Fluorescent-based micellar incorporated hydrogel materials for selective determination of long-chain aldehydes.

A highly sensitive micelle-induced sensory has been developed for detection of long-chain aldehydes as potential biomarkers of respiratory cancers. The micelle-like sensor was fabricated through the partial self-assembly of CTAB and S2 surfactants, containing a fluorescent hydrazine-functionalized dye (Naph-NH2). In principle, long-chain aldehydes with amphiphilic character act as the induced-fit surfactants to form well-entrapped micellar particles, as well as react with Naph-NH2 to form hydrazone derivatives resulting in fluorescent enhancement. The limit of detection (LOD) of micellar Naph-NH2/CTAB/S2 platform was calculated to be ∼  64.09-80.98 µM for detection of long-chain aldehydes, which showed fluorescent imaging in lung cancer cells (A549). This micellar sensory probe demonstrated practical applicability for long-chain aldehyde sensing in human blood samples with an accepted percent recovery of ~ 94.02-102.4%. Beyond Naph-NH2/CTAB/S2 sensor, the milcellar hybrid sensor was successfully developed by incorporating a micelle-like platform with supramolecular gel regarding to carboxylate-based gelators (Gel1), which showed a tenfold improvement in sensitivity. Expectedly, the determination of long-chain aldehydes through these sensing platforms holds significant promise for point-of-care cancer diagnosis and therapy.

Electrocatalytic Hydrogen Evolution of Immobilized Copper Complex on Carbonaceous Materials: From Neutral Water to Seawater.

Electrochemical hydrogen evolution reaction (HER) is an appealing strategy to utilize renewable electricity to produce green H2. Moreover, use of neutral-pH electrolyte such as water and seawater for the HER has long been desired for eco-friendly energy production that aligns with net zero emission goal. Herein, new heterogeneous catalysts were developed by dispersing an HER-active copper complex containing N4-Schiff base macrocycle (CuL) on carbonaceous materials, i. e. multi-walled carbon nanotube (CNT) and graphene oxide (GO), via non-covalent interaction and investigated their HER performance. It was found that CuL/GO exhibited higher HER activity than CuL/CNT, possibly due to its significantly larger amount of CuL immobilized onto GO. In addition, CuL/GO showed satisfactory HER performance in a neutral (pH 7) NaCl electrolyte solution. Notably, the performances of CuL/GO were boosted up when performed in natural seawater sample with the faradaic efficiency of 70 % and 3 times higher amount of H2 at -0.6 V vs reversible hydrogen electrode (RHE), in comparison to the HER in a NaCl electrolyte. Furthermore, it possessed a low overpotential of 139 mV at -10 mA/cm2. This demonstrated the potential use of CuL/GO as an effective HER catalyst in seawater for further sustainable development.

Correction: Turn-on fluorogenic sensors based on an anthraquinone signaling unit for the detection of Zn(II) and Cd(II) ions.

Correction for 'Turn-on fluorogenic sensors based on an anthraquinone signaling unit for the detection of Zn(II) and Cd(II) ions' by Chawanakorn Kongsak et al., Org. Biomol. Chem., 2023, 21, 7367-7381, https://doi.org/10.1039/D3OB01223A.

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.

Turn-on fluorogenic sensors based on an anthraquinone signaling unit for the detection of Zn(II) and Cd(II) ions.

Turn-on fluorescent chemosensors based on an anthraquinone moiety, N,N'-(9,10-dioxo-9,10-dihydroanthracene-1,8-diyl)bis(2-(bis(pyridin-2-ylmethyl)amino)acetamide) (1) and N,N'-(9,10-dioxo-9,10-dihydroanthracene-2,6-diyl)bis(2-(bis(pyridin-2-ylmethyl)amino)acetamide) (2), have been successfully synthesized with the overall yields of 61% and 90%, respectively. The structures of both chemosensors 1 and 2 were elucidated using several spectroscopic techniques such as 1H NMR, 13C NMR, 2D-NMR, FTIR and HRMS. The target chemosensor 1 is a promising tool for the detection of trace levels of d10 metal ions, such as Zn(II) and Cd(II) ions, by exhibiting a significant fluorescence enhancement via a turn-on photoinduced electron transfer (PET) mechanism with a rapid and highly reproducible signal, and low detection limit values of 0.408 µM and 0.246 µM, for Zn(II) and Cd(II), respectively.

