Salivary iodide status as a measure of whole body iodine homoeostasis?

Iodine is a trace element required to produce the thyroid hormones, which are critical for development, growth and metabolism. To ensure appropriate population iodine nutrition, convenient and accurate methods of monitoring are necessary. Current methods for determining iodine status either involve a significant participant burden or are subject to considerable intra-individual variation. The continuous secretion of iodide in saliva potentially permits its use as a convenient, non-invasive assessment of status in populations. To assess its likely effectiveness, we reviewed studies analysing the association between salivary iodide concentration (SIC) and dietary iodine intake, urinary iodide concentration (UIC) and/or 24-h urinary iodide excretion (UIE). Eight studies conducted in different countries met the inclusion criteria, including data for 921 subjects: 702 healthy participants and 219 with health conditions. SIC correlated positively with UIC and/or UIE in four studies, with the strength of relationship ranging from r = 0·19 to r = 0·90 depending on sampling protocol, age, and if salivary values were corrected for protein concentration. Additionally, SIC positively correlated with dietary intake, being strongest when saliva was collected after dinner. SIC varied with external factors, including thyroid function, use of some medications, smoking and overall health status. Evidence provided here supports the use of SIC as a viable, low-burden method for determining iodine status in populations. However, small sample sizes and high variability indicates the need for more extensive analyses across age groups, ethnicities, disease states and dietary groups to clarify the relative accuracy and reliability in each case and standardise procedure.

Heavy atom-induced quenching of fluorescent organosilicon nanoparticles for iodide sensing and total antioxidant capacity assessment.

We present a novel approach for iodide sensing based on the heavy-atom effect to quench the green fluorescent emission of organosilicon nanoparticles (OSiNPs). The fluorescence of OSiNPs was significantly quenched (up to 97.4% quenching efficiency) in the presence of iodide ions (I-) through oxidation by hydrogen peroxide. Therefore, OSiNPs can serve as a fluorescent probe to detect I- with high selectivity and sensitivity. The highly selective response is attributed to the hydrophilic surface enabling good dispersion in aqueous solutions and the lipophilic core allowing the generated liposoluble I2 to approach and quench the fluorescence of OSiNPs. The linear working range for I- was from 0 to 50 µM, with a detection limit of 0.1 µM. We successfully applied this nanosensor to determine iodine content in edible salt. Furthermore, the fluorescent OSiNPs can be utilized for the determination of total antioxidant capacity (TAC). Antioxidants reduce I2 to I-, and the extent of quenching by the remaining I2 on the OSiNPs indicates the TAC level. The responses to ascorbic acid, pyrogallic acid, and glutathione were investigated, and the detection limit for ascorbic acid was as low as 0.03 µM. It was applied to the determination of TAC in ascorbic acid tablets and fruit juices, indicating the potential application of the OSiNP-based I2 sensing technique in the field of food analysis.

Iodine enrichment in the groundwater in South China and its hydrogeochemical control.

In North China, iodine-rich groundwater has been extensively studied, but few in South China. This study aimed to investigate the characteristics of iodine-rich groundwater in South China and identify potential contamination sources. The results revealed that the average concentration of iodine in groundwater was 890 µg/L, with a maximum concentration of 6350 µg/L, exceeding the permitted levels recommended by the World Health Organization (5-300 µg/L). Notably, the enrichment of iodide occurred in acidic conditions (pH = 6.6) and a relatively low Eh environment (Eh = 198.4 mV). Pearson correlation and cluster analyses suggested that the enrichment of iodide could be attributed to the intensified redox process involving Mn(II), iodine (I2), or iodate (IO3-) in the soil. The strong affinity between Mn(II) and I2/IO3- facilitated their interaction, resulting in the formation and mobilization of I- from the soil to the groundwater. Leaching experiments further confirmed that reducing substances (such as sodium sulfides, ascorbic acids, and fulvic acids) in the soil with low dissolved oxygen (DO) levels (< 1.0 mg/L) enhanced the dissolution of iodine species. Conversely, higher DO content (> 3.8 mg/L) promoted the oxidation of I- into I2 or IO3-, leading to its stabilization. This research provides new insights into the characteristics and mechanisms of I- enrichment in groundwater in South China, and emphasizes the significance of the redox reactions involving Mn(II) and I2/IO3-, as well as the influence of soil properties in regulating the occurrence and transportation of iodine species within groundwater systems.

