A novel 3D Cd(ii) coordination polymer generated via in situ ligand synthesis involving C–O ester bond formation

A novel 3D Cd(ii) coordination polymer {[Cd(ddpa)(2,2′-bpy)]·H₂O}_n (1) (H₂ddpa = 5,10-dioxo-5,10-dihydro-4,9-dioxapyrene-2,7-dicarboxylic acid, 2,2′-bpy = 2,2′-bipyridine) is hydrothermally synthesized in situ, and the influencing factors and mechanism for the in situ reaction are briefly discussed. The synthesis of 1 requires the formation of a new C–O ester bond. This current study confirms that metal ions and N-donor ligands play important roles in the domination of the in situ ligand from 6,6′-dinitro-2,2′,4,4′-biphenyltetracarboxylic acid (H₄dbta). Furthermore, the structure, thermal stability and photoluminescent property of 1 are also investigated.

A 3D Cd(ii) coordination polymer comprising ligand molecules not included in the original reaction mixtures but instead formed via in situ ligand synthesis involving a C–O ester bond.     

Synthesis,structure and the Hirshfeld surface analysis of three novel metal-tiron coordination complexes

Three novel metal-tiron (4,5-dihydroxy-1,3-benzenedisulfonic acid disodium salt) and other pillared ligand bpy (4,4′-bipyridyl)-centered coordination polymers of the formulae [Cd(tiron)(bpy)₂(H₂O)₂]·0.5(H₂O), 1, [Co₃(tiron-bpy)₂(bpy)(H₂O)₈]·(H₂O)₂, 2, and [Ba₂(tiron-bpy)₂(H₂O)₄][solvent], 3, were successfully synthesized under hydrothermal conditions. The as-synthesized materials were well characterized by complimentary techniques such as single-crystal X-ray diffraction, powder X-ray diffraction, Fourier-transform infrared spectroscopy and thermogravimetric analysis techniques. The as-synthesized coordination polymers of 1 and 2 featured 1D chains, while 3 shows a layered structure. Co-based 2 shows linear trinuclear Co(ii) ions and these Co(ii) ions have antiferromagnetic interactions among themselves. The structure of 1 features a zig-zag chain formed by the linkage between monodentate tiron ligands and octahedral Cd(ii) ions, interconnected by a twisted bpy ligand, 2 shows a linear chain constructed from corner-sharing trinuclear octahedral Co(ii) ions and coordinated with a tridentate tiron-bpy adduct ligand, whereas 3 shows nona-coordinated Ba(ii) ions sharing edges with other Ba(ii) ions and connected by hexadentate tiron-bridged structures resulting in a layered structure. In 2 and 3, the bpy nitrogen attacks at the ortho position of the tiron ligand and forms an in situ ligand adduct. The central metal ions show an octahedral geometry in 1 (Cd(ii) ions) and 2 (Co(ii) ions), but nona-coordination of Ba(ii) ions in 3. The short interatomic interactions in the crystal structures were evaluated by mapping the Hirshfeld surface process using pseudo-mirrored 2D fingerprint plots. The major short interatomic interactions H⋯H, O⋯H and C⋯H cover the Hirshfeld surfaces.

Three novel metal-tiron (4,5-dihydroxy-1,3-benzenedisulfonic acid disodium salt) and other pillared ligand bpy (4,4-bipyridyl) centered coordination polymers were successfully synthesized and characterized.     

Metal–organic frameworks incorporating azobenzene-based ligands as a heterogeneous Lewis-acid catalyst for cyanosilylation of imines