Molecularly dispersed nickel complexes on N-doped graphene for electrochemical CO2 reduction.

In this work, new hybrid catalysts based on molecularly dispersed nickel complexes on N-doped graphene were developed for electrochemical CO2 reduction (ECR). Nickel(II) complexes (1-Ni, 2-Ni), and a new crystal structure ([2-Ni]Me), featuring N4-Schiff base macrocycles, were synthesized and investigated for their potential in ECR. Cyclic voltammetry (CV) in NBu4PF6/CH3CN solution demonstrated that the nickel complexes bearing N-H groups (1-Ni and 2-Ni) showed a substantial current enhancement in the presence of CO2, while the absence of N-H groups ([2-Ni]Me) resulted in an almost unchanged voltammogram. This indicated the necessity of the N-H functionality towards ECR in aprotic media. All three nickel complexes were successfully immobilized on nitrogen-doped graphene (NG) via non-covalent interactions. All three Ni@NG catalysts exhibited satisfactory CO2-to-CO reduction in aqueous NaHCO3 solution with the faradaic efficiency (FE) of 60-80% at the overpotential of 0.56 V vs. RHE. The ECR activity of [2-Ni]Me@NG also suggested that the N-H moiety from the ligand is less important in the heterogeneous aqueous system owing to viable hydrogen-bond formation and proton donors from water and bicarbonate ions. This finding could pave the way for understanding the effects of modifying the ligand framework at the N-H position toward fine tuning the reactivity of hybrid catalysts through molecular-level modulation.

Polydiacetylene rhodamine-based colorimetric chemosensor for Au3+ detection.

A novel platform of a polydiacetylene combined with rhodamine B (PDA-Rho) colorimetric chemosensor array was prepared from a diacetylene monomer and rhodamine B derivative. Rhodamine B derivative as the ion-recognition element was embedded in the polydiacetylene matrix. To fabricate chemosensor, diacetylene monomer connected rhodamine B derivatives (DA-Rho) was coated onto a filter paper surface via drop-casting technique and transformed to polydiacetylene by polymerisation through ultraviolet (UV) irradiation. From the result, PDA-Rhoen exhibited high sensitivity and selectivity for Au3+ and could be monitored directly by naked eyes providing a fast, portable and easy-to-use as a molecular device in the real system. The DFT calculation results showed a stable complex between PDA-Rho and Au3+. We believe that, this method offers a sensitive and accurate process for Au3+ ion detection in real environmental and biological applications.

Atomic- and Molecular-Level Modulation of Dispersed Active Sites for Electrocatalytic CO2 Reduction.

Global climate changes have been impacted by the excessive CO2 emission, which exacerbates the environmental problems. Electrocatalytic CO2 reduction (CO2 RR) offers the solution for utilising CO2 as feedstocks for value-added products while potentially mitigating the negative effects. Owing to the extreme stability of CO2 , selectivity and efficiency are crucial factors in the development of CO2 RR electrocatalysts. Recently, single-atom catalysts have emerged as potential electrocatalysts for CO2 reduction. They generally comprise of atomically- and molecularly dispersed active sites over conductive supports, which enable atomic-level and molecular-level modulations. In this minireview, catalyst preparations, principle of modulations, and reaction mechanisms are summarised together with related recent advances. The atomic-level modulations are first discussed, followed by the molecular-level modulations. Finally, the current challenges and future opportunities are provided as guidance for further developments regarding the discussed topics.

An ultra-low detection limit gold(III) probe based on rhodamine-covalent hydrogel sensor.

A highly sensitive and selective optical chemosensor (Arg-Rhoen) for determination of Au3+ was prepared by covalent immobilization of rhodamine ethylenediamine on agarose gel. Spectrophotometric studies of complex formation, chemical structures and purity of the hydrogel sensor were carried out using TGA, NMR, TEM, and IR. The complexation study results indicated that this probe can selectively detect Au3+ via a metal ion chelation-induced ring-opening reaction, and then caused a remarkable colour change from colourless to pink and a strong fluorescence enhancement. Theoretical DFT calculation results suggested that the hydrogel sensor Arg-Rhoen formed stable complexes with Au3+ through a large number of cation-dipole interactions. Reusability has been established by repeatedly dipping and rinsing the hydrogel in aqueous Au3+ and EDTA in basic solutions. We believe that this approach may provide an easily measurable and inherently sensitive method for Au3+ detection in environmental and biological applications.

