Cu(II) detection by a fluorometric probe based on thiazoline-amidoquinoline derivative and its application to water and food samples.

Two novel fluorescent probes for Cu2+ detection have been developed based on thiazoline-quinoline conjugates bearing a 4-ethynyl-N,N-dimethylaniline unit (QT1 and QT2). QT2 exhibits instantaneous fluorescence quenching of Cu2+ with an emissive change from bright orange to arctic blue under UV light irradiation (365 nm). The plots of I0/I against Cu2+ concentrations show a good linear relationship that ranges from 0 to 50 µM with a coefficient of determination (R2) = 0.9906 and a limit of detection (LOD) of 76 nM, which is considered low (4.84 ppb). A 1:1 complexation between QT2 and Cu2+ was confirmed by UV-Vis titration, ESI-MS, and SC-XRD. The QT2·Cu2+ complex was dissociated by the addition of EDTA. The fluorescence quenching mechanism involves the ligand-to-metal charge transfer (LMCT) of a paramagnetic Cu2+ complex. The QT2 probe on a paper-based strip was used to determine the amount of Cu2+ in water and food samples (shiitake mushrooms and oysters).

Synthesis, structure and photoluminescence properties of heterometallic-based coordination polymers of trimesic acid.

Reacting trimesic acid (H3TMA, C9H6O6) with CaCl2 and MCl2 at 110 °C under hydrothermal conditions gave the isostructural heterobimetallic coordination polymers (CPs) catena-poly[[tetraaquazinc(II)]-µ-5-carboxybenzene-1,3-dicarboxylato-[tetraaquacalcium(II)]-µ-5-carboxybenzene-1,3-dicarboxylato], [CaZn(HTMA)2(H2O)8]n, 1, and catena-poly[[tetraaquacobalt(II)]-µ-5-carboxybenzene-1,3-dicarboxylato-[tetraaquacalcium(II)]-µ-5-carboxybenzene-1,3-dicarboxylato], [CaCo(HTMA)2(H2O)8]n, 2. Compounds 1 and 2 crystallize in the monoclinic space group C2/c. The solid-state structures consist of eight-coordinate CaII ions and six-coordinate MII ions. These ions are connected by a doubly deprotonated HTMA2- ligand to create a one-dimensional (1D) zigzag chain. Poly[[decaaquabis(µ3-benzene-1,3,5-tricarboxylato)calcium(II)dizinc(II)] dihydrate], {[CaZn2(TMA)2(H2O)10]·2H2O}n, 3, was found incidentally as a minor by-product during the synthesis of 1 at a temperature of 140 °C. It forms crystals in the orthorhombic space group Ccce. The structure of 3 consists of a two-dimensional (2D) layer composed of [Zn(TMA)] chains that are interconnected by CaII ions. The presence of aromatic carboxylic acid ligands and water molecules, which can form numerous hydrogen bonds and π-π interactions, increases the stability of the three-dimensional (3D) supramolecular architecture of these CPs. Compounds 1 and 2 exhibit thermal stability up to 420 °C, as indicated by the thermogravimetric analysis (TGA) curves. The powder X-ray diffraction (PXRD) data reveal the formation of unidentified phases in methanol and dimethyl sulfoxide, while 1 exhibits chemical stability in a wide range of solvents. The luminescence properties of 1 dispersed in various low molecular weight organic solvents was also examined. The results demonstrate excellent selectivity, sensitivity and recyclability for detecting acetone molecules in aqueous media. Additionally, a possible sensing mechanism is also outlined.

Switchable Metal-Ion Selectivity in Sulfur-Functionalised Pillar[5]arenes and Their Host-Guest Complexes.