In this work, two novel metal–organic frameworks (MOFs) were synthesized by the reaction of azobenzene-based ligands and Zn(NO₃)₂/CdCO₃ under solvothermal conditions with the formula of {[Zn₂(abtc)(azpy)(H₂O)₂]·4H₂O}_n (1) and {[Cd(abtc)_0.5(azpy)_0.5(H₂O)]·3H₂O}_n (2) (H₄abtc = 3,3′,5,5′-azobenzene tetracarboxylic acid, azpy = 4,4′-azobipyridine). According to the single-crystal X-ray diffraction (SC-XRD) analysis, complexes 1 and 2 possessed quite similar structures except for the coordination modes of the central metal nodes attributed to the difference between the cationic radius of Zn(ii) and Cd(ii). The Zn(ii) cations in 1 adopted a distorted seesaw coordination geometry and the coordination between Zn(ii) and organic linkers gave two-dimensional (2D) coordination networks, while the Cd(ii) cations in 2 could also bind with the carboxylate groups from neighboring coordination networks to form a three-dimensional (3D) coordination framework. Furthermore, complexes 1 and 2 showed high catalytic activity as heterogeneous Lewis-acid catalysts towards the cyanosilylation of imines with satisfactory reusability under mild conditions and the similar catalytic performance of 1 and 2 could be attributed to the similarity in their structures. A prudent mechanism has been proposed as well to elucidate the role of complexes 1 and 2 in the catalytic process.

Two novel MOFs were synthesized by the reaction of azobenzene-based ligands with Zn(NO₃)₂/CdCO₃ and could both function as heterogeneous Lewis-acid catalysts towards cyanosilylation of imines.     

Simultaneous removal of Sb(iii) and Cd(ii) in water by adsorption onto a MnFe2O4–biochar nanocomposite

In this study, a jacobsite–biochar nanocomposite (MnFe₂O₄–BC) was fabricated and used to simultaneously remove Sb(iii) and Cd(ii) from water via adsorption. The MnFe₂O₄–BC nanocomposite was prepared via a co-precipitation method and analyzed using various techniques. The results confirm the successful decoration of the biochar surface with MnFe₂O₄ nanoparticles. The maximum Sb(iii) removal efficiency was found to be higher from bi-solute solutions containing Cd(ii) than from single-solute systems, suggesting that the presence of Cd(ii) enhances the removal of Sb(iii). The Langmuir isotherm model describes well Sb(iii) and Cd(ii) removal via adsorption onto the MnFe₂O₄–BC nanocomposite. The maximum adsorption capacities are 237.53 and 181.49 mg g⁻¹ for Sb(iii) and Cd(ii), respectively, in a bi-solute system. Thus, the prepared MnFe₂O₄–BC nanocomposite is demonstrated to be a potential adsorbent for simultaneously removing Sb(iii) and Cd(ii) ions from aqueous solutions.

In this study, a jacobsite–biochar nanocomposite (MnFe₂O₄–BC) was fabricated and used to simultaneously remove Sb(iii) and Cd(ii) from water via adsorption.     

New ruthenium polypyridyl complexes as potential sensors of acetonitrile and catalysts for water oxidation

New ruthenium(ii) polypyridyl complexes of formulae [RuCl(Me₂Ntrpy)(bpy-OMe)]Cl, 1, and [Ru(Me₂Ntrpy)(bpy-OMe)(OH₂)](CF₃SO₃)₂, 2, with Me₂Ntrpy = 4′-N,N-dimethylamino-2,2′:6′,2′′-terpyridine and bpy-OMe = 4,4′-dimethoxy-2,2′-bipyridine, were synthetized and characterized by spectroscopic and electrochemical techniques. Besides, [Ru(Me₂Ntrpy)(bpy-OMe)(NCCH₃)]²⁺, 3, was obtained and characterized by UV-vis spectroscopy in acetonitrile solution. All experimental results were complemented with DFT and TD-DFT calculations. The complete structure of complex 1 was determined by X-ray diffraction, evidencing that the Ru–N and Ru–Cl bond lengths are longer than those determined in [RuCl(trpy)(bpy)](PF₆). The strong electron donating properties of the substituents of both bpy and trpy rings in complexes 1 and 2 led to their potential applications for detecting traces of acetonitrile as a contaminant in aqueous solutions of radiopharmaceuticals and to utilization of complex 2 as a promising candidate for catalyzing water oxidation processes.

New mononuclear polypyridyl Ru(ii) complexes were synthesized and fully characterized. These species can be potentially applied for detection of CH₃CN as a contaminant in radiopharmaceuticals used in PET studies or for catalysing water oxidation.     