Bacterial Sulfate Reduction Facilitates Iodine Mobilization in the Deep Confined Aquifer of the North China Plain.

Bacterial sulfate reduction plays a crucial role in the mobilization of toxic substances in aquifers. However, the role of bacterial sulfate reduction on iodine mobilization in geogenic high-iodine groundwater systems has been unexplored. In this study, the enrichment of groundwater δ34SSO4 (15.56 to 69.31‰) and its significantly positive correlation with iodide and total iodine concentrations in deep groundwater samples of the North China Plain suggested that bacterial sulfate reduction participates in the mobilization of groundwater iodine. Similar significantly positive correlations were further observed between the concentrations of iodide and total iodine and the relative abundance of the dsrB gene by qPCR, as well as the composition and abundance of sulfate-reducing bacteria (SRB) predicted from 16S rRNA gene high-throughput sequencing data. Subsequent batch culture experiments by the SRB Desulfovibrio sp. B304 demonstrated that SRB could facilitate iodine mobilization through the enzyme-driven biotic and sulfide-driven abiotic reduction of iodate to iodide. In addition, the dehalogenation of organoiodine compounds by SRB and the reductive dissolution of iodine-bearing iron minerals by biogenic sulfide could liberate bound or adsorbed iodine into groundwater. The role of bacterial sulfate reduction in iodine mobilization revealed in this study provides new insights into our understanding of iodide enrichment in iodine-rich aquifers worldwide.

Freezing-Enhanced Photoreduction of Iodate by Fulvic Acid.

Iodate is a stable form of iodine species in the natural environment. This work found that the abiotic photosensitized reduction of iodate by fulvic acid (FA) is highly enhanced in frozen solution compared to that in aqueous solution. The freezing-induced removal of iodate by FA at an initial pH of 3.0 in 24 h was lower than 10% in the dark but enhanced under UV (77.7%) or visible light (31.6%) irradiation. This process was accompanied by the production of iodide, reactive iodine (RI), and organoiodine compounds (OICs). The photoreduction of iodate in ice increased with lowering pH (pH 3-7 range) or increasing FA concentration (1-10 mg/L range). It was also observed that coexisting iodide or chloride ions enhanced the photoreduction of iodate in ice. Fourier transform ion cyclotron resonance mass spectrometric analysis showed that 129 and 403 species of OICs (mainly highly unsaturated and phenolic compounds) were newly produced in frozen UV/iodate/FA and UV/iodate/FA/Cl- solution, respectively. In the frozen UV/iodate/FA/Cl- solution, approximately 97% of generated organochlorine compounds (98 species) were identified as typical chlorinated disinfection byproducts. These results call for further studies of the fate of iodate, especially in the presence of chloride, which may be overlooked in frozen environments.

Microbial Contributions to Iodide Enrichment in Deep Groundwater in the North China Plain.

Microorganisms play crucial roles in the global iodine cycling through iodine oxidation, reduction, volatilization, and deiodination. In contrast to iodate formation in radionuclide-contaminated groundwater by the iodine-oxidizing bacteria, microbial contribution to the formation of high level of iodide in geogenic high iodine groundwater is poorly understood. In this study, our results of comparative metagenomic analyses of deep groundwater with typical high iodide concentrations in the North China Plain revealed the existence of putative dissimilatory iodate-reducing idrABP1P2 gene clusters in groundwater. Heterologous expression and characterization of an identified idrABP1P2 gene cluster confirmed its functional role in iodate reduction. Thus, microbial dissimilatory iodate reduction could contribute to iodide formation in geogenic high iodine groundwater. In addition, the identified iron-reducing, sulfur-reducing, sulfur-oxidizing, and dehalogenating bacteria in the groundwater could contribute to the release and production of iodide through the reductive dissolution of iron minerals, abiotic iodate reduction of derived ferrous iron and sulfide, and dehalogenation of organic iodine, respectively. These microbially mediated iodate reduction and organic iodine dehalogenation processes may also result in the transformation among iodine species and iodide enrichment in other geogenic iodine-rich groundwater systems worldwide.

[Interpretation of the limit values of iodide in the "Standards for Drinking Water Quality（GB5749-2022）" in China].

The Drinking Water Sanitation Standard (GB 5749-2022) has been officially promulgated and implemented, with the iodide listed as a new reference indicator for water quality. This study interprets the distribution of iodine in environmental media, the impact of water iodine on health, the significance of establishing iodide standard limits, and the use of iodide standard limits, in order to provide a scientific basis for the application of iodide standard limits in this revised standard.

