. In practice, gold nanoparticles (AuNPs) were grafted on turnip yellow mosaic virus (TYMV) capsid, an icosahedral plant virus. Two strategies were considered to covalently bind AuNPs of different sizes (5, 10 and 20 nm) to TYMV. After purification by agarose electrophoresis and digestion by agarase, the resulting nano-bio-hybrid AuNP-TYVM was characterized by different tools. Typically, dynamic light scattering (DLS) confirmed the grafting through the hydrodynamic size increase by comparing AuNPs alone to AuNP-TYMV (up to 33, 50 and 68 nm for 5, 10 and 20 nm sized AuNPs, respectively) or capsids alone (28 nm). Transmission electronic microscopy (TEM) observations revealed that AuNPs were arranged with 5-fold symmetry, in agreement with their grafting around icosahedral capsids. Moreover, UV-vis absorption spectroscopy showed a red-shift of the plasmon absorption band on the grafted AuNP spectrum (530 nm) compared to that of the non-grafted one (520 nm). Finally, by recording in solution the Raman spectra of a dissolved probe molecule, namely 1,2-bis(4-pyridyl)ethane (BPE), in the presence of AuNP-TYVM and bare AuNPs or capsids, a net enhancement of the Raman signal was observed when BPE is adsorbed on AuNP-TYVM. The analytical enhancement factor (AEF) value of AuNP-TYMV is 5 times higher than that of AuNPs. These results revealed that AuNPs organized around virus capsid are able to serve as in-solution SERS-substrates, which is very interesting for the conception of ultrasensitive sensors in biological media.