Charting a new course with plasmon-mediated chemistry.

is pleased to introduce a Collection of articles on the topic of plasmon-mediated chemistry. Here, the Guest Editors discuss different themes within and look towards the future of the field.

Harnessing the resolution power of two-dimensional liquid chromatography (2D-LC) for the screening of bisphenol contaminants in canned food items.

Overlapping peaks can be difficult to avoid in 1D-LC, which make the identification and quantification of compounds ambiguous, especially if the only available detector is a UV/DAD. To overcome this, a two-dimensional liquid chromatography (2D-LC) method to monitor Bisphenols (BPs), and particularly the chosen analogues BPA, BPB, BPF, BPS, BPZ, and BPAF, in a complex matrix (canned food) was developed and validated. BPs are endocrine disruptors present in the lining of the can, which may leach into the content of canned food.

Correction: Electrochemical and X-ray structural evidence of multiple molybdenum precursor candidates from a reported non-aqueous electrodeposition of molybdenum disulfide.

[This corrects the article DOI: 10.1039/D3RA04605B.].

Electrochemical and X-ray structural evidence of multiple molybdenum precursor candidates from a reported non-aqueous electrodeposition of molybdenum disulfide.

A published report of electrodeposited molybdenum(iv) disulfide microflowers at 100 °C in the ionic liquid -methyl--propylpiperidinium bis(trifluoromethane)sulfonimide (PP13-TFSI) from 1,4-butanedithiol and the concentrated filtrate from a reaction mixture of molybdenum(vi) trioxide and ethylene glycol could not be reproduced reliably, affording numerous uniquely coloured reaction mixtures that precipitated a variety of crystalline molybdenum coordination complexes. Further attempts to use the same two of these filtrates to electrodeposit molybdenum(iv) disulfide from 0.1 M PP13-TFSI in tetrahydrofuran with 1,4-butanedithiol at room temperature were unsuccessful.

Thiacloprid Detection by Silver Nanocubes-Based SERS Sensor.

The use of neonicotinoid insecticides leads to environmental problems such as accumulation and death of different insects and even bird species. In this work, we compared the SERS performance of Ag nanocubes- and nanospheres-based substrates for the analysis of thiacloprid, a neonicotinoid, reaching its detection at 1 mM using nanocubes as the active material.

Fabrication of high quality electrochemical SERS (EC-SERS) substrates using physical vapour deposition.

Screen-printed electrodes (SPEs) are an efficient and inexpensive substrate for electrochemical surface-enhanced Raman spectroscopy (EC-SERS) studies. Traditionally, the working electrode of the SPE is modified with either a colloidal paste of metal nanoparticles or an electrodeposited metallic film. These methods can be time-consuming and often produce non-uniform nanostructured films.

Optimization of gold nanorod arrays for surface enhanced Raman spectroscopy (SERS) detection of atrazine.

Recently, there has been increasing concern over the widespread use of the herbicide atrazine which has been reported to have problematic side effects on local ecosystems. This has highlighted the need for rapid and accurate point-of-need assessment tools for analytical determination of herbicides in ground and surface waters. Surface enhanced Raman spectroscopy (SERS) is a sensitive vibrational spectroscopy technique which has recently been employed for the analysis of a variety of analytes in water, ranging from pharmaceuticals to pesticides.

Spectroelectrochemical and computational studies of tetrahydrocannabinol (THC) and carboxy-tetrahydrocannabinol (THC-COOH).

Rapid and accurate detection of tetrahydrocannabinol (THC) and its main secondary metabolite carboxy-tetrahydrocannabinol (THC-COOH) is important to ensure safe roadways and workplaces, particularly in regions of the world where cannabis use is legal. In this work, we seek to demonstrate the usefulness of electrochemical SERS (EC-SERS) for the rapid detection of both THC and THC-COOH, complemented by thorough ab initio calculations for both molecules. These results indicate that application of a voltage is essential for efficient SERS detection of cannabinoids at low concentrations in bodily fluids, allowing for the eventual development of sensitive and quantitative screening tools.

Electrochemical Surface-Enhanced Raman Spectroscopy as a Platform for Bacterial Detection and Identification.

The field of bacterial screening is in need of a rapid, easy to use, sensitive, and selective platform for bacterial detection and identification. Current methods of bacterial identification lack time efficiency, resulting in problems for many sectors of society. Surface-enhanced Raman spectroscopy (SERS) has been investigated as a possible candidate for bacterial screening due to its demonstrated ability to detect biological molecules with a high degree of sensitivity.