Fabrication of a paper-based sensor from graphene quantum dots coated with a polymeric membrane for the determination of gold(III) ions.

A novel paper-based sensor using graphene quantum dots (GQDs) as a colorimetric probe for Au3+ determination has been developed. The paper sensor was fabricated by the adsorption of GQDs onto cellulose filter paper and then coating with a PVC membrane. The PVC membrane was plasticized with o-NPOE containing potassium tetrakis(4-chlorophenyl)borate (KTpClPB) as a lipophilic cation-exchanger. According to the ion-exchanged mechanism between the lipophilic phase and aqueous phase, Au3+ in the aqueous solution was extracted to the lipophilic phase on the paper layer. Then, adsorbed GQDs on the paper could selectively reduce Au3+ to elemental gold (Au0). The generated gold nanoparticles (AuNPs) resulted in the color of the paper turning from pale yellow to pink, which was recorded by using CIE L*a*b* color space. Under optimized conditions, the change in the color difference (ΔE) was related to the concentration of Au3+ in a working linear range of 200-1000 µM and the detection limit was found to be 70 µM. The proposed sensor was successfully applied to the determination of Au3+ in real water samples. The results were in favorable agreement with standard inductively coupled plasma-optical emission spectrometry (ICP-OES) results.

A colorimetric paper-based optode sensor for highly sensitive and selective determination of thiocyanate in urine sample using cobalt porphyrin derivative.

In this work, a highly sensitive colorimetric paper-based optode for the determination of thiocyanate in urine samples was developed for the first time. The cocktail solution of the optode was composed of 5,10,15,20-tetrakis(4-octyloxyphenyl)porphyrin cobalt(II) complex (L), tridodecylmethylammonium chloride (TDMACl), 2-nitrophenyl octyl ether, and polyvinyl chloride as an ionophore, an ion exchanger, a plasticizer, and a polymer, respectively. The paper-based optode responded to thiocyanate by increasing the blue component in the RGB index and a visible change, with the naked-eye, of the optode color from pink to green was observed. From the central composite design, the optimized conditions that yielded the highest sensitivity were 4.70 mmol/kg TDMACl and 13.75 mmol/kg L. The developed optode sensor was highly selective and responded to thiocyanate over other anions, with a working range of 0.001-5 mM and with a coefficient of determination (R2) of 0.9915. The limits of detection using naked-eye and camera were determined to be 50.0 µM and 1.26 µM, respectively. In addition, the LOD and LOQ estimated from the standard deviation of the blank were 0.65 and 1.87 µM, respectively. Furthermore, this sensor was successfully applied to the detection of thiocyanate in urine samples from non-smokers and smokers. The results were in good agreement with the standard ion chromatography (IC) technique. This developed paper-based optode sensor was simple, low-cost, portable, and easy to use as a sensing device without any complicated instrument.

Paper-based cation-selective optode sensor containing benzothiazole calix[4]arene for dual colorimetric Ag+ and Hg2+ detection.

A new paper-based analytical device based on bulk ion-selective optodes (ISOs) for dual Ag+ and Hg2+ detection has been developed. A plasticized PVC hydrophobic phase composed of 25,27-di(benzothiazolyl)-26,28-hydroxycalix[4]arene (CU1) as an ion-selective ionophore, potassium tetrakis(4-chlorophenyl)borate as an ion-exchanger and chromoionophore XIV as a lipophilic pH indicator was entrapped in the pores of cellulose paper. This paper strip showed higher selectivity for Ag+ and Hg2+ over common alkali, alkaline earth and some transition metal ions with a color change from blue to yellow. With the proposed sensor, Ag+ and Hg2+ can be measured with the range of 1.92 × 10-6 to 5.00 × 10-3 M for Ag+ and 5.74 × 10-7 to 5.00 × 10-5 M for Hg2+ with a limit of detection of 1.92 × 10-6 M for Ag+ and 5.74 × 10-7 M for Hg2+. The proposed sensor was successfully applied to determine the amount of mercury in various water sources and the amount of silver in cleaning product samples containing silver nanoparticles (AgNPs). The results were in good agreement with inductively couple plasma-optical emission spectrometric measurements (ICP-OES).