Alkaline earth metal ion coordination increases the radical scavenging efficiency of kaempferol

Flavonoids are used as natural additives and antioxidants in foods, and after coordination to metal ions, as drug candidates, depending on the flavonoid structure. The rate of radical scavenging of the ubiquitous plant flavonoid kaempferol (3,5,7,4′-tetrahydroxyflavone, Kaem) was found to be significantly enhanced by coordination of Mg(ii), Ca(ii), Sr(ii), and Ba(ii) ions, whereas the radical scavenging rate of apigenin (5,7,4′-trihydroxyflavone, Api) was almost unaffected by alkaline earth metal (AEM) ions, as studied for short-lived β-carotene radical cations (β-Car˙⁺) formed by laser flash photolysis in chloroform/ethanol (7 : 3) and for the semi-stable 2,2-diphenyl-1-picrylhydrazyl radical, DPPH˙, in ethanol at 25 °C. A 1 : 1 Mg(ii)–Kaem complex was found to be in equilibrium with a 1 : 2 Mg(ii)–Kaem₂ complex, while for Ca(ii), Sr(ii) and Ba(ii), only 1 : 2 AEM(ii)–Kaem complexes were detected, where all complexes showed 3-hydroxyl and 4-carbonyl coordination and stability constants of higher than 10⁹ L² mol⁻². The 1 : 2 Ca(ii)–Kaem₂ complex had the highest second order rate constant for both β-Car˙⁺ (5 × 10⁸ L mol⁻¹ s⁻¹) and DPPH˙ radical (3 × 10⁵ L mol⁻¹ s⁻¹) scavenging, which can be attributed to the optimal combination of the stronger electron withdrawing capability of the (n − 1)d orbital in the heavier AEM ions and their spatially asymmetrical structures in 1 : 2 AEM–Kaem complexes with metal ion coordination of the least steric hindrance of two perpendicular flavone backbones as ligands in the Ca(ii) complex, as shown by density functional theory calculations.

Radical scavenging activity of kaempferol is notably enhanced by Ca(ii) binding.     

Highly sensitive detection of nitrobenzene by a series of fluorescent 2D zinc(ii) metal–organic frameworks with a flexible triangular ligand

Four fluorescent zinc(ii) metal–organic frameworks, namely [Zn(HCIA)(4,4′-bipy)] (1), [Zn₂(CIA)(OH)(1,4-bibz)_1.5]·H₂O (2), [Zn(CIA)(OH) (4,4′-bbpy)] (3), and [Zn₂(HCIA) (4,4′-bimp)]·H₂O (4), were prepared hydrothermally with a flexible triangular ligand (H₃CIA) and a series of linear N-donor ligands (H₃CIA = 5-(2-carboxybenzyloxy) isophthalic acid, 4,4′-bipy = 4,4′-bipydine, 1,4-bibz = 1,4-bis(1-imidazoly)benzene; 4,4′-bbpy = 4,4′-bis (imidazolyl) biphenyl; 4,4′-bimp = 4,4′-bis (imidazole-1-ylethyl) biphenyl). Structural analyses revealed that complex 1 exhibited a 2D brick-like network structure based on the basic bimetallic ring, 2 was also a 2D interspersed structure from the 1D tubular structure, compound 3 possessed a 2D (4,4) network with 4,4′-bbpy occupying the holes, and complex 4 displayed a 2D network from the 1D ladder-like chain. The thermal stabilities and fluorescent properties of these complexes were investigated in the solid state. The fluorescent sensing experiments revealed that all Zn-MOFs could highly sensitively detect nitrobenzene in aqueous solution, which indicated that these materials can be used as fluorescent probes for the detection of nitrobenzene.

Four fluorescent 2D Zn-MOFs based on a flexible triangular ligand and linear N-donor ligands are hydrothermally prepared and used to detect nitrobenzene in aqueous solution with high sensitivity, demonstrating their potential as fluorescent sensors.     

