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With the growing interest in microalgae as a sustainable food source, concerns about potential chemical contaminants in these products have emerged. In this study, a sensitive and reliable LC-MS/MS method was developed for the simultaneous detection of thiocyanate, perchlorate, and chlorate in edible microalgae samples. The method was validated with excellent linearity (R 2 > 0.998), low detection limits (LOD: 1-8 μg/kg), quantification limits (LOQ: 4-26 μg/kg), and high recovery rates (75-101.9%) across different sample types. We collected a total of 77 microalgae products based on the available varieties in the market, including 43 Spirulina powder samples, 10 Chlorella powder samples, and 24 microalgae-based food products, sourced from key microalgae production regions in China. The contamination levels for thiocyanate (median: 1843.06-2645.72 μg/kg) and perchlorate (median: 23.29-31.4 μg/kg) were consistently quantitated in all samples, while chlorate concentrations showed greater variability (median: 18.94-160.21 μg/kg). Risk assessment revealed a significant dietary exposure risk to thiocyanate, with estimated daily intake (EDI) values exceeding the EPA's subchronic reference dose, whereas no significant risk was identified for perchlorate or chlorate. Monte Carlo simulations further supported the conclusion that perchlorate and chlorate posed minimal dietary risks, while thiocyanate exposure warrants concern. This study not only provides a foundational method for monitoring these contaminants in microalgae but also contributes critical data for future food safety standards and regulatory practices regarding edible microalgae products.

An instrumental-free, high-throughput assay has been developed for the quantification of thiocyanate in human saliva. The proposed green method is based on the rapid reaction of the analyte with Fe(III) under acidic pH in a microplates format to form a colored complex that is captured as an image by an overhead book scanner. Optimization included the effects of the amount concentration of Fe(III), acidity and reaction time / complex stability using a total volume of 300 μL per well. Validation towards the matrix effect was focused on the specific application and was performed using both artificial and human saliva. The linearity of the developed assay was up to 500 μM thiocyanate offering a lower limit of quantification (LLOQ) of 30 μM. The green potentials were evaluated by both the Green Analytical Procedure (GAPI) and Blue Applicability Grade (BAGI) indexes. The thiocyanate content in the saliva of non-smoking volunteers ranged between 750 and 1350 μΜ, while elevated concentrations were verified in smoking individuals (1860-3080 μΜ). Statistical agreement with a corroborative method was assessed using the Bland-Altman plot., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

BIIB104 (formerly PF-04958242), N -((3 S ,4 S )-4-(4-(5-cyanothiophen-2-yl)phenoxy)tetrahydrofuran-3-yl)propane-2-sulfonamide, is an α -amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid receptor potentiator investigated for the treatment of cognitive impairment associated with schizophrenia. Preliminary in vitro metabolism studies with non-radiolabeled BIIB104 in rat, dog, and human liver microsomes (RLM, DLM, and HLM) showed O -dealkylation in all three species, tetrahydrofuran hydroxylation dominating in DLM and HLM, and thiophene hydroxylation prevalent in RLM. However, a subsequent rat mass balance study with [nitrile- 14 C]BIIB104 showed incomplete recovery of administered radioactivity (∼80%) from urine and feces over 7 days following an oral dose, and an exceptionally long plasma total radioactivity half-life. Radiochromatographic metabolite profiling and identification, including chemical derivation, revealed that [ 14 C]cyanide was a major metabolite of [nitrile- 14 C]BIIB104 in RLM, but a minor and trace metabolite in DLM and HLM, respectively. Correspondingly in bile duct-cannulated rats, [ 14 C]thiocyanate accounted for ∼53% of total radioactivity excreted over 48 hours postdose and it, as an endogenous substance, explained the exceptionally long plasma radioactivity half-life. The release of [ 14 C]cyanide from the 2-cyanothiophene moiety is postulated to follow an epoxidation-initiated thiophene-opening based on the detection of non-radiolabeled counterpart metabolites in RLM. This unusual biotransformation serves as a lesson regarding placement of the radioactive label on an aryl nitrile when material will be used for evaluating the metabolism of a new drug candidate. Additionally, the potential cyanide metabolite of nitrile-containing drug molecules may be detected in liver microsomes with liquid chromatography-mass spectrometry following a chemical derivatization. SIGNIFICANCE STATEMENT: Using [nitrile- 14 C]BIIB104, non-intuitive metabolites of BIIB104 were discovered involving a novel cyanide release from the 2-cyanothiophene motif via a postulated epoxidation-initiated thiophene-opening. This unusual biotransformation serves as a lesson regarding placement of the radioactive label on an aryl nitrile when material will be used for evaluating the metabolism of a new drug candidate., (Copyright © 2024 by The American Society for Pharmacology and Experimental Therapeutics.)

This study presents a novel, cost-effective approach involving spectrophotometric and smartphone paper-based (SPB) methods and a distinctive salting-out air-assisted dispersive microextraction procedure to quantify thiocyanate in saliva samples. The method relies on the inhibitory effect of thiocyanate on quinoneimine dye formation during the Emerson reaction with sodium hypochlorite. Spectrophotometry quantifies the extracted dye by monitoring quinoneimine color intensity reduction at 525 nm. In the SPB method, extracted dye is applied to a paper strip, a smartphone captures the colored paper, and an application analyzes red, green, and blue components. All analyte determination and extraction variables were explored. Both methods exhibit good linearity (10-100 μg/L) with a coefficient of determination of 0.9991 and a limit of detection of 7.5 μg/L for the spectrophotometric method, and a coefficient of determination of 0.9988 and a limit of detection of 8.8 μg/L for the SPB method. The calculated values for the enrichment factor and extraction recovery of the developed extraction methodology were 46% and 93%, respectively. The methods detect thiocyanate in saliva samples, producing results comparable to a validated method., (© 2023 Wiley-VCH GmbH.)

At present, the uses of food additives globally are much of a concern due to their after effects upon consumption in higher proportions. Although different sensing strategies are available for their detection, a need for simple, rapid and cost-effective strategy is much of a concern. Herein, we developed a plasmonic nano sensor i.e., AgNP-EBF which was considered as the transducer component for the AND logic gate-based system with Cu 2+ and thiocyanate as inputs. Optimization and detection of thiocyanates were performed through UV-visible colorimetric sensing procedures where the logic gate allowed the detection of thiocyanate in the range of 100 nM-1 µM with LOD of 53.60 nM within 5-10 min. The proposed system showed high selectivity towards the detection of thiocyanate rather than other interferences. To check the credibility of the proposed system, the logic gate was applied for detection of thiocyanates in real milk samples., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

A method was developed for simultaneous determination of cyanide and thiocyanate in milk by gas chromatography-tandem quadrupole mass spectrometry (GC-MS/MS). Cyanide and thiocyanate were derivatized with pentafluorobenzyl bromide (PFBBr) as PFB-CN and PFB-SCN, respectively. Cetyltrimethylammonium bromide (CTAB) was employed both as a phase transfer catalyst and a protein precipitant in the sample pretreatment, which facilitates the separation of the organic and aqueous phases, and greatly simplifies the pretreatment procedures to achieve simultaneous and rapid determination of cyanide and thiocyanate. Under the optimized conditions, the limits of detection (LODs) of cyanide and thiocyanate in milk were 0.006 mg/kg and 0.015 mg/kg, and the spiked recoveries ranged from 90.1% to 98.2% and from 91.8% to 98.9% with relative standard deviations (RSDs) less than 18.9% and 15.2%, respectively. The proposed method was validated as a simple, fast and highly sensitive method for the determination of cyanide and thiocyanate in milk.

