Anion-directed structural tuning of two azomethine-derived Zn2+ complexes with optoelectronic recognition of Cu2+ in aqueous medium with anti-cancer activities: from micromolar to femtomolar sensitivity with DFT revelation.

Herein, two novel mononuclear transition metal Zn2+ complexes i.e. [Zn(HL)(N3)(OAc)] (NS-1) & [Zn(HL)2(ClO4)2] (NS-2) have been synthesised using a tridentate clickable Schiff base ligand, HL (2-methyl-2-((pyridin-2-ylmethyl)amino)propan-1-ol), and the polyatomic monoanions N3- and ClO4- for NS-1 and NS-2 respectively. Interestingly, NS-1 and NS-2 have been explored for the detection of Cu2+ with an LOD of 48.6 fM (response time ∼6 s) and 2.4 µM respectively through two mutually independent pathways that were studied using sophisticated methods like UV-Vis, cyclic voltammetry, ESI-MS etc. with theoretical DFT support. Herein, both chemosensors are equally responsive towards the detection of Cu2+ in aqueous as well as other targeted real field samples with appreciable recovery percentage (74.8-102%), demonstrating their practical applicability. Moreover, the detection of unbound Cu2+ in a human urine specimen was also analysed which may be helpful for the diagnosis of Cu2+-related disorders like Wilson's disease. Taking one step ahead, TLC strips have been employed for on-field detection of the targeted analytes by contact mode analysis. Additionally, the anti-cancer activity of these complexes has also been studied on breast cancer cells with the help of the MTT assay. It has been found that at a 0.5 mM dose, both NS-1 and NS-2 could kill 81.4% and 73.2% of cancer cells respectively. However, it has been found that NS-1 destroys normal cells together with cancer cells. Hence, NS-2 could be administered as a better anticancer drug for MDA-MB-231 cancer cells in comparison with NS-1. In a nutshell, the present work describes how anion-directed synthesis of two architecturally different metal complexes leads toward the detection of the same analyte via an independent chemodosimetric pathway along with their anti-cancer activities on breast cancer cells.

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.

Regioselective synthetic approach for key precursors of 6-arylbenzo[c]phenanthridin-10-ol derivatives: a useful compound for selective chromogenic recognition of fluoride.

A regioselective synthetic strategy for 6-aryl-8,9-dihydrobenzo[c]phenanthridine-10(7H)-ones (4) is accomplished using a one-pot four-component reaction by fine-tuning the reaction temperature. DMSO is excellently used as a reactant-cum-solvent to introduce a carbonyl functionality regioselectively at the C-10 position of the benzophenanthridine backbone, via an MCR, which is unknown yet. The elegant features of this strategy are the formation of two CC, one CN, and one CO bonds in a single step, without using a base and an activator for the oxygenation process. Then, a few compounds (4) are easily aromatised to achieve 6-arylbenzo[c]phenanthridin-10-ol derivatives (7) using I2/DMSO at 100 °C. Nay, a dangling hydroxyl group in 4s, 4u, 4x, and 4z helped them to be employed as promising 'naked eye' colorimetric chemosensors for fluoride with limits of detection of 0.65, 0.60, 0.34, and 2.2 ppm, respectively. Moreover, the reversibility of the chemosensors makes them suitable for combinatorial INHIBIT logic gate formulation. The compounds have also been employed for solid-state F- detection via the spot TLC test.

A Ni(II) Metal-Organic Framework with Mixed Carboxylate and Bipyridine Ligands for Ultrafast and Selective Sensing of Explosives and Photoelectrochemical Hydrogen Evolution.