Development of an electrochemical surface-enhanced Raman spectroscopy (EC-SERS) fabric-based plasmonic sensor for point-of-care diagnostics.

Early disease diagnosis is crucial for timely and effective healthcare monitoring and treatment. Demand for modern point-of-care (POC) technologies has increased during the past decade. Continuous monitoring of patient health status can be achieved through wearable sensors which can be incorporated into clothing and other wearables.

Electrochemical surface-enhanced Raman spectroscopy (EC-SERS) study of the interaction between protein aggregates and biomimetic membranes.

Human diseases characterized by the uncontrolled deposition of insoluble extracellular protein aggregates are collectively referred to as amyloidoses. Such diseases include Alzheimer's, Parkinson's, Huntington's, and prion disease. In Alzheimer's disease, it is believed that amyloid-β proteins may be responsible for pore and defect formation within cellular membranes, leading to a breakdown of cellular homeostasis causing eventual neuronal death.

Quantitative detection of uric acid by electrochemical-surface enhanced Raman spectroscopy using a multilayered Au/Ag substrate.

Uric acid is a potential important biomarker in urine and serum samples for early diagnosis of preeclampsia, a life-threatening hypertensive disorder that occurs during pregnancy. Preeclampsia is a leading cause of maternal death, especially in developing nation settings. Quantitative detection of uric acid for rapid and routine diagnosis of early preeclampsia using electrochemical-surface enhanced Raman spectroscopy (EC-SERS) is presented herein.

The development of "fab-chips" as low-cost, sensitive surface-enhanced Raman spectroscopy (SERS) substrates for analytical applications.

The demand for methods and technologies capable of rapid, inexpensive and continuous monitoring of health status or exposure to environmental pollutants persists. In this work, the development of novel surface-enhanced Raman spectroscopy (SERS) substrates from metal-coated silk fabric, known as zari, presents the potential for SERS substrates to be incorporated into clothing and other textiles for the routine monitoring of important analytes, such as disease biomarkers or environmental pollutants. Characterization of the zari fabric was completed using scanning electron microscopy, energy dispersive X-ray analysis and Raman spectroscopy.

A simple complex on the verge of breakdown: isolation of the elusive cyanoformate ion.

Why does cyanide not react destructively with the proximal iron center at the active site of 1-aminocyclopropane-1-carboxylic acid (ACC) oxidase, an enzyme central to the biosynthesis of ethylene in plants? It has long been postulated that the cyanoformate anion, [NCCO2](-), forms and then decomposes to carbon dioxide and cyanide during this process. We have now isolated and crystallographically characterized this elusive anion as its tetraphenylphosphonium salt. Theoretical calculations show that cyanoformate has a very weak C-C bond and that it is thermodynamically stable only in low dielectric media.

Electrochemical surface-enhanced Raman spectroscopy (E-SERS) of novel biodegradable ionic liquids.

Electrochemical SERS (E-SERS) was used for the first time to study the interfacial behavior of a class of pyridinium-based biodegradable ionic liquids at a silver nanoparticle (AgNP) electrode surface. An isomeric series of ionic liquids (IL) based on 3-butoxycarbonyl-1-methylpyridinium bis(trifluoromethanesulfonyl)imide were prepared, which have demonstrable biodegradability. It was found that all four of the isomeric ionic liquids studied exhibited excellent electrochemical stability as binary mixtures combined with methanol, with the absence of any specific redox processes occurring over nearly 3.

Electrochemical and PM-IRRAS characterization of cholera toxin binding at a model biological membrane.

A mixed phospholipid-cholestrol bilayer, with cholera toxin B (CTB) units attached to the monosialotetrahexosylganglioside (GM1) binding sites in the distal leaflet, was deposited on a Au(111) electrode surface. Polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) measurements were used to characterize structural and orientational changes in this model biological membrane upon binding CTB and the application of the electrode potential. The data presented in this article show that binding cholera toxin to the membrane leads to an overall increase in the tilt angle of the fatty acid chains; however, the conformation of the bilayer remains relatively constant as indicated by the small decrease in the total number of gauche conformers of acyl tails.

Electrochemical-surface enhanced Raman spectroscopy (E-SERS) of uric acid: a potential rapid diagnostic method for early preeclampsia detection.

An increased level of uric acid in urine and plasma is indicative of the development of preeclampsia, a hypertensive disorder that can occur during pregnancy. The preliminary steps towards developing a rapid tool for early diagnosis of preeclampsia using electrochemical SERS (E-SERS) for the detection of uric acid in urine are presented herein. Characterization of the uric acid species was completed using cyclic voltammetry, UV spectroscopy, Raman spectroscopy and electrochemical surface-enhanced Raman spectroscopy (E-SERS).