Introduction: Tobacco smoking is a leading preventable cause of premature death globally. Urinary thiocyanate is a biomarker of cyanide exposure from tobacco smoke; however, few studies have evaluated its utility in diverse populations of smokers., Aims and Methods: We examined the associations between urinary thiocyanate and self-reported never and current smokers among 1000 participants from 14 countries in the Prospective Urban and Rural Epidemiological study. We analyzed urinary thiocyanate in light and heavy smokers as compared to never-smokers from high- (HICs), middle- (MICs), and low-income countries (LICs) using a validated capillary electrophoresis method in conjunction with standardized questionnaires., Results: The median urinary thiocyanate concentration was 31 μM, which ranged from 8.6 μM to 52 μM for never-smokers (n = 335) and current smokers (n = 660), respectively. Urinary thiocyanate was correlated with daily cigarette consumption (r = 0.621) and total nicotine equivalents (r = 0.514). Thiocyanate also displayed a better dose-response than urinary cotinine. A moderate association of urinary thiocyanate was found in biochemically verified never-smokers (r ~0.38) because of intake of vegetables, fruits, and dairy. Receiver-operating characteristic curves established cutoff values for urinary thiocyanate to differentiate current from never-smokers with an optimal threshold of 23.9 μM (Area Under the Curve or AUC = 0.861), which lowered progressively from HICs, MICs, and LICs., Conclusions: Elevated thiocyanate was evident in current smokers from high-income countries likely reflecting differences in smoking topography and greater toxicant burden. Background urinary thiocyanate in never-smokers was associated with goitrogenic food intake that obscured detection of secondhand smoke exposure., Implications: Urinary thiocyanate is a sensitive biomarker of active tobacco smoking relative to cotinine that can be measured by an inexpensive capillary electrophoresis assay. Regional cutoff values are demonstrated to improve discrimination of smoking status in developing countries because of differences in smoking habits and cigarette products consumed, as well as intake of goitrogenic foods. Urinary thiocyanate may allow for more reliable estimates of the hazards of tobacco smoking between countries with varying socioeconomic development as compared to self-reports., (© The Author(s) 2023. Published by Oxford University Press on behalf of the Society for Research on Nicotine and Tobacco. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.)

Sodium thiocyanate (NaSCN) is a naturally antibacterial component in milk, but excessive consumption of thiocyanate may cause potential risks to human health. Currently available methods for the detection of thiocyanate have some disadvantages such as poor sensitivity and high price. Here, we report a robust and cost-effective method to detect NaSCN based on paper substrates deposited with in situ reduced Ag nanoparticles by surface-enhanced Raman spectroscopy (SERS). Densely packed multilayer AgNPs provide uniform narrow nanogaps, which exponentially enhance the Raman signals. Moreover, these homogeneous narrow hotspots ensure that this method has high sensitivity (the limit of detection is 10 -12 mol L -1 ), a wide linear range (from 10 -9 mol L -1 to 10 -4 mol L -1 ), and remarkable reproducibility (the coefficient of variation within a SERS sensor is 6.5%). Spiked milk samples were detected and the recovery rates of NaSCN were in the range of 95.1%-108.0%. This paper-based SERS sensor offers great potential for sensitive NaSCN detection and milk analysis.

The simultaneous detection of cyanide (CN), thiocyanate (SCN), and selenocyanate (SeCN) by a HPLC-fluorescence detector (FLD) with the post-column König reaction was recently reported. SCN and SeCN are also detectable by HPLC-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) because sulfur and selenium can be detected, respectively, without any pre- or post-treatment. ICP-MS has high sensitivity for selenium and sulfur detection and is robust to sample matrices. In this study, we compared HPLC-FLD with the post-column König reaction and HPLC-ICP-MS in terms of SCN and SeCN detection sensitivity and linearity. The limit of detection (LOD) for SCN indicated that HPLC-FLD with the post-column König reaction was 354 times more sensitive than HPLC-ICP-MS. Likewise, the LOD for SeCN indicated that HPLC-FLD was 51 times more sensitive than HPLC-ICP-MS. These results demonstrated that HPLC-FLD was a more suitable technique for SeCN and SCN detection than HPLC-ICP-MS. We previously reported that SeCN was generated in selenite-exposed mammalian cells to detoxify excess selenite. HPLC-FLD with the post-column König reaction enabled good separation and detection for quantifying SCN and SeCN in mammalian cell lines exposed to selenite. The intracellular SCN and SeCN concentrations determined by this technique suggested differences in the metabolic capacity for selenite to form SeCN among the cell lines. In addition, since the amount of intracellular SCN and SeCN were significantly decreased by pretreatment of myeloperoxidase (MPO) inhibitors, SCN and SeCN were resulted from the interaction of sulfur and selenium with endogenous CN, respectively, generated with MPO., (Copyright © 2021 Elsevier B.V. All rights reserved.)

A microcapillary grooved paper-based analytical device capable of dual-mode sensing (colorimetric and electrochemical detection) was demonstrated for analysis of viscous samples (e.g., human saliva). Herein, a hollow capillary channel was constructed via laser engraved micropatterning functions as a micropump to facilitate viscous fluidic transport, which would otherwise impede analysis on paper devices. Using salivary thiocyanate as a model analyte, the proposed device was found to exhibit a promising sensing ability on paper devices without the need for sample pretreatment or bulky instrumentation, as normally required in conventional methods used for saliva analysis. An extensive linear dynamic range covering detection of salivary thiocyanate for both high and trace level regimes (5 orders of magnitude working range) was collectively achieved using the dual-sensing modes. Under optimal conditions, the limit of detection was 6 μmol L -1 with a RSD of less than 5%. An excellent stability for the μpumpPAD was also observed for over 30 days. Real sample analysis using the proposed device was found to be in line with the standard chromatographic method. Benefitting from simple fabrication and operation, portability, disposability, low sample volume (20 μL), and low cost (< 1 USD), the μpumpPAD is an exceptional alternative tool for the detection of various biomarkers in saliva specimens.

This trial was conducted to study the effects of dietary rapeseed cake (RSC) containing high glucosinolates (GLS) on rumen fermentation, nutrient digestion and the rumen microbial community in steers. Eight growing steers and four rations containing RSC (GLS 226·1 μmol/g DM) at 0·00, 2·65, 5·35 and 8·00 % DM were assigned in a replicate 4 × 4 Latin square design. The results indicated that increasing RSC levels increased the ruminal concentration of thiocyanate (SCN) (P < 0·01), decreased the ruminal concentration of ammonia nitrogen (NH3-N) and the molar proportion of isovalerate (P < 0·05), did not affect the ruminal concentration of total volatile fatty acids (P > 0·05), decreased the crude protein (CP) digestibility (P < 0·05) and increased the ether extract (EE) digestibility (P < 0·01). Increasing RSC levels tended to decrease the abundances of ruminal Ruminobacter amylophilus (P = 0·055) and Ruminococcus albus (P = 0·086) but did not affect methanogens, protozoa, fungi and other bacteria (P > 0·05). Increasing RSC levels in the ration did not affect the ruminal bacterial diversity (P > 0·05), but it increased the operational taxonomic units and the bacterial richness (P < 0·05) and affected the relative abundances of some bacteria at the phylum level and genus level (P < 0·05). In conclusion, RSC decreased the ruminal concentration of NH3-N and the CP digestibility, increased the EE digestibility and partly affected the ruminal bacterial community. SCN, as the metabolite of GLS, could be a major factor affecting these indices.