Ultra-Sensitive Determination of Particulate, Gaseous Inorganic and Organic Iodine-129 and Iodine-127 in Ambient Air.

Atmospheric iodine cycling is of significance in climate change and environmental and health impacts. To better explore speciation transformation of atmospheric stable and radioactive iodine, an ultra-sensitive analytical method was established for determination of 129I and 127I in particulate, gaseous inorganic, and gaseous organic species, which was conducted with a self-designed cascade sampling apparatus, followed by their separation with a pyrolysis system and accelerator mass spectrometry and ICP-MS measurements. Combustion protocols for three sampling matrices and NaOH concentration for iodine trapping were optimized to achieve a safe analytical procedure with a high chemical yield of iodine. Based on the lowest concentrations of 129I and 127I, a suitable activated carbon product for adsorption of gaseous organic iodine was carefully selected. The detection limits of the three species were 0.30-2.21 ng m-3 for 127I and 0.05-0.22 × 105 atoms m-3 for 129I. This newly established method was successfully applied to analyze the levels and species of 129I and 127I in ambinet air from Xi'an, China, from May to August, 2020. Gaseous organic iodine was found to be the dominant species of 127I and 129I, accounting for about half of total iodine, and gaseous inorganic iodine and particulate iodine accounted for one-quarter each during the whole sampling period. Speciation variation of 129I and 127I indicates that speciation transformation apparently occurred at the turn of spring and summer, mainly between particulate and gaseous organic iodine. This study has implications on delicate tracing of the atmospheric behavior of iodine with long-lived anthropogenic 129I.

Development and optimization of tibezonium iodide and lignocaine hydrochloride containing novel mucoadhesive buccal tablets: a pharmacokinetic investigation among healthy humans.

OBJECTIVE: It is clinically important to deliver a sustained-release mucoadhesive dosage of local anesthetic and antimicrobial agents for pain control. The current study aimed to develop and evaluate chitosan (CHI) based buccal mucoadhesive delivery for the local release of tibezonium iodide (TBN) and lignocaine hydrochloride (LGN). METHODS: Direct compression technique was employed, aided by other mucoadhesive polymers like hydroxypropylmethylcellulose (HPMC) and sodium alginate (SA) and evaluated for physicochemical and in vivo character. RESULTS: Fourier transform infrared spectral analysis (FTIR), powdered X-ray diffraction (XRPD), and differential scanning calorimetry (DSC) absence of physical interaction between ingredients. The physical parameters complied with USP specifications for all formulations. Optimum swellability (551.9%) was offered from formulation TL15, containing 30% SA. The highest ex vivo mucoadhesive strength (24.79 g) and time (18.39 h) was found with TL8. Formulation TL8 also exhibited maximum in vivo residence time (11.37 h). Almost complete drug release at 6 h was possessed by formulation TL5 (HPMC and CHI, 20% each) for TBN (99.98%) and LGN (99.06%). The optimized formulation TL5 exhibited dosage stability up to 6 months at 75% relative humidity and retained drug contents. TL5 was well tolerated by the volunteers with no inflammation, pain or irritation found. Almost 73% of volunteers reported an increase in salivary secretion. The first-order salivary Cmax of TBN and LGN were found as 16.02 and 7.80 µg/mL within 4 h, respectively. CONCLUSION: Therefore, the sustained release mucoadhesive dosage form of TBN and LGN can be an effective and alternative option to conventional delivery.

HPLC Analysis of the Urinary Iodine Concentration in Pregnant Women.

Iodine is an essential component for fetal neurodevelopment and maternal thyroid function. Urine iodine is the most widely used indicator of iodine status. In this study, a novel validated ion-pair HPLC-UV method was developed to measure iodine concentration in clinical samples. A sodium thiosulfate solution was added to the urine sample to convert the total free iodine to iodide. Chromatographic separation was achieved in a Pursuit XRs C8 column. The mobile phase consisted of acetonitrile and a water phase containing 18-crown-6-ether, octylamine and sodium dihydrogen phosphate. Validation parameters, such as accuracy, precision, limits of detection and quantification, linearity and stability, were determined. Urinary samples from pregnant women were used to complete the validation and confirm the method's applicability. In the studied population of 93 pregnant women, the median UIC was lower in the group without iodine supplementation (117 µg/L, confidence interval (%CI): 95; 138) than in the supplement group (133 µg/L, %CI: 109; 157). In conclusion, the newly established ion-pair HPLC-UV method was adequately precise, accurate and fulfilled validation the criteria for analyzing compounds in biological fluids. The method is less complicated and expensive than other frequently used assays and permits the identification of the iodine-deficient subjects.