We report a Ni-MOF (nickel metal-organic framework), Ni-SIP-BPY, synthesized by using two linkers 5-sulfoisophthalic acid (SIP) and 4,4'-bipyridine (BPY) simultaneously. It displays an orthorhombic crystal system with the Ama2 space group: a = 31.425 Å, b = 19.524 Å, c = 11.2074 Å, α = 90°, ß = 90°, γ = 90°, and two different types of nickel(II) centers. Interestingly, Ni-SIP-BPY exhibits excellent sensitivity (limit of detection, 87 ppb) and selectivity toward the 2,4,6-trinitrophenol (TNP)-like mutagenic environmental toxin in the pool of its other congeners via "turn-off" fluorescence response by the synergism of resonance energy transfer, photoinduced electron transfer, intermolecular charge transfer, π-π interactions, and competitive absorption processes. Experimental studies along with corroborated theoretical experimentation, vide density functional theory studies, shed light on determining the plausible mechanistic pathway in selective TNP detection, which is highly beneficial in the context of homeland security perspective. Along with the sensing of nitroaromatic explosives, the moderately low band gap and the p-type semiconducting behavior of Ni-SIP-BPY make it suitable as a photoanode material for visible-light-driven water splitting. Highly active surface functionalities and sufficient conduction band minima effectively reduce the water and result in a seven times higher photocurrent density under visible-light illumination.

Selective recognition of ammonia and aliphatic amines by C-N fused phenazine derivative: A hydrogel based smartphone assisted 'opto-electronic nose' for food spoilage evaluation with potent anti-counterfeiting activity and a potential prostate cancer biomarker sensor.

In real day scenario, it is an urge to provide a single solution of multiple problems. In this regard, herein rapid, selective and highly efficient chromo-fluorogenic detection of ammonia/aliphatic amines over aromatic amines has been investigated by means of a novel "opto-electronic nose", CN-2, synthesized in a single-step via multiple inter/intramolecular C-N fusion reactions. The in-situ generated mono-protonated CN-2 can selectively detect primary to secondary to even tertiary aliphatic amines over aromatic amines within ∼40 S with extremely low detection threshold values of 27.2 ppb, 0.7 ppm, 5.4 ppm, 1.7 ppm from UV-Vis and 42.5 ppb, 1.61 ppm, 5.5 ppm, 6.14 ppm from fluorescence spectral data for NH3, hydrazine (primary amine), diethanolamine (secondary amine) and triethylamine (tertiary amine) respectively with the hypsochromic shift in the UV-Vis spectra along with fluorescence attenuation via target-specific deprotonation. The colorimetric signal can also be examined by Smartphone APP, which is well correlated with spectrophotometric outcomes. Interestingly, due to presence of a unique protonated antenna centre CN-2 with anti-oxidant activity can also detect aliphatic biogenic amines, like putrescine, spermidine, which are frequently released from spoiled food. Therefore, it may be exploited as smart food-spoilage indicator in real-time. Again, the aliphatic biogenic amines recognition capability from human urine made it as a potential prostate cancer biomarker sensor for clinical use, which alleviates the need of biopsies. CN-2 could also be employed towards one-to-two decoder logic-circuitry formulation to monitor the ammonia levels. Moreover, CN-2-functionalized hydrogel-membrane based portable, handy prototype could be utilized for easy on-site recognition of amine vapour. Reversible sensing behaviour in presence of HCl enables CN-2 to exhibit anti-counterfeiting activity. To the best of our knowledge, this is the first all-in-one phenazine-based Smartphone-assisted chromo-fluorogenic-chemosensor, which would be of enormous interest in food-packaging industry, information technology as well as in early-stage-cancer diagnosis.

Knoevenagel condensation triggered synthesis of dual-channel oxene based chemosensor: Discriminative spectrophotometric recognition of F-, CN- and HSO4- with breast cancer cell imaging, real sample analysis and molecular keypad lock applications.

A novel oxene based unusual sensory receptor (HyMa) has been synthesized via.Knoevenagel condensation triggered carbon-heteroatom (oxygen) intramolecular bond formation reaction at room temperature for discriminative detection of multi-analytes like HSO4-, CN- & F- by spectro-photometric alterations with profound selectivity with the detection limit of 38 ppb, 18 ppb & 94 ppb respectively. Examination of the sensing mechanism was exhaustively investigated through several spectroscopic means like 1H NMR, FT-IR, absorption and fluorescence spectra etc. In addition, quantum mechanical calculations like DFT and Loewdin spin population analyses also validated the rationality of the host-guest interaction. Apart from these, the reversible spectroscopic responses of HyMa towards F- and Al3+ can imitate several complex logic functions that in turn help in preparing molecular keypad lock. This molecular keypad lock has the potential to protect the confidential information at the molecular scale. Additionally, the MTT assay of HyMa showed low cytotoxicity and membrane permeability indicating its attractive capability for bio-imaging towards triple negative breast cancer. HyMa-coated test strips could also be employed towards on-site detection of these deadly contaminants via "Dip Stick" approach without help of any instrumentation. In addition, HyMa has also been exploited for quantitative determination of HSO4- from various real water samples. In a nutshell, detection of lethal contaminants like CN-, F- & HSO4- at ppb level with in vitro live cell imaging has been explored with proper photophysical characterisation and theoretical calculations with real field applications.