Dual Naked-Eye Optical Sensor Based on Imidazolium Cation and Napthalamide for Specific Detection of Fluoride.

A novel naked eye fluorescence sensor (ANI) based on naphthalimide and imidazolium moieties for fluoride detection has been designed and synthesized by multiple step synthesis. The fluorescence response of ANI sensor was significantly quenched in the presence of fluoride ion upon the interaction between an acidic amide proton and acidic C2 proton (-C(2)H-) of imidazolium compound. The binding behavior of ANI and F- ion was extensively explored by using NMR titration. Comparison of binding ability of ANI and AN sensors addressed the dominant electrostatic and hydrogen bonding interaction with F- ion. Consequently, ANI sensor highlights a strong binding with F- ions with a high selectivity over AN. Interestingly, ANI demonstrated a naked-eye response with colorimetric and fluorometric assay.

Gold sensing with rhodamine immobilized hydrogel-based colorimetric sensor.

A highly sensitive and selective optical membrane for determination of Au3+ was synthesized by immobilization of a rhodamine derivative on agarose hydrogel. The sensing dye was synthesized by solvatochromism of rhodamine B via rhodamine lactone-zwitterion equilibrium. UV-vis spectroscopy, scanning electron microscopy (SEM), thermal gravimetric analysis (TGA) and attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) were employed to confirm that the rhodamine-lactone (RhoL) was incorporated into the agarose hydrogel. The results showed that the sensor was highly selective for recognizing Au3+ over other metal ions in real systems. In addition, DFT calculation results suggested that the membrane sensor formed stable complexes with Au3+ through a large number of cation-dipole and ion-ion interactions. In addition, according to changes in signaling upon adding various Au3+ concentration, the limit of detection of Arg-RhoL for Au3+ is calculated to be 5 µM. This approach may provide an easily measurable and inherently sensitive method for Au3+ ion detection in environmental and biological applications.

5-Methyl-1,3-phenyl-ene bis-[5-(di-methyl-amino)-naphthalene-1-sulfonate]: crystal structure and DFT calculations.

The title compound, C31H30N2S2O6, possesses crystallographically imposed twofold symmetry with the two C atoms of the central benzene ring and the C atom of its methyl substituent lying on the twofold rotation axis. The two dansyl groups are twisted away from the plane of methyl-phenyl bridging unit in opposite directions. The three-dimensional arrangement in the crystal is mainly stabilized by weak hydrogen bonds between the sulfonyl oxygen atoms and the hydrogen atoms from the N-methyl groups. Stacking of the dansyl group is not observed. From the DFT calculations, the HOMO-LUMO energy gap was found to be 2.99 eV and indicates n→π* and π→π* transitions within the mol-ecule.

Stabilisation of copper(i) polypyridyl complexes toward aerobic oxidation by zinc(ii) in combination with acetate anions: a facile approach and its application in ascorbic acid sensing in aqueous solution.

A new and facile approach to stabilise copper(i) complexes in aqueous solution by the addition of zinc(ii) ions in combination with acetate ions (OAc-) was demonstrated. This stability enhancement toward the aerobic oxidation of copper(i) species was investigated by various techniques including UV-vis spectroscopy, 1H-NMR, FT-IR, and ESI-MS. Our experimental results together with DFT calculations led to a proposed structure of [(adpa)Cu-OAc-Zn(OAc)(H2O)2]+/2+. It was also postulated that zinc(ii) with its Lewis acidity may attract electrons from the Cu centre through the bridging ligands (OAc-), resulting in the lower reactivity of Cu(i) with O2. In addition, this strategy was shown to be applicable to ascorbic acid detection by monitoring a change in the redox states of copper complexes using fluorescence spectroscopy. Moreover, it was demonstrated that the method was sensitive and accurate for the quantitative analysis of ascorbic acid in vitamin C tablets.

Tuning the reactivity of copper complexes supported by tridentate ligands leading to two-electron reduction of dioxygen.