Making the substrates form highly dense, homogeneous, and stable hotspots regions is important for the sensitive detection of surface-enhanced Raman spectroscopy (SERS). A new strategy based on solvent-induced (SI) SERS substrate to form a stable interval of the hotspot for detection was explored and the enhancement factor (EF) of our SERS substrates could reach about 1.4 × 10 9 . By preferential adsorption of alcohol solutions by Q-Sepharose microsphere (QSS) in mixed water and alcohol solutions, the size of QSS@AuNPs was dynamically adjusted and the spacing between gold nanoparticles (AuNPs) was adjusted to keep the substrate in the optimal hotspot mode for the sensitive detection of SERS in the liquid state. As a real application case, such a SI-SERS strategy was employed to determine SCN - in saliva and a limit of detection (LOD) of about 10 -10 M could be achieved.

In this work, 1.8 nm graphene quantum dots (GQDs), exhibiting bright blue fluorescence, were prepared using a bottom-up synthesis from citric acid. The fluorescence of the GQDs could be almost completely quenched (about 96%) by adding Hg 2+ . Quenching was far less efficient with other similar heavy metals, Tl + , Pb 2+ and Bi 3+ . Fluorescence could be near quantitatively restored through the introduction of thiocyanate. This "turn-on" fluorescence can thus be used to detect both or either environmental and physiological contaminants mercury and thiocyanate and could prove useful for the development of simple point-of-care diagnostics in the future. Graphical Abstract.

Saliva could be an optimal sample for non-invasive cancer detection, as it contains plenty of proteins and metabolites which can reflect the health status of an individual. Moreover, pairing it with high-sensitivity, label-free detection techniques could prove successful for early cancer diagnosis. In this study, we explore the enhancement of salivary characteristic Raman bands by using label-free, ultrasensitive surface-enhanced Raman scattering (SERS) based on gold nanoparticles. SERS maps were acquired from dry samples of saliva supernatant mixed with Au colloidal nanoparticles, which was then pipetted on clean glass slides. The SERS spectra presented a high variability of signal intensities and frequency shifts. However, several reproducible SERS spectra showing well-resolved bands were obtained at certain locations on the maps, where Au nanoparticles clustered together during the air-drying. The healthy and oral cancer saliva could be differentiated using principal components analysis based on several SERS bands assigned mainly to amino acids and proteins. Moreover, thiocyanate Raman modes were detected in saliva samples of both smoking and non-smoking volunteers and cancer patients. The analysis indicated that the cancer group displayed an overall higher level of the 2126 cm -1 band area assigned to C-N stretching vibrations of thiocyanate.

A new solid-contact potentiometric ion-selective electrode for the determination of SCN - (SCN-ISE) has been described. Synthesized phosphonium derivative of calix[4]arene was used as a charged ionophore. The research included selection of the ion-selective membrane composition, determination of the ISEs metrological parameters and SCN-ISE application for thiocyanate determination in human saliva. Preparation of the ISEs included selection of a plasticizer for the ion-selective membrane composition and type of the electrode material. The study was carried out using ISE with liquid internal electrolyte (LE-ISE) and solid-contact electrodes made of glassy carbon (GC-ISE) and gold rods (Au-ISE). The best parameters were found for GC sensors for which the ion-selective membrane contained chloroparaffin as a plasticizer (S = 59.9 mV/dec, LOD = 1.6 ´ 10 -6 M). The study of potentiometric selectivity coefficients has shown that the thiocyanate-selective sensor could be applied in biomedical research for determination of SCN - concentration in human saliva. The accuracy of the SCN - determination was verified by testing 59 samples of volunteers' saliva by potentiometric sensors and UV-Vis spectrophotometry as a reference technique. Moreover, SCN - concentrations in the smokers' and non-smokers' saliva were compared. In order to investigate the influence of various factors (sex, health status, taken medications) on the thiocyanate level in the saliva, more extensive studies on a group of 100 volunteers were carried out. Additionally, for a group of 18 volunteers, individual profiles of SCN - concentration in saliva measured on a daily basis for over a month were collected.

A cysteamine functionalized core shelled nanoparticles (Au@Ag-CysNPs) was presented for simultaneous and rapid detection of sodium thiocyanate (STC) and benzoic acid (BA) preservatives in liquid milk using surface-enhanced Raman spectroscopy (SERS) technique. A spectrum covering 350-2350 cm -1 region was selected to detect STC with concentrations ranging from 0.5 to 10 mg/L and BA with concentrations ranging from 15 to 240 mg/L in milk samples. Characterization of nanoparticles using high-resolution TEM confirmed that the successful synthesis of Au@AgNPs with core (gold) size of 28 nm and shell (silver) thickness of about 5 nm was grafted with 120 μL of 0.1 nM cysteamine hydrochloride. Results showed that Au@Ag-CysNPs could be used to detect STC up to 0.03 mg/L with a limit of quantification (LOQ) of 0.039 mg/L and a coefficient of determination (R 2 ) of 0.9833 in the milk sample. For detecting BA, it could be screened up to 9.8 mg/L with LOQ of 10.2 mg/L and R 2 of 0.9903. The proposed substrate was also highly sensitive and the employed method involved only minor sample pretreatment steps. It is thus hoped that the new substrate could be used in the screening of prohibited chemicals in complex food matrices in future studies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Thiocyanate (SCN - ) is harmful to a wide range of organisms, and its removal is essential for environmental protection. A neutrophilic halophile capable of thiocyanate degradation, Thiohalobacter sp. strain FOKN1, was highly enriched (relative abundance; 98.4%) from activated sludge collected from a bioreactor receiving thiocyanate-rich wastewater. The enrichment culture degraded 3.38 mM thiocyanate within 140 h, with maximum activity at pH 8.8, 37°C, and 0.18 M sodium chloride. Thiocyanate degradation was inhibited by 30 mg L -1 phenol, but not by thiosulfate. Microbial thiocyanate degradation is catalyzed by thiocyanate dehydrogenase, while limited information is currently available on the molecular mechanisms underlying thiocyanate degradation by the thiocyanate dehydrogenase of neutrophilic halophiles. Therefore, (meta)genomic and proteomic analyses of enrichment cultures were performed to elucidate the whole genome sequence and proteome of Thiohalobacter sp. strain FOKN1. The 3.23-Mb circular Thiohalobacter sp. strain FOKN1 genome was elucidated using a PacBio RSII sequencer, and the expression of 914 proteins was identified by tandem mass spectrometry. The Thiohalobacter sp. strain FOKN1 genome had a gene encoding thiocyanate dehydrogenase, which was abundant in the proteome, suggesting that thiocyanate is degraded by thiocyanate dehydrogenase to sulfur and cyanate. The sulfur formed may be oxidized to sulfate by the sequential oxidation reactions of dissimilatory sulfite reductase, adenosine-5'-phosphosulfate reductase, and dissimilatory ATP sulfurylase. Although the Thiohalobacter sp. strain FOKN1 genome carried a gene encoding cyanate lyase, its protein expression was not detectable. The present study advances the understanding of the molecular mechanisms underlying thiocyanate degradation by the thiocyanate dehydrogenase of neutrophilic halophiles.