Nucleophilic substitution of pertosylated pillar[5]arene (P-OTs) with commercially available sulfur containing nucleophiles (KSCN, KSAc, and thiophenol), yields a series of sulfur-functionalised pillar[5]arenes. DLS results and SEM images imply that these pillararene macrocycles self-assemble in acetonitrile solution, while X-ray crystallographic evidence suggests solvent-dependent assembly in the solid state. The nature of the sulfur substituents decorating the rim of the pillararene controls binding affinities towards organic guest encapsulations within the cavity and dictates metal-ion binding properties through the formation of favorable S-M2+ coordination bonds outside the cavity, as determined by 1 H NMR and fluorescence spectroscopic experiments. Addition of a dinitrile guest containing a bis-triazole benzene spacer (btn) induced formation of pseudorotaxane host-guest complexes. Fluorescence emission signals from these discrete macrocycles were significantly attenuated in the presence of either Hg2+ or Cu2+ in solution. Analogous titrations utilizing the corresponding pseudorotaxanes alter the binding selectivity and improve fluorescence sensing sensitivity. In addition, preliminary liquid-liquid extraction studies indicate that the macrocycles facilitate the transfer of Cu2+ from the aqueous to the organic phase in comparison to extraction without pillar[5]arene ligands.

A novel "turn-on" fluorescent probe based on thiocarbamoyl-DHP for Hg2+ detection in water samples and living cells.

In this study, two fluorescent sensing probes, dihydropyridine (DHP) derivatives (DHP-CT1 and DHP-CT2) bearing phenoxy thiocarbonyl group, have been developed for Hg2+ detection. The tandem trimerization-cyclization of methylpropiolate with ammonium acetate gave 1.4-DHP and 1,2-DHP derivatives, which were reacted with O-phenylcarbonochloridothioate to produce DHP-CT1 and DHP-CT2, respectively. DHP-CT1 exhibits superior sensitivity and selectivity of fluorescence enhancement towards Hg2+ in aqueous media. The fluorescence intensity shows a good linear relationship with the concentration of Hg2+ in the range of 0-10 µM providing the extremely low LOD of 346 nM (69.4 ppb). The fluorescence enhancement is caused by the Hg2+ promoted hydrolysis of the thioamide bond releasing the fluorescent 1,4-DHP that was confirmed by NMR and HRMS. The quantitative analysis of Hg2+ in water samples using DHP-CT1 probe was demonstrated in aqueous solution and paper-based sensing strips. Furthermore, DHP-CT1 was also applied for monitoring intracellular Hg2+ in living RAW264.7 macrophages through fluorescence cell imaging.

NaI-Mediated Electrochemical Cyclization-Desulfurization for the Synthesis of N-Substituted 2-Aminobenzimidazoles.

An electrochemical method for the synthesis of N-substituted 2-aminobenzimidazoles through a NaI-mediated desulfurization-cyclization process is reported. This electrosynthesis method utilizes cost-effective NaI as both a mediator and an electrolyte in a catalytic amount (0.2 equiv), replacing traditional oxidizing reagents. N-Substituted o-phenylenediamines and isothiocyanates undergo a thiourea formation/cyclization/desulfurization process to provide N-substituted 2-aminobenzimidazoles (55 examples, up to 98% yield) in a single reaction vessel. Importantly, this electrochemical methodology is applicable to gram-scale synthesis, maintaining reaction efficiency.

Electrochemical NaI-mediated one-pot synthesis of guanidines from isothiocyanates via tandem addition-guanylation.

In this study, we present an electrochemical approach for the synthesis of guanidines from isothiocyanates and amines in a single reaction vessel. This one-pot operation takes place in aqueous media, utilizing an undivided cell setup with NaI serving as both the electrolyte and mediator. The process involves the in situ generation of thiourea, followed by electrolytic guanylation with amines. Under ambient temperature conditions, we successfully demonstrated the formation of 30 different guanidine compounds, achieving yields ranging from fair to excellent. Furthermore, the synthesis method could be carried out on a gram scale with a good yield. This protocol stands out for its cost-effectiveness, step-economical design, high tolerance towards various functional groups, and environmentally friendly reaction conditions.

Selective copper-catalysed atom transfer radical addition (ATRA) in water under environmentally benign conditions.