Poor groundwater quality and high potential health risks in the Datong Basin, northern China: research from published data.

Datong Basin in China is a typical arid-semiarid inland basin, with high levels and wide distributions of arsenic (As), fluoride (F-), and iodine (I). To better understand the presence of low-quality groundwater in Datong Basin and assess the health risks for local residents, groundwater samples were collected from the shallow aquifer and in medium-deep groundwater and analyzed for As, F-, I, and nitrate (NO3-). Maxima of 1932 µg/L for As, 80.89 mg/L for F-, 2300 µg/L for I, and 3854.74 mg/L for NO3- were detected in shallow groundwater, which greatly exceeded the WHO limits for drinking purpose. High-As groundwater was present in both shallow and medium-deep aquifers. High-F- and high-NO3- groundwater was widely distributed in the shallow aquifer, and high-I groundwater was mainly present in the medium-deep aquifers. Poor-quality groundwater in the Datong Basin is mainly caused by local geological and climatic conditions, which are characterized by strong evaporation, active water-rock interactions, thick lacustrine sediment, low groundwater flow rate, and reducing and weak alkaline environments. However, groundwater quality was further impacted by agricultural activities in some areas, as shallow groundwater was also polluted by nitrate. Datong Basin inhabitants face high health risk caused by high concentrations of As, F-, I, and NO3-. The mean noncarcinogenic risk values (HQtotal) were 18.40 for children, 10.94 for adult females, and 9.47 for adult males due to exposure to contaminants in shallow groundwater; and 13.76 for children, 8.18 for adult females, and 7.08 for adult males because of exposure to medium-deep groundwater. Further, the carcinogenic risks (CR) caused by exposure to As were very high for local inhabitants, with the mean and median CR values of 4.20×10-3 and 4.13×10-4 in shallow groundwater and 3.44×10-3 and 1.71×10-4 in medium-deep groundwater, respectively.

Trace Analysis of 61 Emerging Br-, Cl-, and I-DBPs: New Methods to Achieve Part-Per-Trillion Quantification in Drinking Water.

Disinfection byproducts (DBPs) are a ubiquitous source of chemical exposure in drinking water and have been associated with serious health impacts in human epidemiologic studies. While toxicology studies have pinpointed DBPs with the greatest toxic potency, analytical methods have been lacking for quantifying complete classes of most toxic DBPs at sufficiently low quantification limits (ng/L). This new method reports the parts-per-trillion quantification for 61 toxicologically significant DBPs from 7 different chemical classes, including unregulated iodinated haloacetic acids (HAAs) and trihalomethanes (THMs), haloacetaldehydes, haloketones, haloacetonitriles, halonitromethanes, and haloacetamides, in addition to regulated HAAs and THMs. The final optimized method uses salt-assisted liquid-liquid extraction in a single extraction method for a wide range of DBPs, producing the lowest method detection limits to-date for many compounds, including highly toxic iodinated, brominated, and nitrogen-containing DBPs. Extracts were divided for the analysis of the HAAs (including iodinated HAAs) by diazomethane derivatization and analysis using a GC-triple quadrupole mass spectrometer with multiple reaction monitoring, resulting in higher signal-to-noise ratios, greater selectivity, and improved detection of these compounds. The remaining DBPs were analyzed using a GC-single quadrupole mass spectrometer with selected ion monitoring, utilizing a multimode inlet allowed for lower injection temperatures to allow the analysis of thermally labile DBPs. Finally, the use of a specialty-phase GC column (Restek Rtx-200) significantly improved peak shapes, which improved separations and lowered detection limits. Method detection limits for most DBPs were between 15 and 100 ng/L, and relative standard deviations in tap water samples were mostly between 0.2 and 30%. DBP concentrations in real samples ranged from 40 to 17 760 ng/L for this study.

Label-free iodide detection using functionalized carbon nanodots as fluorescent probes.