SERS of beta-thioglucose adsorbed on nanostructured silver electrodes.

Highly ordered microporous films of silver-containing regular arrays of spherical pores of differing diameters were prepared by electrochemical deposition into the interstitial spaces of a template formed by nanosphere lithography. These nanostructured electrodes in conjunction with a Raman microprobe spectrometer were used to obtain surface-enhanced Raman spectra (SERS) of beta-thioglucose (beta-TG) under potential control. The SERS results were compared with SERS of beta-TG on an electrochemically roughened silver electrode surface.

Surface-enhanced Raman spectroscopy of dyes: from single molecules to the artists' canvas.

This perspective presents recent surface-enhanced Raman spectroscopy (SERS) studies of dyes, with applications to the fields of single-molecule spectroscopy and art conservation. First we describe the development and outlook of single-molecule SERS (SMSERS). Rather than providing an exhaustive review of the literature, SMSERS experiments that we consider essential for its future development are emphasized.

Surface-enhanced Raman spectroscopy: a direct method to identify colorants in various artist media.

Surface-enhanced Raman spectroscopy (SERS) has been developed as a direct, extractionless, nonhydrolysis tool to detect lake pigments and colorants of various classes used in a variety of artist materials. Presented first is the SERS analysis of the natural colorant turmeric (Curcuma longa L.), main component curcumin, as present in dry lake pigment grains, dyed textile yarns, and reference paint layers containing the lake pigment bound in animal glue painted on glass.

Ad-hoc surface-enhanced Raman spectroscopy methodologies for the detection of artist dyestuffs: thin layer chromatography-surface enhanced Raman spectroscopy and in situ on the fiber analysis.

Tailored ad-hoc methods must be developed for successful identification of minute amounts of natural dyes on works of art using Surface-Enhanced Raman Spectroscopy (SERS). This article details two of these successful approaches using silver film over nanosphere (AgFON) substrates and silica gel coupled with citrate-reduced Ag colloids. The latter substrate functions as the test system for the coupling of thin-layer chromatography and SERS (TLC-SERS), which has been used in the current research to separate and characterize a mixture of several artists' dyes.

AFM studies of the effect of temperature and electric field on the structure of a DMPC-cholesterol bilayer supported on a Au(111) electrode surface.

Atomic force microscopy (AFM) was used to characterize a phospholipid bilayer composed of 70 mol % 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) and 30 mol % cholesterol, at a Au(111) electrode surface. Results indicate that addition of cholesterol relaxes membrane elastic stress, increases membrane thickness, and reduces defect density. The thickness and thermotropic properties of the mixed DMPC-cholesterol bilayer supported at the gold electrode surface are quite similar to the properties of the mixed membrane in unilamellar vesicles.

AFM studies of solid-supported lipid bilayers formed at a Au(111) electrode surface using vesicle fusion and a combination of Langmuir-Blodgett and Langmuir-Schaefer techniques.

Atomic force microscopy (AFM) has been used to characterize the formation of a phospholipid bilayer composed of 1,2-dimyristyl-sn-glycero-3-phosphocholine (DMPC) at a Au(111) electrode surface. The bilayer was formed by one of two methods: fusion of lamellar vesicles or by the combination of Langmuir-Blodgett (LB) and Langmuir-Schaefer (LS) deposition. Results indicate that phospholipid vesicles rapidly adsorb and fuse to form a film at the electrode surface.

In situ STM study of potential-driven transitions in the film of a cationic surfactant adsorbed on a Au(111) electrode surface.

Electrochemical scanning tunneling microscopy (EC-STM) has been employed to study the structure of a film formed by cationic surfactant N-decyl-N,N,N-trimethylammonium triflate (DeTATf) adsorbed on the Au(111) electrode surface. The film is disordered at potentials corresponding to either large negative charge densities or to positive charge densities. At small negative charge densities, an ordered adlayer of flat-lying DeTATf molecules is formed.

Adsorption of N-Decyl-N,N,N-trimethylammonium triflate (DeTATf), a cationic surfactant, on the Au(111) electrode surface.

The adsorption behavior of the cationic surfactant N-decyl-N,N,N-trimethylammonium triflate (DeTATf) on the Au(111) electrode surface was characterized using cyclic voltammetry, differential capacity, and chronocoulometry. The thermodynamics of the ideally polarized electrode have been employed to determine the Gibbs excess and the Gibbs energy of adsorption. The results show that the adsorption of DeTATf has a multistate character.