A simple, small and inexpensive photometer that uses a pair of light-emitting diodes (LEDs) and a simple operational amplifier was developed for investigating thiocyanate levels in saliva obtained from smokers and non-smokers. The photometer is based on paired emitter-detector diodes (PEDDs), and the entire system can be purchased for less than a hundred US dollars. The PEDD-based photometer can measure the transmittance of a solution in a 1-cm disposable polystyrene cuvette using only rechargeable dry-cell batteries, which makes it suitable for analysis outside of equipped laboratories. The metal complex formation between Fe (III) and thiocyanate ions in an acidic condition permits colorimetric detection of thiocyanate ions using LEDs emitting at 465 nm, because the complex shows maximum absorption at 457 nm. The developed photometer exhibits excellent performance with linearity ranging from 0.05 mmol L -1 to 0.75 mmol L -1 and a correlation coefficient (r 2 ) > 0.999. The limits of detection and quantification were 0.01 mmol L -1 and 0.05 mmol L -1 , respectively. Both intra- and inter-day precision were obtained with relative standard deviations (RSD) of less than 1% in the determination of thiocyanate. The proposed method is simple, facile, and sensitive enough to investigate the levels of thiocyanate in the saliva samples of smokers and non-smokers with centrifugation being the only special treatment for samples. The results showed that the concentrations of thiocyanate were approximately 5-fold higher in smokers than in non-smokers., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The aim of the study was to estimate the thiocyanate levels in saliva of cigarette smokers in comparison to e-cigarette smokers and nonsmokers. To improve our understanding of the influence of smoking on the oral level of thiocyanate, we conducted an assessment of human saliva, in 24 individuals (eight tobacco smokers, eight e-cigarette smokers, and eight nonsmokers). High-Performance Liquid Chromatography with ultraviolet detection (HPLC-UV) using a unique phosphatidylcholine column was applied in this assay. Thiocyanate ion was detected directly by its absorbance at 210 nm. The method presents a new application of the IAM (Immobilized Artificial Membrane) column for quantification of inorganic anions. The whole process meets the criteria of green chemistry because it was carried out without the use of organic solvents. For compensating matrix effects, an eight-point standard addition protocol was used to quantify the thiocyanate level in saliva samples. The calibration graphs were linear in the range of 5-100 mg L -1 with a correlation coefficient higher than 0.99. The thiocyanate concentrations in the saliva of tobacco smokers, e-cigarette smokers, and nonsmokers were found in the range of 121.25-187.54 mg L -1 , 121.24-244.11 mg L -1 , 33.03-79.49 mg L -1 , respectively. The present study indicates an obvious statistically significant elevation in salivary thiocyanate level in tobacco smokers in comparison to nonsmokers. The phosphatidylcholine-based stationary phase proved to be suitable for the detection and quantification of the thiocyanate ion. The salivary thiocyanate levels in e-cigarette smokers were not significantly different in comparison to tobacco smokers but higher if compared to nonsmokers. The criterion for statistical significance was p < 0.05., Competing Interests: The authors declare no conflict of interest.

The aim of this study was to evaluate chemical and biological potential of garden cress (Lepidium sativum L.) to receive valuable plant extracts with potential application in pharmacy or food industry. Four techniques of extraction and three environmentally friendly solvents such as water, supercritical CO 2 and ethanol have been tested. Biological activity and chemical profile were evaluated in obtained extracts. GC/MS analysis showed that SFE extract from dried sprouts of L. sativum was especially rich in such glucosinolate derivatives as benzyl cyanide and benzyl thiocyanate. However, the extract obtained from freeze-dried sprouts by SFE with addition of 96% ethanol as co-solvent was especially rich in flavonoids and simultaneously exhibited the best antimicrobial activity. Comparison of MALDI-TOF-MS spectra of all obtained extracts clearly indicates that both SFE and maceration with water are the most selective techniques of extraction due to the lowest level of interfering substances with high molecular masses., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

SCN- is one of the most important anions in metabolic processes. However, the investigation of SCN- in living systems is restricted by the lack of stable functional molecular tools. Herein, the first fluorene-based polymer fluorescent probe V1 was synthesized through rational design. Compared with small molecule fluorescent probes, V1 exhibited excellent fluorescence stability in bovine serum albumin (BSA) solution. Furthermore, the V1-based paper sensor was highly selective toward SCN- in aqueous solution. Significantly, these merits of the probe V1 enable the detection of SCN- in different living cell lines and zebrafish.

The spatiotemporal sensing of specific cationic and anionic species is crucial for understanding the processes occurring in living systems. Herein, we developed new fluorescence sensors derived from tetrapyrazinoporphyrazines (TPyzPzs) with a recognition moiety that consists of an aza-crown and supporting substituents. Their sensitivity and selectivity were compared by fluorescence titration experiments with the properties of known TPyzPzs (with either one aza-crown moiety or two of these moieties in a tweezer arrangement). Method of standard addition was employed for analyte quantification in saliva. For K + recognition, the new derivatives had comparable or larger association constants with larger fluorescence enhancement factors compared to that with one aza-crown. Their fluorescence quantum yields in the ON state were 18× higher than that of TPyzPzs with a tweezer arrangement. Importantly, the sensitivity toward cations was strongly dependent on counteranions and increased as follows: NO 3 - < Br - < CF 3 SO 3 - < ClO 4 - ≪ SCN - . This trend resembles the chaotropic ability expressed by the Hofmeister series. The high selectivity toward KSCN was explained by synergic association of both K + and SCN - with TPyzPz sensors. The sensing of SCN - was further exploited in a proof of concept study to quantify SCN - levels in the saliva of a smoker and to demonstrate the sensing ability of TPyzPzs under in vitro conditions.

Soils in areas affected by konzo (a cassava cyanide intoxication paralytic disorder) are predominantly infertile and probably unable to supply cultivated cassava with the nutrients it needs to achieve optimal growth. Soil nutrient supply in these areas could also be influencing cyanogenic glucoside production in cassava, however there is hardly any knowledge on this. An assessment of soil nutrient levels on crop fields in konzo-affected areas was therefore carried out to determine their adequacy for optimal cassava growth. Konzo-affected Mtwara region of Tanzania, was used as a case study. Whether soil nutrient supply influences cyanogenic glucoside production in cassava cultivated in konzo-affected areas and how it could be doing this, was additionally investigated. To investigate this, correlations between total hydrogen cyanide (HCN) levels (a measure of cyanogenic glucoside content) in cassava roots and various soil nutrient levels on crops fields were carried out. This was followed by an investigation of relationships between cases of cassava cyanide intoxication and soil nutrient levels on crop fields from which the consumed toxic cassava roots had been harvested. Cases of cassava cyanide intoxication were used as a proxy for high cyanogenic glucoside levels in cassava roots. Logistic regression analysis was used in the latter investigation. Other important non-nutrient soil chemical characteristics, like pH and soil organic carbon, were also included in all analysis performed. The results revealed that most soil nutrients known to have reducing effects on cassava cyanogenic glucosides, like potassium (mean = 0.09 cmol/kg, SD = 0.05 cmol/kg), magnesium (mean = 0.26 cmol/kg, SD = 0.14 cmol/kg) and zinc (mean = 1.34 mg/kg, SD = 0.26 mg/kg) were deficient on several crop fields. The results also showed that cyanogenic glucosides in cassava roots could be increased with the increased supply of sulphur in soils in bitter cassava varieties (rs = 0.593, p = 0.032), and with the increased supply of P in soils in all cassava varieties (rs = 0.486, p = 0.026). The risk of cassava cyanide intoxication occurring (and thus high cyanogenic glucoside levels in cassava) was found to be likely increased by cultivating cassava on soils with high pH (X2 = 8.124, p = 0.004) and high iron (X2 = 5.740, p = 0.017). The study managed to establish that cassava grows under conditions of severe nutrient stress and that soil nutrient supply influences cyanogenic glucoside production in cassava cultivated in konzo-affected areas of Mtwara region. Despite the multiple soil nutrient deficiencies on crop fields, low soil fertility was however not the only probable cause of increased cyanogenic glucosides in cassava, as high soil nutrient levels were also found to be potential contributors., Competing Interests: The authors have declared that no competing interests exist.