A label-free fluorescent nanoprobe for iodide ion (I-) detection was developed based on the direct fluorescence quenching of spermine-functionalized carbon dots (SC-dots), whether in complex biological fluids or living cells. The positively charged SC-dots were fabricated via one-step microwave synthesis and exhibited excellent optical properties. Due to the strong quenching ability of I-, SC-dots were utilized for I- detection with high sensitivity and excellent selectivity, which offered a relatively low detection limit of 0.18 µM. This strategy was also successfully applied for I- detections in human serum and HeLa cells. The detection process is facile, highly sensitive and selective, providing a new insight into the potential applications of SC-dots for anion nanoprobe designs in clinical diagnosis and other biologically related areas. Graphical abstract.

[Iodine nutritional status and intake levels in adult from different water iodine content areas of Xinjiang Uygur Autonomous Region in 2017].

OBJECTIVE: To understand the iodine nutrition status of adults in Xinjiang Uygur Autonomous Region under the effective control of iodine deficiency disease. METHODS: Using stratified cluster random sampling method, in the district to determine water iodine median<10 µg/L and ≥10 µg/L of urban and rural areas, a total of 10 survey points, deals from the collecting water deals of extracting water iodine content detection. Adults over 18 years old were randomly selected from 30 households at each survey site to carry out a survey on dietary iodine intake, and the contents of dietary salt iodine and adult urine iodine were tested. RESULTS: The median iodine content in water in Xinjiang Uygur Autonomous Region was 4. 4(2. 3, 13. 6)µg/L. The median iodine content of household salt was 27(24, 30) mg/kg. The median urinary iodine content in adults was 168(103, 259)µg/L. The average dietary iodine intake of adults in the region was 312 µg/d. CONCLUSION: The water iodine content in the environment outside Xinjiang Uygur Autonomous Region is relatively low, and the iodine nutritional status and dietary iodine intake of adults are generally at the appropriate level. However, urban adults with relatively low water iodine content and good economic status have a higher risk of iodine deficiency. Iodized salt is the main source of dietary iodine for adults in Xinjiang Uygur Autonomous Region. Adults in poorer rural and urban areas rely more heavily on iodized salt.

Ionic liquids as mobile phase additives for determination of thiocyanate and iodide by liquid chromatography.

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 C18 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 C18 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.

X-ray Structure Elucidation of a Pt-Metalloporphyrin and Its Application for Obtaining Sensitive AuNPs-Plasmonic Hybrids Capable of Detecting Triiodide Anions.

The development of UV⁻vis spectrophotometric methods based on metalloporphyrins for fast, highly sensitive and selective anion detection, which avoids several of the practical challenges associated with other detection methods, is of tremendous importance in analytical chemistry. In this study, we focused on achieving a selective optical sensor for triiodide ion detection in traces based on a novel hybrid material comprised of Pt(II) 5,10,15,20-tetra(4-methoxy-phenyl)-porphyrin (PtTMeOPP) and gold nanoparticles (AuNPs). This sensor has high relevance in medical physiological tests. The structure of PtTMeOPP was investigated by single crystal X-ray diffraction in order to understand the metal surroundings and the molecule conformation and to assess if it qualifies as a potential sensitive material. It was proven that the Pt-porphyrin generated 1D H-bond supramolecular chains due to the weak C-H···O intermolecular hydrogen bonding. The presence of ordered voids in the crystal encouraged us to use PtTMeOPP as the sensing material for triiodide ion and to enhance its potential in a novel AuNPs/PtTMeOPP hybrid by the synergistic effects provided by the plasmonic gold nanoparticles. The spectrophotometric sensor is characterized by a detection limit of 1.5 × 10-9 M triiodide ion concentration and a remarkable confidence coefficient of 99.98%.

HPLC-DAD Determination of Iodide in Mineral Waters on Phosphatidylcholine Column.

Iodine is an essential nutrient necessary for the production of thyroid hormones. A valuable source of iodide, which is the bio-available iodine form could be mineral waters offered by different spas. In this work, the method capable of direct determination of iodide in mineral water samples based on IAM liquid chromatography on the phosphatidylcholine column (IAM.PC.DD2 Regis HPLC) with DAD detection without sample pretreatment or any pre-concentration steps is presented. The calibration graph for iodide was linear in the range of 0.5⁻10.0 mg L-1 with a correlation coefficient of 0.9996. The limit of detection was 22.84 ng mL-1. The relative recoveries were in the interval of 98.5⁻100.2% and the repeatability, expressed as a relative standard deviation (RSD) was less than 5%. The RSA (Response Surface Analysis) investigated the effect of the sample concentration and the injection volume. The iodide concentrations in the mineral water samples ranged from 0.58 to 2.88 mg L-1. The accuracy of the method was assessed through independent analysis by ICP-MS. Iodide levels measured by these two procedures did not significantly differ. The effects of interfering ions like HCO3-, Cl-, SO42-, F-, and Br- were also tested. The analysis has shown insignificant differences in the values of the iodide peak area and its height measured in multicomponent mixtures with an error smaller than 5%.

