AIEE activated Pyrene-Dansyl coupled FRET probe for discriminating detection of lethal Cu2+ and CN-: Bio-Imaging, DNA binding studies and prompt prognosis of Menke's disease.

In present work a pyrene-dansyl dyad functionalized chemoreceptor, DPNS is unveiled towards ultrasensitive chromo-fluorogenic detection of heavy and transition metal ions (HTMs) like Cu2+ and pernicious CN-. It demonstrated distinct chromogenic responses; colorless to faint yellow (Cu2+), intense yellow (CN-) from contaminant aqueous sources. Cu2+ instigated alteration in DPNS fluorescence from feeble emission to sparkling green with LOD: 37.75 × 10-9 M, cyan emission for CN- having LOD 61.51 × 10-8M. In particular, chemical scaffold of DPNS consists of -C = N, O = S = O donor entitities that escalates overall polarity thereby providing an excellent binding pocket for simultaneous Cu2+ and CN- recognition with distinct photophysical signaling. Impressively, presence of two fluorophoric moieties triggers FRET, CHEF phenomenon. The conceivable host:guest interactive pathway is manifested by LMCT- FRET-PET-CHEF, C = N isomerization for Cu2+ and ICT-H-bonding for CN-. An exquisite experimental and theoretical corroboration further strengthened the recognition phenomenon. In addition owing to pyrene excimer formation, DPNS exhibits AIEE with increasing water fraction. Notably, DPNS could successfully undergo intracellular tracking of Cu2+ in Tecoma Stans, Peperomia Pellucida. DPNS•••Cu2+ adduct displayed significant intercalative DNA binding activity rationalized by spectral investigation, competitive EB binding, viscosity study. The overall findings, excellent properties endows DPNS a potential contender towards discriminative detection of Cu2+ and CN- like toxic industrial contaminants.

A strategically synthesized arseno-discriminatory tetra-phenoxido hetero-trinuclear complex envisioned for the recognition of iAs and oAs from Oryza sp. and aquatic crustaceans.

A heterotrimetallic [MnII(CuII)2(C18H18N2O2)2] complex VBCMERI has been unveiled herein to monitor its synergistic propensity towards aqueous phase As3+ (iAs and oAs) detection. VBCMERI was structurally probed by numerous analytical tools like ESI-MS, FT-IR, and SCXRD. The aqueous phase selective chromogenic alteration of the sensory probe from greenish-yellow to colorless was observed owing to interaction with As3+ (cationic form, iAs). This phenomenon can be ascribed to the displacement of the Mn2+ center with As3+, which has further been experimentally validated through cyclic voltammetric titration studies, FT-IR, and ESI-MS, and theoretically corroborated with density functional theory calculations. Interestingly, aqueous phase selective turn-on fluorogenic enhancement of the sensory probe was observed upon interaction with AsO2- (anionic form, iAs) owing to the displacement of the arsenite anion with the pivalic acid group. The distinct chromogenic alteration from greenish-yellow to colorless and the fluorogenic enhancement of VBCMERI upon interaction with the respective As3+ (iAs) and AsO2- (iAs) were successfully implemented for monitoring arsenic contamination in groundwater samples and diverse types of Oryza sp. grains from the assorted arsenic-affected zones. The competitive accumulation of arsenobetaine (oAs) in the exoskeleton and muscles of aquatic crustaceans (herein, Penaeus sp.) can be distinctly differentiated based on the turn-on fluorogenic response. Based on the sensing response and competitive accumulation tendency of different forms of arsenic in different environments, arseno-adducts with VBCMERI have been theoretically modeled for corroboration with experimental findings. The VBCMERI-AsO2- adduct was also highly efficient in regenerating the VBCMERI sensor selectively in the presence of contaminants like Pb2+. This reversible behavior was further exploited to mimic a molecular-level 3-input-2-output logic gate ensemble.

Electrochemical Nanosensors for Sensitization of Sweat Metabolites: From Concept Mapping to Personalized Health Monitoring.

Sweat contains a broad range of important biomarkers, which may be beneficial for acquiring non-invasive biochemical information on human health status. Therefore, highly selective and sensitive electrochemical nanosensors for the non-invasive detection of sweat metabolites have turned into a flourishing contender in the frontier of disease diagnosis. A large surface area, excellent electrocatalytic behavior and conductive properties make nanomaterials promising sensor materials for target-specific detection. Carbon-based nanomaterials (e.g., CNT, carbon quantum dots, and graphene), noble metals (e.g., Au and Pt), and metal oxide nanomaterials (e.g., ZnO, MnO2, and NiO) are widely used for modifying the working electrodes of electrochemical sensors, which may then be further functionalized with requisite enzymes for targeted detection. In the present review, recent developments (2018-2022) of electrochemical nanosensors by both enzymatic as well as non-enzymatic sensors for the effectual detection of sweat metabolites (e.g., glucose, ascorbic acid, lactate, urea/uric acid, ethanol and drug metabolites) have been comprehensively reviewed. Along with this, electrochemical sensing principles, including potentiometry, amperometry, CV, DPV, SWV and EIS have been briefly presented in the present review for a conceptual understanding of the sensing mechanisms. The detection thresholds (in the range of mM-nM), sensitivities, linear dynamic ranges and sensing modalities have also been properly addressed for a systematic understanding of the judicious design of more effective sensors. One step ahead, in the present review, current trends of flexible wearable electrochemical sensors in the form of eyeglasses, tattoos, gloves, patches, headbands, wrist bands, etc., have also been briefly summarized, which are beneficial for on-body in situ measurement of the targeted sweat metabolites. On-body monitoring of sweat metabolites via wireless data transmission has also been addressed. Finally, the gaps in the ongoing research endeavors, unmet challenges, outlooks and future prospects have also been discussed for the development of advanced non-invasive self-health-care-monitoring devices in the near future.