An analytical method was developed for the simultaneous determination of thiocyanate and iodide by reversed-phase liquid chromatography with UV detection using imidazolium ionic liquids as mobile phase additives. The chromatographic behaviors of the two anions on a C 18 column were studied and compared with four types of reagents including imidazolium ionic liquids, pyridinium ionic liquids, 4-aminophenol hydrochloride and tetrabutylammonium as mobile phase additives. The effects of the concentrations of imidazolium ionic liquids, organic solvents and detection wavelength on separation and detection of the anions were investigated. The role of ionic liquids, retention rules and mechanisms were discussed. The separation of the anions was performed on the C 18 reserved-phase column using acetonitrile-0.3 mmol/L 1-amyl-3-methylimidazolium tetrafluoroborate (10:90, v/v) as mobile phase, with column temperature of 35°C, flow rate of 1 mL/min and detection wavelength of 210 nm. Under these conditions, the two anions can be completely separated within 6 min. The limits of detection were 0.05 mg/L. The method was applied for the determination of thiocyanate and iodide in ionic liquid samples and iodide drugs, and the spiked recoveries ranged from 97 to 101%. The method is simple, accurate and meets the requirements of quantitative analysis for thiocyanate and iodide., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A method is developed for detecting the concentration of sodium thiocyanate (NaSCN) in milk based on surface-enhanced Raman scattering (SERS) technology. A trichloroacetic acid solution can be used to enhance the SERS signal because of its function in promoting the aggregation of Ag nanoparticles (Ag NPs). Meanwhile, the protein in milk would be precipitated as trichloroacetic acid added and the interference from protein could be reduced during the detection. In this work, the enhancement factor (EF) is 7. 56 × 10⁵ for sodium thiocyanate in water and the limit of detection (LOD) is 0.002 mg/L. Meanwhile, this method can be used to detect the concentration of sodium thiocyanate in milk. Results show that SERS intensity increased as the concentration of sodium thiocyanate increase from 10 to 100 mg/L. The linear correlation coefficient is R² = 0.998 and the detection limit is 0.04 mg/L. It is observed that the concentration of sodium thiocyanate does not exceed the standard in the three kinds of milk. The confirmed credibility of SERS detection is compared with conventional methods.

Strategies to detect and characterize myeloperoxidase (MPO) are needed, given that this "split personality" enzyme kills harmful microorganisms but also damages a host tissue. Here, we describe electrochemical approaches to measure MPO by using the pseudohalogenation (MPO/SCN - /H 2 O 2 ) and catalase-like (MPO/H 2 O 2 ) cycles. Their kinetics were determined by monitoring the consumption of H 2 O 2 with a nitrogen-doped carbon nanotubes (N-CNT) electrode, which could detect 0.50 μM H 2 O 2 at -0.20 V. The unique design of internally calibrated electrochemical continuous enzyme assay (ICECEA) and electrode stability allowed use of one N-CNT electrode for over half a year to reliably determine MPO. The kinetic measurements showed that (a) SCN - did not affect the affinity of MPO for H 2 O 2 , (b) catalase-like cycle was slower, and (c) MPO retained enzymatically active conformation after complexation with its antibody Ab both in a solution and on the surface of an antibody dipstick (d/Ab). The homogeneous assays could detect 5.2 μg L -1 MPO (35 pM) via a faster cycle. The heterogeneous immunoassays with the capture of MPO on d/Ab could detect 60 μg L -1 , which was suitable for the accurate detection of MPO in human saliva (101% recovery). Replacing a detection antibody of ELISA with ICECEA as a signal transducer for immunoassays offers a rapid method for the selective determination of enzymes; for example, time of MPO quantification was cut from 3-4 h (sandwich ELISA) to ∼20 min (ICECEA-dipstick).

Our previous results showed higher level of anti-Hib IgG (2.41 μg/ml) average geometric mean concentration (GMC) regardless of age and gender, followed by levels of IgM (0.91 μg/ml) and IgA (0.34 μg/ml), reflecting the prevalence of immunity against Hib. Current study was evaluated the avidity profile for these high anti-Hib concentration. The IgM avidity analysis did not revealed any significant results between male and female values. While, the average of IgA avidity in male samples were significantly (P< 0.05) higher than the average of female. Also, The result showed that high percentage of population has moderate to high IgG avidity. The study showed lower avidity percentages of both IgM and IgA comparing to IgG. More studies are suggested to be done on individuals with low avidity considering the secondary immunodeficiency in participant's history.

Leptospirillum ferriphilum is the dominant iron-oxidising bacterium in traditional microbial communities utilised in bioprocesses for gold recovery from sulfidic minerals. Ferrous iron oxidation activity and growth of unadapted and thiocyanate-adapted L. ferriphilum HT was studied in batch culture across increasing thiocyanate (SCN - ) concentrations in the range 0-2 mg/L to assess the feasibility of recycling remediated cyanidation wastewaters. Thiocyanate concentrations of 1 mg/L and 1.4 mg/L induced an inhibitory effect in the unadapted culture wherein ferrous iron oxidation rate and cell growth were compromised. A substantial lag in the onset of ferrous iron oxidation occurred at concentrations above 0.5 mg/L SCN - , with no oxidation activity above 1.75 mg/L SCN - . The adapted culture, however, was uninhibited across the SCN - concentration range investigated and demonstrated a higher specific ferrous iron oxidation rate owing to reduced growth. It is postulated that SCN - exposure in the absence of adaptation induces osmotic stress. Moreover, upregulation of genes associated with the synthesis of osmo-protectants may be responsible for the preservation of activity observed in the adapted culture. As L. ferriphilum is dominant within the biooxidation tank community, evidence of sustained iron oxidation activity at low-level SCN - concentrations affirms the potential of recycling bioremediated cyanidation wastewater., (Copyright © 2018 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.)

Background: Use of tobacco is often implicated in the development of oral diseases. Questionable accuracy of the traditional questionnaires to assess cigarette exposure necessitates the use of biomarkers like thiocyanate which provide a definitive quantitative measure., Objective: To assess the rise in the level of thiocyanate for measurement of smoking behaviour in adults., Materials and Methods: Serum and salivary thiocyanate levels were estimated in 20 non-smokers, 20 ex-smokers and 40 smokers. Smokers were divided into two groups based on the presence or absence of oral mucosal lesions., Results: The mean serum and salivary thiocyanate levels were increased significantly in smokers when compared to non-smokers and ex-smokers. The levels were not significantly different between ex-smokers and non-smokers and between smokers with tobacco related oral mucosal lesions and those without. Statistically significant correlation was seen between the serum and salivary levels of thiocyanate., Conclusion: This study highlights the high level of thiocyanate in the serum and saliva of smokers when compared to non-smokers and ex-smokers. Significant increase in thiocyanate level was also seen in saliva. Hence it can be stated that saliva can be used as a reliable, non-invasive tool to assess smoking behaviour in the population and its changes over time.