Sonochemical synthesis of a trinuclear Cu(ii) complex with open coordination sites for the differentiable optical detection of volatile amines

A discrete trinuclear Cu(ii) complex, namely, [Cu₃(pzdc)₂(dpyam)₂(H₂O)₄] (1) (H₃pzdc = pyrazole-3,5-dicarboxylic acid, dpyam = 2,2′-dipyridylamine) was simply synthesized by the sonochemical process and structurally characterized. The single-crystal X-ray diffraction analysis revealed that three adjacent Cu(ii) centers are linked via two bridging pzdc ligands to form a trinuclear Cu(ii) unit. Each trinuclear Cu(ii) unit contains open coordination sites with two trigonal bipyramidal Cu(ii) centers and one elongated octahedral geometry. Moreover, the open coordination site of 1 was occupied by a small molecule, leading to the guest-induced structural transformation with chromism that was verified by FT-IR, UV-vis diffuse reflectance spectra, elemental analysis, PXRD, and SEM techniques. Compound 1 exhibits color change along with structural transformation in methanol media and after the dehydration process. Also, 1 shows different color responses after exposure to different amine vapors. In addition, compound 1 was conveniently deposited onto a filter paper by a sonochemical method used as a portable test strip for the discriminative qualitative detection of amines.

A trinuclear Cu(ii) complex with open coordination sites for the differentiable optical detection of volatile amines.     

Metallo-supramolecular complexes from mPEG/PDPA diblock copolymers and their self-assembled strip nanosheets

Herein we designed and synthesized mPEG/PDPA copolymers containing two 4-([2,2′:6′,2′′-terpyridin]-4′-yl) phenyl (Tpyp) groups at the junction point of the two blocks (mPEG(-b-Tpyp)₂-b-PDPA_x, x = 23, 33, and 44). Interestingly, after a hierarchical pattern from the coordination of mPEG(-b-Tpyp)₂-b-PDPA_x with Ru(ii) ions followed by the self-assembly in water, 2D strip nanosheets with a monomolecular layer were obtained. In contrast, mPEG(-b-Tpyp)₂-b-PDPA_x without coordination self-assembled into spherical micelles in the similar condition. The formation of the rigid and charged ⋯Tpyp-Ru(ii)⋯ chain, the brush-shaped polymer architecture and the presence of the hexafluorophosphate (PF₆⁻) counterions should be responsible for the unique self-assembly behavior of the metallo-supramolecular complexes. It is expected that the hierarchical self-assembly pattern can provide a new strategy for preparation of self-assemblies with different morphologies.

Copolymers mPEG(-b-Tpyp)₂-b-PDPA_x were synthesized. After a hierarchical pattern from the coordination of the copolymers with Ru(ii) ions followed by the self-assembly in water, 2D strip nanosheets were obtained.     

Microwave-assisted synthesis of ruthenium(ii) complexes containing levofloxacin-induced G2/M phase arrest by triggering DNA damage

Ru(ii) complexes have attracted increasing attention as promising antitumor agents for their relatively low toxicity, high affinity to DNA molecules, and correlation with multiple targets. Meanwhile, quinolones are synthetic antibacterial agents widely used in the clinical practice. In this paper, two novel Ru(ii) complexes coordinated by levofloxacin (LOFLX), [Ru(bpy)₂(LOFLX)]·2ClO₄ (1), and [Ru(dmbpy)₂(LOFLX)]·2ClO₄ (2) (bpy = 2,2′-bipyridine, dmbpy = 4,4′-dimethyl-2,2′-bipyridine) were synthesized with high efficiency under microwave irradiation and characterized by ESI-MS, ¹H NMR, and ¹³C NMR. The binding behavior of these complexes with double-strand calf thymus DNA(CT-DNA) was investigated using spectroscopy, molecular docking, and density functional theory calculations. Results showed that 2 exhibited higher binding affinity than 1 and LOFLX. Further studies showed that 2 could induce the G2/M phase arrest of A549 cells via DNA damage. In summary, these results indicated that 2 could be developed as a potential anticancer agent in treatment of lung cancer through the induction of cell cycle arrest at G2/M phase by triggering DNA damage.

This study showed that levofloxacin-based ruthenium(ii) complex 2 effectively inhibited the growth of A549 cells by inducing G2/M phase arrest through triggering DNA damage.     