Strategic optimization of phase-selective thermochemically amended terra-firma originating from excavation-squander for geogenic fluoride adsorption: a combined experimental and in silico approach.

An inimitable adsorbent "FI-TM-BWCC," emanated from meta-phase-selective thermochemical modulation of excavation-squander (mine waste)-derived terra-firma (blackish white china clay, i.e., BWCC), is explored in the present work for fluoride (F-) adsorption purpose. FI-TM-BWCC portrayed an excellent adsorption efficiency (95% removal capacity and Qe: 99 mg/g, at initial adsorbate dose: 10 mg/L, pH: 7±0.5, adsorbent dosage: ~600 mg, exposure time: 60 min). At identical experimental conditions, the F- scavenging phenomenon was superior than two analogous adsorbents: (i) biopolymer chitosan and glutaraldehyde cross-linked BWCC (CG@BWCC, wherein F- removal efficiency: 74%) and (ii) meta-phase-selective thermally moduled BWCC (TM-BWCC, removal efficiency: 75%). BWCC predominantly comprises kaolinite and a trace amount of anatase along with prime elemental compositions: 41.71% Al2O3, 49.80 % SiO2, 4.25% Fe2O3, and 3.93% TiO2, as revealed by PXRD and XRF analyses. The thermochemical modulation pathway significantly escalated the BET surface area of BWCC (~11.92 m2/g, avg. pore radius: 23.64 Å, i.e., mesoporous in nature) to FI-TM-BWCC (216.95 m2/g, avg. pore radius: 31.41 Å). The fluoride-adsorbed F-•••FI-TM-BWCC species revealed a reduced surface area of 21.5 m2/g, which was explained in the light of ion exchange pathway on FI-TM-BWCC's non-uniform surface (surface roughness/SA of 1597 nm, reduced to 1179 nm after F- uptake). The spontaneous F-•••FI-TM-BWCC interaction (ΔG0 = -6.25 kJ) occurred following chemisorption-controlled ion exchange (CCIE) pathway as appearance of a F1s band at 685.5 eV was rationalized for Si-F bond formation; corroborating pseudo second-order (PSO) kinetics and resembling Freundlich isotherm. The usefulness of FI-TM-BWCC was diversified through field validation with natural groundwater specimens and proposition of a gravity-fed defluoridation unit. The flow rate was documented to be ~11 liters per hour (LPH) by implementing viscous turbulence fluent model. The experimental findings certainly followed the premise conventions of sustainability metrics upholding socio-economic equipoise.

Unveiling of a smartphone-mediated ratiometric chemosensor towards the nanomolar level detection of lethal CN-: combined experimental and theoretical validation with the proposition of a molecular logic circuitry.

A promising naphthalene-functionalized ratiometric chemosensor (E)-1-((naphthalen-5-yl) methylene)-2-(2,4-dinitrophenyl) hydrazine (DNMH) is unveiled in the present work. DNMH demonstrates brisk discernible colorimetric response from yellow to red in the presence of CN-, a lethal environmental contaminant, in a near-perfect aqueous medium with a LOD of 278 nM. The "key role marker" controlling the electrochemical and non-covalent H-bonding interaction between DNMH and CN- is through the commendable role of acidic -NH functionalities. Kinetic studies reveal a pseudo second order reaction rate and the formation of an unprecedented photostable adduct. The negative value of ΔG as evaluated from ITC substantiates the spontaneity of the DNMH⋯CN- interaction. The sensing mechanism was further reinforced with state-of-the-art theoretical investigations, namely DFT, TDDFT and Fukui indices (FIs). Moreover, the proposition of a reversible multi-component logic circuitry implementing Boolean functions in molecular electronics has also been triggered by the turn-over spectrophotometric response of the ditopic ions CN- and Cd2+. The cytotoxicity of DNMH towards Bacillus thuringiensis and Escherichia coli is successfully investigated via the MTT assay. Impressively, "dip stick" and "easy to prepare" test paper device and silica gel-based solid-phase CN- recognition validate the on-site analytical application of DNMH. Furthermore, the involvement of a synergistic approach between 'chemistry beyond the molecule' and 'engineering' via an exquisitely implemented smartphone-assisted colorimetric sensory prototype makes this work unprecedented among its congeners and introduces a new frontier in multitudinous material-based functional product development.

Coumarin functionalized molecular scaffolds for the effectual detection of hazardous fluoride and cyanide.

Fluoride and cyanide contamination in drinking water imposes detrimental impacts on human health above their permissible limits. Hence, the quantitative detection of these colourless water-soluble toxins has attracted attention. Even though a plethora of chemosensors have been reported so far for the detection of fluoride and cyanide from various matrices, still their applicability is limited to a few examples. Nevertheless, recent advances in the syntheses of coumarin derivatives have shown significant impact on fluoride and cyanide detection. Therefore, this present review provides a brief overview of the application of coumarin-coupled molecular scaffolds towards the detection of perilous fluoride and cyanide along with their sensing mechanisms in order to develop more innovative, simple, sensitive, real-time responsive and cost-effective coumarin-based supramolecular chemosensors to promote next generation approaches towards the ultra-trace quantitative detection of these toxic anions.