Bladder cancer is a significant health burden due to its high prevalence, risk of mortality, morbidity, and high cost of medical care. Epidemiologic evidence suggests that diets rich in cruciferous vegetables, particularly broccoli, are associated with lower bladder cancer risk. Phytochemicals in cruciferous vegetables, such as glucosinolates, which are enzymatically hydrolyzed to bioactive isothiocyanates, are possible mediators of an anticancer effect. In vitro studies have shown inhibition of bladder cancer cell lines, cell cycle arrest, and induction of apoptosis by these isothiocyanates, in particular sulforaphane and erucin. Although not yet completely understood, many mechanisms of anticancer activity at the steps of cancer initiation, promotion, and progression have been attributed to these isothiocyanates. They target multiple pathways including the adaptive stress response, phase I/II enzyme modulation, pro-growth, pro-survival, pro-inflammatory signaling, angiogenesis, and even epigenetic modulation. Multiple in vivo studies have shown the bioavailability of isothiocyanates and their antitumoral effects. Although human studies are limited, they support oral bioavailability with reasonable plasma and urine concentrations achieved. Overall, both cell and animal studies support a potential role for isothiocyanates in bladder cancer prevention and treatment. Future studies are necessary to examine clinically relevant outcomes and define guidelines on ameliorating the bladder cancer burden., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The enzymatic system in saliva, consisting of salivary peroxidase (SPO), hydrogen peroxide (H 2 O 2 ), and thiocyanate (SCN - ), produces hypothiocyanite (OSCN - ) as a high effective antibacterial compound. OSCN - is of great importance for the natural non-specific antibacterial resistance in the oral cavity. However, no analytical method currently exists to selectively quantify OSCN - in saliva samples. A robust and specific analytical method for the determination of OSCN - was developed based on ion chromatography with combined UV and electrochemical detection. Calibration was achieved by calculating a derived calibration factor based on the known ratio of molar extinction coefficients of SCN - and OSCN - . Thus, the specific quantification of OSCN - in saliva samples is possible, as demonstrated here. The median value of 200 saliva samples was determined to be 0.56 mg L -1 (median), with a maximum of 3.9 mg L -1 ; the minimum value was below the detection limit (< 0.09 mg L -1 ). The recovery rate in individual saliva samples was 95 ± 8%.

In order to protect human health, it is necessary to biomonitor toxic substances originating from tobacco smoke in biological materials sampled from persons with different exposures to tobacco smoke constituents. Thiocyanate anion is a biomarker of exposure to tobacco smoke components which is characterized by a relatively long half-life in the human body, i.e. 6 days. In this work, we present the results of thiocyanate determinations performed on samples of placenta, meconium, saliva, breast milk, sweat and blood. The placenta samples were subjected to accelerated solvent extraction with water. The thiocyanate concentrations were determined using ion chromatography. The analyzed biological materials were compared with regard to their applicability for biomonitoring toxic substances originating from tobacco smoke. The highest mean concentrations of thiocyanate were observed in the samples of biological materials collected from active smokers., (Copyright © 2017 John Wiley & Sons, Ltd.)

In this work, core-shell Au@Pt nanocatalysts (Au@Pt NCs) with ultrathin Pt shell were synthesized and demonstrated high peroxidase-like activity. Thiocyanate ions (SCN - ) were found to effectively inhibit the peroxidase-like activity of Au@Pt NCs, and the mechanism was discussed by the characterization of TEM, DLS, EPR and XPS, etc. The inhibition of the catalytic activity of Au@Pt NCs by SCN - was mainly due to the decreased ability of the Au@Pt NCs for capturing • OH radicals and the increased ratio of Pt 2+ to Pt° on the surface of the Au@Pt NCs. A sensitive colorimetric detection of thiocyanate (SCN - ) was developed, based on the activity inhibition of Au@Pt NCs by SCN - . Interestingly, cystine modification of Au@Pt NCs was found to significantly improve the selectivity of SCN - recognition. After optimization, a colorimetric assay for SCN - was established with a detection limit of 5.0nM and a broad linear calibration over the range of 20nM to 40µM. This assay has the advantages of highly sensitive, selective and low-cost. Moreover, this assay demonstrated highly potential application in the quantitative determination of SCN - in water and raw milk samples., (Copyright © 2017. Published by Elsevier B.V.)

Better milk safety control can offer important means to promote public health. However, few technologies can detect different types of contaminants in milk simultaneously. In this regard, the present work proposes a single-drop Raman imaging (SDRI) strategy for semiquantitation of multiple hazardous factors in milk solutions. By developing SDRI strategy that incorporates the coffee-ring effect (a natural phenomenon often presents in a condensed circle pattern after a drop evaporated) for sample pretreatment and discrete wavelet transform for spectra processing, the method serves well to expose typical hazardous molecular species in milk products, such as melamine, sodium thiocyanate and lincomycin hydrochloride, with little sample preparation. The detection sensitivity for melamine, sodium thiocyanate, and lincomycin hydrochloride are 0.1 mg kg -1 , 1 mg kg -1 , and 0.1 mg kg -1 , respectively. Theoretically, we establish that the SDRI represents a novel and environment-friendly method that screens the milk safety efficiently, which could be well extended to inspection of other food safety.

We report on the development of optochemical sensor based on Mn(III)-salophen ionophore. The sensor was prepared by embedding the ionophore in a plasticized poly (vinyl chloride) impregnated with the chromoionophore ETH7075. Optical response to thiocyanate occurred due to thiocyanate extraction into the polymer via formation of strong complex with the ionophore and simultaneous protonation of the indicator dye yielding the optical response at 545nm. The developed optochemical sensor exhibited high selectivity for thiocyanate over other anions including the most lipophilic species such as salicylate and perchlorate. For instance, the optical selectivity coefficients, logK SCN,anion opt , were as follow: ClO 4 - =-5.8; Sal - =-4.0; NO 3 - ˂-6. Further, the thiocyanate optical selectivity obtained using the present optochemical sensor was greatly enhanced in comparison with that obtained using an anion-exchanger based sensor. Also, the optimized optochemical sensor exhibited micro-molar detection limit with 2min response time at pH4.5 using acetate buffer. The reversibility of the optimized sensor was poor due to strong ligation of the thiocyanate to the central Metal ion, log K=14.1, which can be overcome by soaking the optode in sodium hydroxide followed by soaking in buffer solution. The developed sensor was utilized successfully for the determination of thiocyanate in human saliva and in spiked saliva samples., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The feasibility of using anaerobic ammonium oxidation (anammox) process to treat industrial wastewater containing thiocyanate (SCN - ) was examined in this study. Anammox activity decreased with increasing thiocyanate concentration and pre-exposure time in batch tests. A typical noncompetitive model was used to fit the data for thiocyanate inhibition, and the 50% inhibition concentration (IC 50 ) of thiocyanate on anammox was 620.4mgL -1 at 200mgL -1 total nitrogen level. The influent thiocyanate concentration of test reactor (R 1 ) in phase II gradually increased from 10 to 120mgL -1 , and the average nitrogen removal efficiency (NRE) of R 1 was maintained at 83.0±7.82%. This robustness was attributed to the self-adaptation ability of anammox biomass through long-term acclimatization. The NRE was decreased to 57.1% under 130mgL -1 thiocyanate within two days. However, the NRE of control reactor (R 0 ) in absence of thiocyanate was 91.23±4.11% in this phase. Under thiocyanate stress, the specific anammox activity, settling velocity and heme c content of the granules significantly decreased, and the extracellular polymeric substances content slightly increased. The short- and long-term performance inhibition could be reversed in the presence of 10mgL -1 Fe(III)., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Dietary supplementation with inorganic nitrate (NO 3 - ) has been reported to improve cardiovascular health indices in healthy adults. Cigarette smoking increases circulating thiocyanate (SCN - ), which has been suggested to competitively inhibit salivary nitrate (NO 3 - ) uptake, a rate-limiting step in dietary NO 3 - metabolism. Therefore, this study tested the hypothesis that dietary NO 3 - supplementation would be less effective at increasing the circulating plasma nitrite concentration ([NO 2 - ]) and lowering blood pressure in smokers (S) compared to non-smokers (NS). Nine healthy smokers and eight healthy non-smoking controls reported to the laboratory at baseline (CON) and following six day supplementation periods with 140 mL day -1 NO 3 - -rich (8.4 mmol NO 3 -  day -1 ; NIT) and NO 3 - -depleted (0.08 mmol NO 3 -  day -1 ; PLA) beetroot juice in a cross-over experiment. Plasma and salivary [SCN - ] were elevated in smokers compared to non-smokers in all experimental conditions (P < 0.05). Plasma and salivary [NO 3 - ] and [NO 2 - ] were elevated in the NIT condition compared to CON and PLA conditions in smokers and non-smokers (P < 0.05). However, the change in salivary [NO 3 - ] (S: 3.5 ± 2.1 vs. NS: 7.5 ± 4.4 mM), plasma [NO 3 - ] (S: 484 ± 198 vs. NS: 802 ± 199 μM) and plasma [NO 2 - ] (S: 218 ± 128 vs. NS: 559 ± 419 nM) between the CON and NIT conditions was lower in the smokers compared to the non-smokers (P < 0.05). Salivary [NO 2 - ] increased above CON to a similar extent with NIT in smokers and non-smokers (P > 0.05). Systolic blood pressure was lowered compared to PLA with NIT in non-smokers (P < 0.05), but not smokers (P > 0.05). These findings suggest that dietary NO 3 - metabolism is compromised in smokers leading to an attenuated blood pressure reduction compared to non-smokers after NO 3 - supplementation. These observations may provide novel insights into the cardiovascular risks associated with cigarette smoking and suggest that this population may be less likely to benefit from improved cardiovascular health if they increase dietary NO 3 - intake., (Copyright © 2016 Elsevier Inc. All rights reserved.)