Effects of template molecules on the structures and luminescence intensities of a series of porous Tb-MOFs based on the 2-nitroterephthalate ligand

Four novel porous Tb(iii) metal–organic frameworks (Tb-MOFs) have been designed and prepared hydrothermally from 2-nitroterephthalate (2-H₂ntp), namely {[Tb(2-ntp)_1.5(H₂O)]·H₂O}_n (1), {[Tb(2-ntp)₂(H₂O)]·4,4′-Hbipy}_n (2), {[Tb(2-ntp)₂(H₂O)]·2,4-Hbipy}_n (3), and {[Tb(2-ntp)₂(H₂O)]·(1,4-H₂bbi)_0.5}_n (4) (4,4′-bipy = 4,4′-bipyridine; 2,4-bipy = 2,4-bipyridine; 1,4-bbi = 1,4-bisbenzimidazole). X-ray diffraction structural analyses show these Tb-MOFs are porous and are based on Tb³⁺ ions and 2-nitroterephthalate, in which water molecules (1) or protonated N-donor ligands (2–4) exist as templates. The fluorescence properties of complexes 1–4 could be associated with the characteristic peaks of Tb(iii) ions, and the existence of different guest molecules affects the intensities of peaks, which means that these could be potential fluorescence materials, with intensities adjusted using guests.

Four porous Tb-MOFs based on 2-nitroterephthalate are described, in whose pores water (1) or co-ligands (2–4) exist in the pores as templates. The emissions could be related to the characteristic peaks of Tb(iii) ions, and their intensities are affected and adjusted by templates.     

Temperature tuned syntheses of two new d10-based Cd(ii) cluster metal–organic frameworks: luminescence sensing and photocatalytic properties

The solvothermal reactions of 5,5′-(1,4-phenylenebis(methyleneoxy))diisophthalic acid (H₄L) and the N-donor ancillary ligand 3,3′,5,5′-tetramethyl-4,4′-bipyrazole (bpz) with cadmium(ii) salts at two different reaction temperatures yielded two new metal–organic frameworks (MOFs), viz., [Cd(H₂L)(bpz)]_n (1) and [Cd₂(H₄L)(L)(bpz)₂]_n (2), which have been characterized by FTIR and single crystal X-ray diffraction. The single crystal X-ray diffraction studies revealed that 1 displays a 3-periodic network with monometallic SBU, while 2 exhibits a 3-periodic network with a 2-fold interpenetration feature. The effects of variation in reaction temperature on the architecture of MOFs 1 and 2 have been discussed. The luminescence investigation indicates that both 1 and 2 displayed good turn-off luminescence sensing against nitroaromatic compounds (NACs), especially m-nitrophenol (MNP), via a decrease in their luminescence intensities with a K_sv value of 6.43 × 10³ for 1 and 2.03 × 10⁴ for 2 and LOD values of 1.09 and 0.81 ppm for 1 and 2, respectively. The plausible mechanism for the decline in luminescence intensity of the MOFs with NACs has been addressed using theoretical calculations. The photocatalytic properties for both the MOFs demonstrated that they display efficient photocatalytic performances to degrade methyl violet (MV) under UV irradiation. The plausible mechanism through which these MOFs exhibited photocatalytic properties has been suggested using band gap calculations.

Two new d¹⁰-based Cd(ii) MOFs were synthesized and their photoluminescence sensing to selectively detect m-nitrophenol (MNP) and ability to decompose the organic dye methyl violet (MV) were explored.     

Electronic effects on the mechanism of the NAD+ coenzyme reduction catalysed by a non-organometallic ruthenium(ii) polypyridyl amine complex in the presence of formate