Mixing-to-Answer Iodide Sensing with Commercial Chemicals.

We develop a convenient, colorimetric assay (Au/PEI) for rapid iodide (I-) determination that can be prepared facilely by mixing commercially available chemicals including tetrachloroauric acid (HAuCl4) and poly(ether imide) (PEI), and the assay can be carried out directly by adding the samples to the assay without any pretreatment and additional procedure. Au/PEI operates on the principle that I- accelerates the formation of Au NPs, which leads to a visible color change from light yellow to red for naked-eye readout with high specificity. We integrate our assay on solid devices including gel hybrids (Au/PEI/GH) and filter paper (Au/PEI paper) to satisfy the demand of point-of-care testing and justify the practicality by detecting I- in lake water that was supplemented with 10, 20, or 40 µM of I-. Au/PEI/GH with the limit of detection of 0.35 µM can satisfy the detection of drinking water based on the guidelines (1.2 µM) set by the Chinese government, and Au/PEI paper can be used even after 1 year of storage. Such assays provide a convenient and straightforward choice for routine, on-site I- tests.

Method for the Determination of Iodide in Dried Blood Spots from Newborns by High Performance Liquid Chromatography Tandem Mass Spectrometry.

Dried blood spots (DBS), collected for newborn screening programs in the United States, have been used to screen for congenital metabolic diseases in newborns for over 50 years. DBS provide an easy and inexpensive way to collect and store peripheral blood specimens and present an excellent resource for studies on the assessment of chemical exposures in newborns. In this study, a selective and sensitive method was developed for the analysis of iodide in DBS by high performance liquid chromatography electrospray tandem mass spectrometry. Accuracy, inter- and intraday precision, matrix effects, and detection limits of the method were determined. Further validation of the method was accomplished by concurrent analysis of whole blood and fortified blood spotted on a Whatman 903 filter card. A significant positive correlation was found between measured concentrations of iodide in venous whole blood and the same blood spotted as DBS. The method limit of detection was 0.15 ng/mL iodide. The method was further validated by the analysis of a whole blood sample certified for iodide levels (proficiency testing sample) by spotting on a filter card. Twenty DBS samples collected from newborns in New York State were analyzed to demonstrate the applicability of the method. The measured concentrations of iodide in whole blood of newborns from New York State ranged between

Successive and Specific Detection of Hg2+ and I- by a DNA@MOF Biosensor: Experimental and Simulation Studies.

A 2D metal-organic framework (MOF) of {[Cu(Dcbb)(Bpe)]·Cl} n (1, H2DcbbBr = 1-(3,5-dicarboxybenzyl)-4,4'-bipyridinium bromide, Bpe = trans-1,2-bis(4-pyridyl)ethylene)) has been prepared. MOF 1 associates with the thymine-rich (T-rich), single-stranded probe DNA (ss-DNA, denoted as P-DNA) labeled with fluorophore FAM (FAM = carboxyfluorescein) and quenches the FAM emission to give a nonemissive P-DNA@1 hybrid (off state). The P-DNA in the hybrid subsequently captures the Hg2+ to give a rigid double-stranded DNA featuring T-Hg2+-T motif (ds-DNA@Hg2+) and detach from MOF 1, triggering the recovery of the FAM fluorescence (on state). Upon subsequent addition of I-, Hg2+ was further sequestrated from the ds-DNA@Hg2+ duplex, driven by the stronger Hg-I coordination. The released P-DNA is resorbed by MOF 1 to regain the initial P-DNA@1 hybrid (off state). The P-DNA@1 sensor thus detects Hg2+ and I- sequentially via a fluorescence "off-on-off" mechanism. The sensor is highly selective and sensitive, yielding detection limits of 3.2 and 3.3 nM, respectively. The detection process was conformed by circular dichroism (CD) and the detection mechanism was verified by fluorescence anisotropy, binding constant, and simulation of the binding free energy at each stage.