Simple and green conditions for copper-catalysed ATRA reactions in water have been developed. Firstly, [Cu(ADPA)(H2O)(ClO4)2] (1b, ADPA = 9-[(2,2'-dipicolylamino)methyl]anthracene) was demonstrated to be capable of selectively catalysing the ATRA of CCl4 to styrene using L-ascorbic acid (AsH2) as a reducing agent in organic solvent mixtures under ambient atmosphere. Mechanistic investigation suggested that our ATRA reaction proceeded via a single-electron transfer (SET) mechanism through an inner-sphere complex, which is consistent with the widely accepted mechanism for copper-catalysed ATRA. To perform the reaction in water as a sole solvent, a biocompatible surfactant (2 wt% Tween 20 or Tween 80) was added to improve solubility and increase the local concentration of organic reagents and the copper catalyst. Without the need for a complicated oxygen-free set-up, the ATRA reaction catalysed by this simple aqueous-dispersed system can be performed at a mild temperature (60 °C) and a relatively short reaction time (6 h) using 1 mol% of the catalyst. Furthermore, this facile protocol is also applicable for other alkene substrates demonstrated in this work, resulting in satisfactory to excellent substrate conversion and product yields.

Ultrafast synthesis of silicone elastomers using silsesquioxane cages as crosslinkers.

Cross-linked siloxane/silsesquioxane-based elastomers were easily prepared in 15 min via the anionic ring-opening polymerization of cyclotetrasiloxane (D4) and a polyhedral oligomeric silsesquioxane, using K2CO3 as a catalytic base in dimethylformamide at 70 °C. The resulting silicone elastomers have high mechanical strength, good thermal stability, and good superhydrophobic properties.

Four series of lanthanide coordination polymers based on the tetrabromobenzene-1,4-dicarboxylate ligand: structural diversity and multifunctional properties.

Four series of lanthanide-based coordination polymers (LnCPs), namely [Ln(Br4bdc)1.5(MeOH)3] (1Ln; Ln = Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy), [Ln2(Br4bdc)2(NO3)2(MeOH)4] (2Ln; Ln = Ce, Pr, Nd, Sm), [Ln(Br4bdc)(NO3)(MeOH)] (3Ln; Ln = Gd, Tb, Dy), and [Ln2(Br4bdc)3(H2O)2.3(MeOH)2.7] (4Ln; Ln = Gd, Tb, Dy) have been synthesized by reacting hydrated lanthanide(III) salts with tetrabromobenzene-1,4-dicarboxylic acid (H2Br4bdc) in different solvents under solvothermal conditions. The structural diversity found in the system mainly resulted from the effects of anions, solvents, and the variation in the ionic radii of the lanthanide(III) ions. Compounds in series 1Ln feature a two-dimensional (2D) layered structure with sql topology based on {(Ln(COO)2)2(µ-COO)2} secondary building units (SBUs). Compounds in series 2Ln and 3Ln comprise, respectively, infinite uniform and alternate chains of {Ln(COO)2}n SBUs that are assembled into a similar network topology to 1Ln. Meanwhile, compounds in series 4Ln feature 3D coordination networks of a pcu α-Po topological net consisting of binuclear {Ln2(COO)3} SBUs. The formation of polymeric networks in series 1Ln-4Ln is facilitated by the numerous coordination sites of the ligand Br4bdc2- and the fact that its bromine atoms can participate in the formation of various types of intermolecular interactions. The solid-state photoluminescence studies on Eu- (1Eu) and Tb- (1Tb, 3Tb, 4Tb) containing compounds indicate that the Br4bdc2- ligands can efficiently sensitize Eu3+ and Tb3+ emission. Notably, such compounds exhibit highly sensitive fluorescence sensing for acetone, water, and Fe3+ ions via the fluorescence quenching effect. As the representatives of the series, activated 1Eu, 2Pr, 3Tb, and 4Tb show the maximum CO2 uptake capacities of 170.4, 273.7, 255.3, and 303.5 cm3 g-1, respectively, at 50 bar and 298 K with good repeatability of the adsorption-desorption properties. Magnetic studies indicate that the Gd- and Dy-based compounds 1Gd, 1Dy, 3Gd, 3Dy, and 4Gd show simple paramagnetic behaviours, whereas compound 4Dy exhibits weak ferromagnetic interactions.