In the present study, electronic effects on the mechanism of the NAD⁺ coenzyme reduction in the presence of formate, catalysed by a non-organometallic ruthenium(ii) polypyridyl amine complex, were investigated. The [Ru^II(terpy)(ampy)Cl]Cl (terpy = 2,2′:6′,2′′-terpyridine, ampy = 2-(aminomethyl)pyridine) complex was employed as the catalyst. The reactions were studied in a water/ethanol mixture as a function of formate, catalyst, and NAD⁺ concentrations at 37 °C. The overall process was found to be 11 to 18 times slower than for the corresponding ethylenediamine (en) complex as the result of π-back bonding effects of the ampy ligand. The mechanistic studies revealed a complete set of reactions that accounted for the overall catalytic cycle based on a formate-induced hydride transfer reaction to form the reduced coenzyme, NADH. The geometries of the ruthenium(ii)-ampy complexes involved in the catalytic cycle and free energy changes for the main steps were predicted by DFT calculations. Similar calculations were also performed for the analogues ruthenium(ii)-en and ruthenium(ii)-bipy complexes (bipy = 2,2′-bipyridine). The DFT calculated energies show that both the solvent-formato exchange and the formato-hydrido conversion reactions have negative (favourable) energies to proceed spontaneously. The reactions involving the en complex have the more negative (favourable) reaction energies, followed by the ampy complex, in agreement with faster reactions for en complexes and slower reactions for bipy complexes than for ampy complexes.

The graphical abstract represents the overall catalytic cycle in which the non-organometallic Ru(ii) formato complex releases CO₂ and transfers hydride to NAD⁺ to form NADH coenzyme.     

Pd(ii) and Pt(ii) complexes of tridentate ligands with selective toxicity against Cryptococcus neoformans and Candida albicans

Novel Pd(ii) and Pt(ii) complexes of the tridentate 2,6-bis(1-ethyl-benzimidazol-2′-yl)pyridine (L^BZ), and 4′-(2-pyridyl)-2,2′:6′,2′′-terpyridine (L^PY) ligands were synthesized, characterized using a variety of analytical and spectroscopic tools, and screened for their potential antimicrobial properties against some bacterial and fungal strains as well as cytotoxicity against healthy human embryonic kidney (HEK293) cells. The electronic structures of the complexes were investigated by time-dependent density functional theory calculations. The free ligand L^PY and benzimidazole complexes exhibited selective toxicity against Cryptococcus neoformans and Candida albicans, while displaying no cytotoxicity against HEK293. In the case of Cryptococcus neoformans, the antifungal activities of the benzimidazole-based complexes (MIC = 1.58–2.62 μM) are higher than those of the reference drug fluconazole (26.1 μM).

The terpyridine ligand and the Pd(ii) and Pt(ii) benzimidazole complexes exhibited selective toxicity against Cryptococcus neoformans and Candida albicans, while displaying no cytotoxicity against healthy HEK293 cells.     

The (CF3C(O)NH)(C6H5CH2NH)2P(O) phosphoric triamide as a novel carrier with excellent efficiency for Cu(ii) in a liquid membrane transport system

Transport of Ag(i), Cd(ii), Co(ii), Cu(ii), Ni(ii), Pb(ii) and Zn(ii) cations across a bulk liquid membrane (BLM) containing N,N′-dibenzyl-N′′-(2,2,2-trifluoroacetyl)-phosphoric triamide (PTC) as a new carrier is studied by atomic absorption spectrometry. The results show selective and efficient transport of the copper(ii) cation from aqueous solution in the presence of the other cations. Various factors are optimized in order to obtain maximum transport efficiency. The PTC ligand is characterized by single crystal X-ray diffraction analysis, IR, NMR (¹⁹F, ³¹P, ¹H, ¹³C) and mass spectroscopy. The complex formation reaction between copper(ii) and PTC is studied by a conductometric method, which shows the 1 : 1 stoichiometry for ligand and copper(ii).

Selective transport of Cu(ii) cation in the presence of six other cations across a bulk liquid membrane containing a novel phosphoric triamide carrier is studied.     

Pyrene-appended bipyridine hydrazone ligand as a turn-on sensor for Cu2+ and its bioimaging application