Trace-Level Humidity Sensing from Commercial Organic Solvents and Food Products by an AIE/ESIPT-Triggered Piezochromic Luminogen and ppb-Level "OFF-ON-OFF" Sensing of Cu2+: A Combined Experimental and Theoretical Outcome.

Selective and sensitive moisture sensors have attracted immense attention due to their ability to monitor the humidity content in industrial solvents, food products, etc., for regulating industrial safety management. Herein, a hydroxy naphthaldehyde-based piezochromic luminogen, namely, 1-{[(2-hydroxyphenyl)imino]methyl}naphthalen-2-ol (NAP-1), has been synthesized and its photophysical and molecular sensing properties have been investigated by means of various spectroscopic tools. Owing to the synergistic effect of both aggregation-induced emission (AIE) and excited-state intramolecular proton transfer (ESIPT) along with the restriction of C=N isomerization, the probe shows bright yellowish-green-colored keto emission with high quantum yield after the interaction with a trace amount of water. This makes NAP-1 a potential sensor for monitoring water content in the industrial solvents with very low detection limits of 0.033, 0.032, 0.034, and 0.033% (v/v) from tetrahydrofuran (THF), acetone, dimethyl sulfoxide (DMSO), and methanol, respectively. The probe could be used in the food industry to detect trace moisture in the raw food samples. The reversible switching behavior of NAP-1 makes it suitable for designing an INHIBIT logic gate with an additional application in inkless writing. In addition, an Internet of Things-(IoT) based prototype device has been proposed for on-site monitoring of the moisture content by a smartphone via Bluetooth or Wi-Fi. The aggregated probe also has the ability to recognize Cu2+ from a purely aqueous medium via the chelation-enhanced quenching (CHEQ) mechanism, leading to ∼84% fluorescence quenching with a Stern-Volmer quenching constant of 1.46 × 104 M-1 and with an appreciably low detection threshold of 57.2 ppb, far below than recommended by the World Health Organization (WHO) and the United States Environmental Protection Agency (U.S. EPA). The spectroscopic and theoretical calculations (density functional theory (DFT), time-dependent DFT (TD-DFT), and natural bond orbital (NBO) analysis) further empower the understanding of the mechanistic course of the interaction of the host-guest recognition event.

Selective Identification and Encapsulation of Biohazardous m-Xylene among a Pool of Its Other Constitutional C8 Alkyl Isomers by Luminescent d10 MOFs: A Combined Theoretical and Experimental Study.

Separation of C8 alkyl-aromatics (o-xylene, m-xylene, and p-xylene) remains one of the most challenging tasks to date due to their similar physical and chemical properties. Cd2+- and Zn2+-based luminescent metal-organic frameworks (MOFs) have been synthesized for the selective identification of m-xylene in a pool of other isomers by fluorometric methods. Inhibition of the photoinduced electron transfer process is the prime reason for fluorescence enhancement, owing to the comparable molecular orbital energies for m-xylene in comparison with o- and p-xylene. Density functional theory calculations signify that the extraordinary selectivity is mainly due to the high dipole moment of m-xylene that might enhance the ring current, leading to a strong π-π interaction with the MOF's co-ligand. As a practical application, fluorometric sensing could be used for the estimation of m-xylene in different solvent media. Moreover, X-ray structural analysis reveals that the Zn2+-MOF can encapsulate m-xylene selectively within its framework among other constitutional isomers, which also emphasizes its capability for practical implementation.