Novel selective "on-off" fluorescence sensor based on julolidine hydrazone-Al3+ complex for Cu2+ ion: DFT study.

A hydrazone (T1) was synthesized by reacting 8-hydroxyjulolidine-9-carboxaldehyde with 2-furoic hydrazide and then modified with Al3+ ion to form a novel hydrazone Al3+ complex (T1-Al3+) in an aqueous solution (8% propylene glycol in 10 mM HEPES pH 5.5). The T1-Al3+ complex was studied as a Cu2+ selective sensor due to its highly efficient capacibility of paramagnetic quenching. The results showed that the T1-Al3+ complexed sensor possesses remarkable sensitivity and selectivity for Cu2+ ion in 8% propylene glycol in 10 mM HEPES pH 5.5 as compared with other tested analytes. Notably, this sensor has a broad linear detection range of 10-110 µM for Cu2+ ion and a detection limit level of 0.62 µM, which is lower than the Cu2+ concentration threshold in drinking water designated by the United States Environmental Protection Agency (EPA). Additionally, it was detectable for the presence of Cu2+ ion in mineral water and tap water samples. The selectivity of T1-Al3+ complexed sensor with Cu2+ ion could be explained by the basis of computation with Gaussian software complied with the basis sets of B3LYP/6-31 G(d,p)/LANL2DZ. Furthermore, only T1 exhibited anticancer efficacy against HeLa and U251 cells with MTT assay.

Indomethacin-based near-infrared photosensitizer for targeted photodynamic cancer therapy.

Near-IR fluorescent sensitizers based on heptamethine cyanine (Cy820 and Cy820-IMC) were synthesized and their abilities to target and abolish tumor cells via photodynamic therapy (PDT) were explored. Some hepthamethine cyanine dyes can be transported into cancer cells via the organic anion transporting polypeptides (OATPs). In this study, we aimed to enhance the target ability of the sensitizer by conjugation Cy820 with indomethacin, a non-steroidal anti-inflammatory drug (NSAID), to obtain Cy820-IMC that aimed to target cyclooxygenase-2 (COX-2) which overexpresses in cancer cells. The results showed that Cy820-IMC internalized the cancer cells faster than Cy820 which was verified to be related to COX-2 level and OATPs. Based on PDT experiments, Cy820-IMC has higher photocytotoxicity index than Cy820, >7.13 and 4.90, respectively, implying that Cy820-IMC showed better PDT property than Cy820. However, Cy820 exhibits slightly higher normal-to-cancer cell toxicity ratio than Cy820-IMC, 6.58 and 3.63, respectively. Overall, Cy820-IMC has superior cancer targetability and enhanced photocytoxicity. These characteristics can be further improved towards clinically approved sensitizers for PDT.

Selective Extraction, Recovery, and Sensing of Hydroquinone Mediated by a Supramolecular Pillar[5]quinone Quinhydrone Charge-Transfer Complex.

Intermolecular interactions between an electron-rich aromatic hydroquinone (HQ) with its electron deficient counterpart, benzoquinone (BQ), result in the formation of a quinhydrone charge-transfer complex. Herein, we report a novel quinhydrone-type complex between pillar[5]quinone (P[5]Q) and HQ. Characterized by a suite of spectroscopic techniques including 1H NMR, UV-visible, and FTIR together with PXRD, SEM, BET, CV, and DFT modeling studies, the stability of the complex is determined to be due to an electron-proton transfer reaction coupled with a complementary donor-acceptor interaction. The selectivity of P[5]Q toward HQ over other dihydroxybenzene isomers allows for not only the naked-eye detection of HQ but also its selective liquid-liquid extraction and recovery from aqueous media.

Ratiometric Fluorescent Sensor for Copper(II) and Phosphate Ions from Aminopyrene Derivatives.