A pyrene-appended bipyridine hydrazone-based ligand, HL, was synthesized and characterized by spectroscopic methods. Upon complexation with Cu(ii), HL formed a hexanuclear paddlewheel metal–organic macrocycle (MOM) via self-assembly with a high association constant with the molecular formula of [Cu₆L₆(NO₃)₆]. Intermolecular and intramolecular π–π interactions were demonstrated in this hexanuclear Cu(ii) complex. Further, it was observed that HL had the potential to detect a trace level of Cu(ii) ion selectively among a wide range of biologically relevant metal ions in aqueous medium at physiological pH. Using HL, it was feasible to sense copper(ii) ions in living cells due to its good cell permeability and high solubility under physiological conditions along with its high IC₅₀ value. The low detection limit, high sensitivity and good reproducibility make this Cu–sensor very promising. The complex (MOM) formed between the ligand and Cu(ii) was found to be 1 : 1 on the basis of fluorescence titrations and was confirmed by ESI-MS. Moreover, single-crystal study of the hexanuclear self-assembled fluorescent species provided better insight into its chemistry, e.g. coordination environment and binding mode, unlike most of the metal sensors due to the lack of a single-crystal structure of the metal sensor complex. Cytotoxicity assay and bioimaging were performed in living cells (Vero cells), giving green fluorescent images. Fluorescence lifetime measurements and theoretical calculations were carried out. The morphology and topographic details on the surface of the metal–organic macrocycle (MOM) were studied by field-emission scanning electron microscopy (FESEM).

A pyrene-based “turn-on” Cu(ii) sensor provides a chemiluminescent Cu₆ metal organic macrocycle (MOM) applicable for live cell imaging.     

Synthesis of FeO@SiO2–DNA core–shell engineered nanostructures for rapid adsorption of heavy metals in aqueous solutions

Creating novel and innovative nanostructures is a challenge, aiming to discover nanomaterials with promising properties for environmental remediation. In this study, the physicochemical and adsorption properties of a heterogeneous nanostructure are evaluated for the rapid removal of heavy metal ions from aqueous solutions. Core–shell nanostructures are prepared using iron oxide cores and silica dioxide shells. The core is synthesized via the co-precipitation method and modified in situ with citric acid to grow a carboxyl layer. The shell was hydrolyzed/condensed and then functionalized with amine groups for ds-DNA condensation via electrostatic interaction. The characterization techniques revealed functional FeO@SiO₂–DNA nanostructures with good crystallinity and superparamagnetic response (31.5 emu g⁻¹). The predominant superparamagnetic nature is attributed to the citric acid coating. This improves the dispersion and stability of the magnetic cores through the reduction of the dipolar–dipolar interaction and the enhancement of the spin coordination. The rapid adsorption mechanism of FeO@SiO₂–DNA was evaluated through the removal of Pb(ii), As(iii), and Hg(ii). A rapid adsorption rate is observed in the first 15 min, attributed to a heterogeneous chemisorption mechanism based on electrostatic interactions. FeO@SiO₂–DNA shows higher adsorption efficiency of 69% for Pb(ii) removal compared to As(iii) (51%) and Hg(ii) (41%). The selectivity towards Pb(ii) is attributed to the similar acid nature to ds-DNA, where the ionic strength interaction provides good affinity and stability. The facile synthesis and rapid adsorption suggest a promising nanostructure for the remediation of water sources contaminated with heavy metal ions and can be extended to other complex molecules.

Facile synthesis of well-dispersed and magnetic FeO@SiO₂–DNA nanostructures with electrostatic active sites for interaction and rapid adsorption of heavy metals.     

Fluorination in enhancing photoactivated antibacterial activity of Ru(ii) complexes with photo-labile ligands

Fluorination in enhancing photoactivated antibacterial activity of Ru(ii) complexes with photo-labile ligands was studied. Ru(ii) polypyridine complexes containing a di-fluorinated dppz (dipyrido[3,2-a:2′,3′-c]phenazine) or mono-trifluoromethylated dppz bidentate ligand and four pyridine monodentate ligands (complexes 3 and 4) were found to show potent photoactivated antibacterial activity against methicillin-resistant Staphylococcus aureus (MRSA), vancomycin-resistant Enterococcus (VRE), and Escherichia coli (E. coli) in both normoxic and hypoxic conditions. The bactericidal effect of complexes 3 and 4 under hypoxic conditions may stem from the fluorine-containing Ru(ii) aqua species after photo-induced pyridine dissociation, and DNA may be the potential antibacterial target. Photosensitized singlet oxygen may also account for their antibacterial activity under normoxic conditions. Moreover, negligible hemolysis rates as well as low dark- and photo-cytotoxicity toward human normal liver cells (L-O2) were also observed for both complexes. Our work may provide new insights into the development of novel and efficient Ru(ii) complex based photoactivatable antibacterial agents against antibiotic-resistant bacteria.