Aims: To evaluate the levels of salivary thiocyanate and its relation with the occurrence of micronuclei (MN) using exfoliative cytology in smokers and nonsmokers., Materials and Methods: One hundred and twenty patients were divided into 3 groups: nonsmoker group 1 (control), smokers group 2, and smokers group 3. Their saliva was collected and analyzed for thiocyanate levels, and exfoliative cytology was evaluated for the presence of MN., Statistical Analysis Used: Fisher's exact test and ANOVA test were used., Results: It was seen that as the grade of smoking increased, the levels of salivary thiocyanate and occurrence of MN increased., Conclusions: Detection and quantification of "biomarkers" such as salivary thiocyanate and MN in noninvasive and painless procedures such as oral exfoliative cytology can be an upcoming research domain in the field of cancer prevention and therapeutics.

A simple, low cost and efficient headspace sorptive solid phase microextraction (HS-SPME) method for determination of cyanide has been developed. The system comprises of a glass tube with two valves and a moveable glass slide fixed at its centre. It includes an acceptor phase polyurethane foam treated mercury (II) dithizonate [Hg(HDz)2-PUF] complex fixed inside by a septum cap in a cylindrical configuration (5.0cm length and 1.0cm diameter). The extraction is based upon the contact of the acceptor phase to the headspace and subsequently measuring the absorbance of the recovered mercury (II) dithizonate from PUFs sorbent. Unlike other HSSE, extraction and back - extractions was carried out in a closed system, thereby improving the analytical performance by preventing the analyte loss. Under the optimized conditions, a linear calibration plot in the range of 1.0-50.0µmolL(-1) was achieved with limits of detection (LOD) and quantification (LOQ) of 0.34, 1.2µmolL(-1) CN(-), respectively. Simultaneous analysis of cyanide and thiocyanate in saliva was also performed with satisfactory recoveries., (Copyright © 2016. Published by Elsevier B.V.)

Saliva provides a valuable tool for assessing oral and systemic diseases, but concentrations of salivary components are very small, calling the need for precise analysis methods. In this work, Fourier transform infrared (FT-IR) spectroscopy using transmission and photoacoustic (PA) modes were compared for quantitative analysis of saliva. The performance of these techniques was compared with a calibration series. The linearity of spectrum output was verified by using albumin-thiocyanate (SCN(-)) solution at different SCN(-) concentrations. Saliva samples used as a comparison were obtained from healthy subjects. Saliva droplets of 15 µL were applied on the silicon sample substrate, 6 drops for each specimen, and dried at 37 ℃ overnight. The measurements were carried out using an FT-IR spectrometer in conjunction with an accessory unit for PA measurements. The findings with both transmission and PA modes mirror each other. The major bands presented were 1500-1750 cm(-1) for proteins and 1050-1200 cm(-1) for carbohydrates. In addition, the distinct spectral band at 2050 cm(-1) derives from SCN(-) anions, which is converted by salivary peroxidases to hypothiocyanate (OSCN(-)). The correlation between the spectroscopic data with SCN(-) concentration (r > 0.990 for transmission and r = 0.967 for PA mode) was found to be significant (P < 0.01), thus promising to be utilized in future applications., (© The Author(s) 2016.)

The PVC based-ion selective electrode viz., bis nitrato[4-hydroxyacetophenone semicarbazone] nickel(II) as an ionophore was prepared for the determination of thiocyanate ion. The ionophore was characterized by FT-IR, UV-vis, XRD, magnetic moment and elemental analysis (CHN). On the basis of spectral studies an octahedral geometry has been assigned. The best performance was obtained with a membrane composition of 31% PVC, 63% 2-nitrophenyl octylether, 4.0% ionophore and 2.0% trioctylmethyl ammonium chloride. The electrode exhibited an excellent Nernstian response to SCN(-) ion ranging from 1.0 × 10(-7) to 1.0 × 10(-1)M with a detection limit of 8.6 × 10(-8)M and a slope of -59.4 ± 0.2 mV/decade over a wide pH range (1.8-10.7) with a fast response time (6s) at 25 °C. The proposed electrode showed high selectivity for thiocyanate ion over a number of common inorganic and organic anions. It was successfully applied to direct determination of thiocyanate in biological (urine and saliva) samples in order to distinguish between smokers and non-smokers, environmental samples and as an indicator electrode for titration of thiocyanate ions with AgNO3 solution., (Copyright © 2016 Elsevier B.V. All rights reserved.)

A capillary electrophoresis approach with capacitively coupled contactless conductivity detection method has been developed for the determination of inorganic metabolites (thiocyanate, nitrite and nitrate) in human saliva. Field amplified sample injection, as a simple sample stacking technique, was used in conjunction for online preconcentration of above inorganic anions. A selective separation for the target anions from other coexisting constituents present in saliva could be obtained within 14min in a 10mmol/L His-90mmol/L HAc buffer (pH 3.70) at the separation voltage of -18kV. The limits of detection and limits of quantification of the three analytes were within the range of 3.1-4.9ng/mL (S/N=3) and 10-16ng/mL (S/N=10), respectively. The average recovery data were in the range of 81-108% at three different concentrations. This method provides a simple, rapid and direct approach for metabolite analyses of nitric oxide and cyanide based on noninvasive saliva sample, which presents a potential fast screening tool for clinical test., (Copyright © 2016 Elsevier B.V. All rights reserved.)