Three derivatives of 1-aminopyrene are functionalized with 2-picolyl and 2-picolinyl groups and are tested as fluorescent sensors for metal ions. The target compounds are successfully synthesized in yields of 50-90% and characterized by 1 H-NMR, 13 C-NMR, and HRMS. The compound with an amino picolyl group (P1) exhibits an excellent selectivity toward Cu(II) ion as the fluorescent signal shifts from 433 to 630 nm. From a fluorescence titration experiment, the limit of detection for Cu(II) ion is estimated as 0.19 µm. The fluorescence spectral shift by Cu(II) ion is reliant on the use of acetonitrile as a co-solvent, and the results from cyclic voltammetry and UV-Vis spectroscopy suggest that the sensing mechanism involves a coordination complex between the P1, acetonitrile and Cu(II) ion. Furthermore, this P1-Cu complex can also be used as a selective fluorescent sensor for PO4 3- ion with a detection limit of 0.44 µm.

A Dihydropyridine Derivative as a Highly Selective Fluorometric Probe for Quantification of Au3+ Residue in Gold Nanoparticle Solution.

Novel dihydroquinoline derivatives (DHP and DHP-OH) were synthesized in one pot via a tandem trimerization-cyclization of methylpropiolate. DHP and DHP-OH possess strong blue fluorescence with high quantum efficiencies over 0.70 in aqueous media. DHP-OH displays a remarkable fluorescence quenching selectively to the presence of Au3+ through the oxidation of dihydropyridine to pyridinium ion as confirmed by NMR and HRMS. DHP-OH was used to demonstrate the quantitative analysis of Au3+ in water samples with the limit of detection of 33 ppb and excellent recovery (>95%). This fluorescent probe was also applied for the determination of Au3+ residue in the gold nanoparticle solution and a paper-based sensing strip for the on-site detection of Au3+.

Charge neutral halogen bonding tetradentate-iodotriazole macrocycles capable of anion recognition and sensing in highly competitive aqueous media.

A series of neutral tetradentate halogen bonding (XB) macrocycles, comprising of two bis-iodotriazole XB donors were synthesised in 60-70% yields via a stepwise CuAAC-mediated cyclisation strategy. Extensive 1H NMR anion titration experiments reveal halide binding affinities are critically dependent on the substitution pattern of the xylyl spacer unit. The meta-substituted macrocycle remarkably displays cooperative tetradentate XB-halide anion recognition in highly competitive 40% aqueous-organic D2O/acetone-d6 (40 : 60, v/v) solvent mixtures. Integration of para-xylyl and naphthyl spacer units generates extended macrocyclic cavities, capable of selective oxalate recognition. Furthermore, preliminary fluorescence exeperiments reveal dicarboxylate specific sensing can be achieved through monitoring of the naphthylene centred emission.

Self-Assembly of 1D Double-Chain and 3D Diamondoid Networks of Lanthanide Coordination Polymers through In Situ-Generated Ligands: High-Pressure CO2 Adsorption and Photoluminescence Properties.

Two new lanthanide-based coordination polymers, [Sm2(bzz)(ben)6(H2O)3]·0.5H2O (1) and [Eu(bbz)(ben)3] (2), were synthesized and characterized. The described products were formed from in situ-generated benzoate (ben) and N'-benzoylbenzohydrazide (bbz) ligands, which were the products of transformation of originally added benzhydrazide (bzz) under hydrothermal conditions. Compound 1 exhibits a one-dimensional (1D) double-chain structure built up from the connection of the central Sm3+ ions with a mixture of bzz and ben ligands. On the other hand, 2 features a 3D network with a 4-connected (66) dia topology constructed from dinuclear [Eu2(ben)6] secondary building units and bbz linkers. High-pressure CO2 sorption studies of activated 1 show that maximum uptake increases to exceptionally high values of 376.7 cm3 g-1 (42.5 wt%) under a pressure of 50 bar at 298 K with good recyclability. Meanwhile, 2 shows a typical red emission in the solid state at room temperature with the decay lifetime of 1.2 ms.

Flavylium-Based Hypoxia-Responsive Probe for Cancer Cell Imaging.