Fluorination in the dppz ligand efficiently enhanced the photoactivated antibacterial activity of Ru(ii) complexes with photo-labile ligands against antibiotic-resistant bacteria both under normoxic and hypoxic conditions.     

Single molecule magnets of cobalt and zinc homo- and heterometallic coordination polymers prepared by a one-step synthetic procedure

The synthesis of 1D cobalt and zinc monometallic and heterometallic coordination polymers (CPs) was carried out applying one-pot synthetic methods by using either supercritical carbon dioxide or ethanol as the solvent. A collection of four 1D CPs were thus obtained by the combination of a metal (or a mixture of metals) with the linker 1,4-bis(4-pyridylmethyl)benzene. The used metallic complexes were zinc and cobalt hexafluoroacetylacetonate, which can easily incorporate pyridine ligands in the coordination sphere of the metal centre. Independently of the used solvent, the precipitated phases involving Zn(ii), i.e., homometallic CP of Zn(ii) and bimetallic CP of Zn(ii)/Co(ii), were isostructural. Contrarily, homometallic CPs of Co(ii) were precipitated as an isostructural phase of Zn(ii) or with a different structure, depending on the used solvent. All the structures were resolved by XRD using synchrotron radiation. In addition, the magnetic properties of the new CPs involving Co(ii) were studied. Remarkably, at low temperatures with the application of an external field, they acted as field-induced single molecule magnets.

One-pot synthesis of heterometallic (Zn(ii)/Co(ii)) nodes directing CP magnetic behaviour to single molecule magnets.     

Functionalized biochar-supported magnetic MnFe2O4 nanocomposite for the removal of Pb(ii) and Cd(ii)

In this study, a novel magnetic biochar-MnFe₂O₄ nanocomposite (BC/FM) was prepared using low-cost corn straw and MnFe₂O₄ by sol–gel/pyrolyzing route using egg white, which has abundant functional groups (–NH₂ and –COOH). Following that, its composition, morphology and structure was characterized by various techniques including SEM-EDX, BET, XRD, and VSM. Batch experiment of the adsorption for Pb(ii) and Cd(ii) including influence of pH, kinetics, isotherm and thermodynamics was also studied. The results demonstrated that biochar could effectively support MnFe₂O₄, which displayed high dispersion on the surface of the biochar and possessed abundant functional groups and high surface area contributing to superior performance on Pb(ii) and Cd(ii) removal. Therein, MnFe₂O₄ with high magnetism is convenient for separating the magnetic BC/FM from an aqueous medium. Adsorption experiment results indicate that Pb(ii) and Cd(ii) removal by BC/FM was closely related to pH with the best value of pH 5.0, and the process reached equilibrium in 2 h. The adsorption process is well-described by the pseudo-second-order kinetic model and Sips (Freundlich–Langmuir) model. Thermodynamic studies suggest that the adsorption process is spontaneous and exothermic. The maximum experimental adsorption capacity of BC/FM is 154.94 and 127.83 mg g⁻¹ for Pb(ii) and Cd(ii), respectively, in single-solute system, which is higher than that of some of the other adsorbents of biochar or biochar-based composites. In bi-solute system, the preferential adsorption order of BC/FM for the two metals is Pb(ii) prior to Cd(ii). Finally, FTIR and XPS analysis verified that the main mechanism of Pb(ii) and Cd(ii) removal by BC/FM is by forming Pb/Cd–O or complexation of carboxyl and hydroxyl and ion exchange. Therefore, the prepared magnetic BC/FM composite, as an excellent adsorbent, exhibited potential applications for the removal of Pb(ii) and Cd(ii) from wastewater.

In this study, a novel magnetic biochar-MnFe₂O₄ nanocomposite (BC/FM) was prepared using low-cost corn straw and MnFe₂O₄ by sol–gel/pyrolyzing route using egg white, which has abundant functional groups (–NH₂ and –COOH).