This work describes a fast and simple assay for in situ detection of thiocyanate, i.e., a biomarker of tobacco smoke exposure, in human saliva. The assay is based on the formation of an iron(III)-thiocyanate colored complex in a paper-based sensing platform and subsequent image analysis using a scanner as detection device. Experimental parameters influencing the color intensity of the complex were fully evaluated, including the selection of detection conditions, type of paper substrate, test zone dimensions and composition as well as the stability of the paper-based device. Under optimal conditions, the detection limit was 0.06mM of thiocyanate, and the repeatability, expressed as relative standard deviation, was 3%. The proposed method, characterized by its simplicity, portability and low sample consumption, was applied to the detection of thiocyanate in a series of human saliva samples. Average thiocyanate levels in the ranges 0.28-0.87mM and 0.78-4.28mM were found for non-smokers and smokers, respectively. Recovery studies were carried out at two concentration levels, showing recovery values in the range of 96.1-103.6%., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Aim: This study was conducted to estimate and correlate salivary thiocyanate (SCN) levels in periodontally healthy subjects, smokers, nonsmokers, and gutka-chewers with chronic periodontitis., Methodology: The study population consisted of 40 systemically healthy subjects in the age group of 18-55 years that was further divided into four groups: Control, smokers, nonsmokers, and gutka-chewers with chronic periodontitis. Gingival index (GI) (Loe and Silness-1963), probing depth (PD), clinical attachment loss was assessed. Estimation of SCN was performed by ultraviolet spectrophotometer at 447 nm wavelength. Statistical analysis was performed using the one-way ANOVAs Welch test and Pearson's correlation test using SPSS version 17 software., Results: Results showed statistically significant increase in SCN levels in smokers as compared to gutka-chewers with chronic periodontitis, control, and nonsmokers with chronic periodontitis subjects. Significantly higher PD and loss of attachment were seen in smokers group compared with other groups. A negative correlation observed between the GI and thiocyanate levels., Conclusion: The present study revealed a significant increase in SCN levels in smokers with periodontitis as compared to nonsmokers.

A novel, highly sensitive and selective dual-readout (colorimetric and fluorometric) sensor based on fluorescent carbon dots (CDs) and unmodified gold nanoparticles (AuNPs) for the detection of thiocyanate (SCN(-)) was proposed. Amino-functionalized CDs could be readily adsorbed onto the surface of citrate-stabilized AuNPs through Au-N interactions, leading to the aggregation of AuNPs and the nonfluorescent off-state of CDs arising from potential fluorescence resonance energy transfer (FRET). However, SCN(-) had a stronger affinity toward AuNPs and could compete with CDs to bind onto the surface of AuNPs in priority, which prevented the aggregation of AuNPs and fluorescence quenching of CDs. Correspondingly, both the colorimetric and fluorometric signals remained "light-on". The color of the sensing solution remained red and the fluorescence remained unquenched. A distinguishable change in the color was observed at a SCN(-) concentration of 1 μM by the naked eye and a detection limit as low as 0.036 μM was obtained by virtue of fluorescence spectroscopy. Both colorimetric and fluorometric sensors exhibited excellent selectivity toward SCN(-) over other common metallic ions and anions. In addition, such a sensing assay featured simplicity, rapidity, cost-effectiveness and ease of operation without further modification. The accuracy and precision were evaluated based on the quantitative detection of SCN(-) in tap water and saliva samples with satisfactory results.

We have found that hydroxyl-rich carbon dots (C-dots) have the ability to reduce Au(3+) to form gold nanoparticles (AuNPs). Thiocyanate (SCN(-)) can be absorbed on the surface of the AuNPs due to its high affinity toward the AuNPs, which inhibits the growth of the AuNPs. Meanwhile, SCN(-) has the ability to etch the as-synthesized big AuNPs to small AuNPs, which can also cause the absorption peak of the AuNPs to decrease. Therefore, an optical sensor is developed for the detection of SCN(-) based on measuring the plasmon resonance absorption peak change of the AuNPs. Under optimal conditions, this method yields excellent sensitivity (the limit of detection is 0.16 μM) and selectivity toward SCN(-). This method can detect SCN(-) in raw milk with satisfactory results. This work gives new insight into monitoring the quality of milk.

In the present study, a comparison of five peroxide analytical methods was performed using oxidized ghee. The methods included the three iodometric titration viz. Bureau of Indian Standard (BIS), Association of Analytical Communities (AOAC) and American Oil Chemists' Society (AOCS), and two colorimetric methods, the ferrous xylenol orange (FOX) and ferric thiocyanate (International Dairy Federation, IDF) methods based on oxidation of iron. Six ghee samples were stored at 80 °C to accelerate deterioration and sampled periodically (every 48 h) for peroxides. Results were compared using the five methods for analysis as well as a flavor score (9 point hedonic scale). The correlation coefficients obtained using the different methods were in the order: FOX (-0.836) > IDF (-0.821) > AOCS (-0.798) > AOAC (-0.795) > BIS (-0.754). Thus, among the five methods used for determination of peroxide value of ghee during storage, the highest coefficient of correlation was obtained for the FOX method. The high correlations between the FOX and flavor data indicated that FOX was the most suitable method tested to determine peroxide value in oxidized ghee., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Introduction: Xanthine oxidase (XO) is distributed in mammals largely in the liver and small intestine, but also is highly active in milk where it generates hydrogen peroxide (H2O2). Adult human saliva is low in hypoxanthine and xanthine, the substrates of XO, and high in the lactoperoxidase substrate thiocyanate, but saliva of neonates has not been examined., Results: Median concentrations of hypoxanthine and xanthine in neonatal saliva (27 and 19 μM respectively) were ten-fold higher than in adult saliva (2.1 and 1.7 μM). Fresh breastmilk contained 27.3 ± 12.2 μM H2O2 but mixing baby saliva with breastmilk additionally generated >40 μM H2O2, sufficient to inhibit growth of the opportunistic pathogens Staphylococcus aureus and Salmonella spp. Oral peroxidase activity in neonatal saliva was variable but low (median 7 U/L, range 2-449) compared to adults (620 U/L, 48-1348), while peroxidase substrate thiocyanate in neonatal saliva was surprisingly high. Baby but not adult saliva also contained nucleosides and nucleobases that encouraged growth of the commensal bacteria Lactobacillus, but inhibited opportunistic pathogens; these nucleosides/bases may also promote growth of immature gut cells. Transition from neonatal to adult saliva pattern occurred during the weaning period. A survey of saliva from domesticated mammals revealed wide variation in nucleoside/base patterns., Discussion and Conclusion: During breast-feeding, baby saliva reacts with breastmilk to produce reactive oxygen species, while simultaneously providing growth-promoting nucleotide precursors. Milk thus plays more than a simply nutritional role in mammals, interacting with infant saliva to produce a potent combination of stimulatory and inhibitory metabolites that regulate early oral-and hence gut-microbiota. Consequently, milk-saliva mixing appears to represent unique biochemical synergism which boosts early innate immunity.

A novel method for the determination of salivary thiocyanate is presented. Thiocyanate was converted into ethyl thiocyanate by single-step aqueous derivatization based on triethyloxonium tetrafluoroborate and measured by gas chromatography-mass spectrometry (15 min runtime). The ethyl thiocyanate derivative is volatile and can be sampled from the headspace. The derivatization chemistry proposed allows for separation of the analyte from saliva matrix whose introduction in the measurement system is avoided. Quantitation of the analyte was obtained by isotope dilution, employing a (13)C-enriched thiocyanate as internal standard. Technical details and fundamental aspects of derivatization chemistry and calibration strategy are presented. The method was validated by comparison with a standard method based on ion chromatography. The two independent methodologies produced results in agreement within 3%. Also a three level spike recovery test was carried out for validation purpose and quantitative recoveries were attained. The method is fast, simple, safe, and sensitive. Measurement of a 1 mL volume 50 ng/g of thiocyanate standard produced a signal-to-noise ratio of 250 for the analytical peak. This method is therefore suitable for ultra-trace determination of thiocyanate (low part-per-billion range). For the application described the full detection potential of the method was not required and the sample preparation presented has been designed for quantitation of saliva samples containing 1-400 μg/g of thiocyanate with a combined standard uncertainty of 2% relative for saliva samples containing 25 μg/g of thiocyanate. This method was applied for the determination of thiocyanate in human saliva samples., (Crown Copyright © 2015. Published by Elsevier B.V. All rights reserved.)