A series of copper complexes bearing polypyridyl tridentate ligands have been prepared to fine tune their reactivity toward the oxygen reduction reaction (ORR). During the process of preparation of our copper complexes, we successfully obtained two new crystal structures which are [Cu2(µ-Cl)2(adpa)2](ClO4)2 (2b) and [Cu2(addpa)(CH3CN)2(ClO4)2](ClO4)2 (3a) and a new structure [Cu2(addpa)(CH3CN)2(H2O)2](ClO4)4 (3b) captured after the catalytic ORR. Electrochemical studies and stoichiometric chemical reduction of copper(ii) complexes by ascorbic acid indicated that the presence of an anthracene unit helps to facilitate the reduction of Cu(ii) as well as the stabilisation of Cu(i) species. Regarding oxygen activation, the dinuclear Cu(i) complex 3a showed significantly higher ORR activity than its analogous mononuclear complex 2a. Complex 3a was also found to be relatively robust and competent in catalytic O2 reduction. The observed H2O2 product after this catalysis, together with the data obtained from DFT calculations supported that 3a exhibited a 2H+, 2e- catalytic activity towards the ORR as opposed to the expected 4H+, 4e- process usually found in copper complexes with tridentate ligands. The proton (H+) source for this process was expected from ascorbic acid which also serves as a reducing agent in this reaction. This work highlighted an approach for tuning the ORR activity of the copper complexes by the introduction of a conjugated-π moiety to the supporting ligand.

A new formaldehyde sensor from silver nanoclusters modified Tollens' reagent.

A selective colorimetric assay for detecting formaldehyde (FA) was proposed based on silver nanoclusters (AgNCs) templated by polymethacrylic acid (PMAA). The chemodosimeter was easily fabricated by the formation of Tollens' reagent in the presence of AgNCs (AgNCs@Tollens). The detection principle was based on the change in the color caused by the change in the particle size from nanoclusters (no LSPR) to nanoparticles (with LSPR) upon the reduction of Tollens' reagent by FA. In the presence of FA, the intensity of a new absorbance band with a maximum at a wavelength of 430 nm corresponding to the LSPR of the AgNPs linearly increased as a function of the FA concentration, exhibiting a color change that could be observed by the naked eye. This method provided a working range of 30-50 µM with lower detection limit (LOD) of 27.99 µM. The proposed method exhibited excellent selectivity towards FA over other aldehyde-containing compounds.

Cysteamine-capped copper nanoclusters as a highly selective turn-on fluorescent assay for the detection of aluminum ions.

A new type of copper nanoclusters was synthesized by a one-pot reaction using cysteamine as a capping agent and reducing agent (Cys-CuNCs). The synthesized CuNCs exhibited a spherical shape and a monodisperse and strong fluorescent emission characteristic peak at 430nm when exciting at 330nm. The Cys-CuNCs were demonstrated as a fluorescent chemodosimeter for the selective detection of Al3+. In the presence of Al3+, the fluorescent emission of the Cys-CuNCs was considerably enhanced, while other studied metal ions did not show this phenomenon. The fluorescent intensity near 380nm linearly increased with an increasing Al3+ concentration. The proposed method provided a working range of 1-7µM with a low detection limit of 26.7nM and was applied to determine Al3+ in drinking water samples with satisfactory results.

Self-assembly of Gd3+/SDS/HEPES complex and curcumin entrapment for enhanced stability, fluorescence image in cellular system.

At present, strategies to disperse hydrophobic molecules in water without altering their chemical structures include conventional surfactant-based micellar and vesicular systems, encapsulation into water dispersible polymeric nanoparticles, and loading onto the surface of various metal nanoparticles. Here, we report a simple and low cost platform to incorporate hydrophobic molecules into a stable water dispersible nanostructure that can significantly increase the stability of the encapsulated materials. The platform is based on the incorporation of hydrophobic molecules into the self-assembled complex of gadolinium ion (Gd3+), sodium dodecyl sulfate (SDS), and 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) called GdSH. After being incorporated, the two model hydrophobic dyes, curcumin and curcumin borondifluoride show approximately 50% and 30% improved stability, respectively. Investigation of the self-assembled 10-14 multilayered 60nm spheres with inter-layer distances of 4.25nm indicates coordination of SDS and HEPES with Gd3+. Incorporation of the hydrophobic molecules into the multilayered spheres results in reduction of the interlayer distance of the multilayer spheres to 4.17nm, suggesting enhanced packing of the hydrophobic chain of SDS and HEPES around the Gd3+. The incorporation of the two curcuminoids into the self-assembled complex also causes an increase in fluorescence quantum yield of the two dyes, thus suggesting spatial confinement of the packed dye molecules. The better cellular uptake of the nanoparticles is responsible for the expected enhancement in fluorescence image of the encapsulated materials.