A hypoxia-responsive probe based on a flavylium dye containing an azo group (AZO-Flav) was synthesized to detect hypoxic conditions via a reductase-catalyzed reaction in cancer cells. In in vitro enzymatic investigation, the azo group of AZO-Flav was reduced by a reductase in the presence of reduced nicotinamide adenine dinucleotide phosphate (NADPH) followed by fragmentation to generate a fluorescent molecule, Flav-NH2. The response of AZO-Flav to the reductase was as fast as 2 min with a limit of detection (LOD) of 0.4 µM. Moreover, AZO-Flav displayed high enzyme specificity even in the presence of high concentrations of biological interferences, such as reducing agents and biothiols. Therefore, AZO-Flav was tested to detect hypoxic and normoxic environments in cancer cells (HepG2). Compared to the normal condition, the fluorescence intensity in hypoxic conditions increased about 10-fold after 15 min. Prolonged incubation showed a 26-fold higher fluorescent intensity after 60 min. In addition, the fluorescence signal under hypoxia can be suppressed by an electron transport process inhibitor, diphenyliodonium chloride (DPIC), suggesting that reductases take part in the azo group reduction of AZO-Flav in a hypoxic environment. Therefore, this probe showed great potential application toward in vivo hypoxia detection.

Fluorescent Sensor for Copper(II) and Cyanide Ions via the Complexation-Decomplexation Mechanism with Di(bissulfonamido)spirobifluorene.

A novel spirobifluorene derivative bearing two bissulfonamido groups is successfully synthesized by Sonogashira coupling. This compound exhibits a strong fluorescence quenching by Cu(II) ion in a 50% mixture between acetonitrile and 20 mM pH 7.0 N-(2-hydroxyethyl)piperazine-N'-ethanesulfonic acid (HEPES) buffer with a detection limit of 98.2 nM. However, this sensor also shows ratiometric signal shifts from blue to yellow in the presence of Zn(II), Pb(II), and Hg(II) ions. The static quenching mechanism is verified by the signal reversibility using ethylenediaminetetraacetic acid (EDTA) and the Stern-Volmer plots at varying temperatures. The Cu(II)-spirobifluorene complex shows a highly selective fluorescence enhancement upon the addition of CN- ion with the detection limit of 390 nM. The application of this complex for quantitative analysis of spiked CN- ion in real water samples resulted in good recoveries.

Coordination-driven self-assembly of a series of dinuclear M2L2 mesocates with a bis-bidentate pyridylimine ligand.

Four isostructural dinuclear M2L2 mesocates of the general formula [M2(NCS)4(L)2]·4.5MeOH (1M; M = Mn, Fe, Co, Zn) were constructed by using the coordination-driven self-assembly of the [M(NCS)2] precursor and the flexible bis-bidentate pyridylimine Schiff base ligand L (L = 4,4'-(1,4-phenylenebis(oxy))bis(N-(pyridin-2-ylmethylene)aniline). The centrosymmetric M2L2 mesocate forms through the side-by-side coordination of two L ligands to a pair of M(ii) ions. The mesocates exhibit a reversible temperature induced desolvation-solvation behavior without losing their structural integrity. The activated 1Co, as the representative M2L2 mesocate, shows an exceptionally high MeOH vapour uptake capacity of 481.9 cm3 g-1 (68.8 wt%) at STP with good recyclability. Notably, it also exhibits CO2 adsorption with an uptake capacity of 20.2 cm3 g-1 (3.6 wt%) at room temperature and 1 bar.

Fluorescence Sensors for Bismuth (III) Ion from Pyreno[4,5-d]imidazole Derivatives.

Three pyreno[4,5-d]imidazole derivatives are synthesized and evaluated as fluorescent sensors for bismuth (III) ion. The target compounds are prepared in 55-86% yields from a condensation reaction between pyrene-4,5-dione and aromatic aldehydes. The compound bearing a phenolic group can selectively detect bismuth (III) ion via fluorescence enhancement with a detection limit of 1.20 µm in CH3 CN-DMSO mixture and 3.40 µm in 10% pH5 aqueous in CH3 CN-DMSO mixture. The sensing mechanism involving a formation of coordination complex is investigated by UV-VIS and fluorescence titrations, 1 H-NMR and the decomplexation of the bismuth complex by sulfide ion. The application of this sensor for quantitative analysis of spiked bismuth (III) ion in real water samples from two different sources is demonstrated.