Complex Ions Research Articles

Synthesis, crystal structure, Hirshfeld surface analysis, DFT studies and biological evaluation of bis(acetonitrile)bromido(η6-1-isopropyl-4-methylbenzene)osmium(II) hexafluoroantimonate

The complex bis(acetonitrile)bromido(η6-1-isopropyl-4-methylbenzene)osmium(II) hexafluoroantimonate, [OsBr(C10H14)(CH3CN)2]SbF6 (1) crystallizes as a triclinic system in space group P1 (no. 2), consisting of two cationic osmium(II) complex ions and two anionic hexafluoroantimonate counterions in each cell. Density Functional Theory (DFT) calculations were performed at the B3LYP/LanL2DZ and B3LYP/Def2 − SVP/Def2 − TZVP levels of theory. Reactivity descriptors and charge transfer properties were computed using frontier molecular orbital analysis. The DFT-optimized model systems from both basis sets were comparable to the experimentally determined X-ray diffraction results. Hirshfeld surface analysis shows significant non-covalent interactions including hydrogen bonds and halogen interactions. The MTT technique was utilized to conduct an in vitro cytotoxicity assay of 1 against cancerous cell lines (MCF-7 and A549) and normal cells (HEK293). Complex 1 is potent towards cancer cells as evidenced by the IC50 values of 5.02 ± 0.05 µM for MCF-7 cells and 13.36 ± 0.04 µM for A549 cells. Complex 1 demonstrated lower toxicity to normal cells with an IC50 value of 26.76 ± 0.08 µM for the HEK293 cell line compared to the doxorubicin standard with an IC50 value of 1.2 ± 0.1 µM.

Synthesis of cadmium(II) complexes with polyamines: Crystal structure, theoretical calculation, photocatalytic, DNA interaction and biological studies

Three cadmium(II) complexes of N-(2-aminoethyl)-1, 2-ethanediamine (DETA) (1), N-(3-aminopropyl)-1, 3-propanediamine (DPTA) (2) and N,N'-(ethane-1,2-diyl)bis(propane-1,3-diamine) (DPETA) (3) have been synthesized and characterized by single crystal X-ray crystallography, UV–visible spectroscopy, IR and conductivity measurements. Complexes 1 and 3 show octahedral geometry while complex 2 show five coordinated square pyramidal geometry. Two molecules of DETA ligand are coordinated to the Cd(II) ion in complex 1. But one molecule each of DPTA and DPETA ligands and two bromide ions are coordinated to the Cd(II) ions to form square pyramidal (2) and octahedral structure (3). DFT results show that complex 3 is the most favoured complex thermodynamically while complex 1 is the least. The complexes exhibit good photocatalytic activity with reference to the intensity of organic dye methylene blue. The complexes were investigated for DNA interaction by absorption and fluorescence spectroscopy suggesting both hypochromism (internal contact or intercalative interaction) and hyperchromism (external contact or electrostatic binding). The cadmium (II) complexes show growth inhibitory activity against four pathogenic bacteria, two gram +ve, viz., Staphyloccus aureus, Bacillus subtilis and two gram –ve, viz., Escherichia coli, Salmonella typhi. Albumin denaturation assay and Heat Induced Haemolysis were studied for the complexes for anti-inflammatory activity.

Mineralization and stabilization of toxic Pb2+ ions using CMC loaded S/P co-doped biochar composite

Creating more stable chemical precipitates containing lead using biochar composite represents a significant and promising strategy for the treatment of lead contamination. Biochar, a porous and carbonaceous material, was fabricated by pyrolyzing plant biomasses (i.e., soybean straw) under anoxic conditions. In this research, a high capacity of adsorbent called carboxymethyl cellulose-loaded sulfur-phosphorus co-doped biochar composite was prepared, and the optimal lead adsorption parameters and mechanism were also investigated. The experimental results showed that CMC@SP2BC exhibited excellent Pb2+ removal capacity, reaching 829.3 mg/g maximum adsorption under optimum conditions (dosage 0.5 g/L, temperature 308 K, initial pH 5, initial lead concentration 2000 mg/L), which was in agreement with the Langmuir and second-order kinetic models. Moreover, the sequential extraction results indicated that the predominant passivation mechanism for Pb was chemical precipitation, followed by ion exchange, complexation, and physical adsorption. In addition, structural characterization revealed that the passivated lead was mainly in the form of minerals such as PbSO4, Pb3(PO4)2, Pb5(PO4)3OH, and Pb5(PO4)3Cl, which was also further confirmed by PHREEQC model simulation at different pH value and Pb2+ concentrations. Finally, Pb2+ was effectively removed from actual ground water by CMC@SP2BC to achieve Class I and Class II ground water standard. The current work offers an efficient solution for immobilizing Pb2+, which has enormous promise for stabilizing heavy metals.

Novel MOF(Zr)–on-MOF(Ce/La) adsorbent for efficient fluoride and phosphate removal

A one-pot method with formic acid regulation was adopted to fabricate a novel MOF(Zr)–on-MOF(Ce/La) adsorbent for fluoride and phosphate removal. Compared to traditional adsorbents, MOF(Zr)–on-MOF(Ce/La) boasted abundant active sites and a wide application range, with adsorption capacities of 173.2 and 92.85 mg g−1 for fluoride and phosphate, respectively. Comprehensive characterization techniques like SEM-EDS, BET, XRD, FTIR, and TGA were employed to analyze the material’s properties. Adsorption experiments investigated multiple effect factors. BET analysis disclosed a specific surface area of 332 m2 g−1, mainly composed of micropores and mesopores. The adsorbent showed rapid adsorption rates for both ions, with low reliance on adsorption time. The adsorption process was exothermic and spontaneous, favored by higher temperatures. Kinetic and thermodynamic studies favored the pseudo-second-order kinetic and Langmuir models, suggesting monolayer chemical adsorption. Through combined analyses including XPS, XRD, and studies on kinetics and thermodynamics, the fluoride removal mechanism involved electrostatic interaction and ion exchange, while phosphate removal encompassed ion exchange, electrostatic interactions, and complexation. Field wastewater experiments met Chinese standards, and recycling experiments revealed sustained removal efficiencies of 90.20 % for fluoride and 87.27 % for phosphate after two regeneration cycles, highlighting the significant potential of this approach in alleviating fluoride and phosphorus pollution.

Synthesis of biobased Phosphorus-Nitrogen-Silicon ceramizable flame retardant and its flame retardancy effects on EPS

The rising interest in eco-friendly flame retardants marks a notable trend in the industry. However, the challenge remains that most flame retardants, while achieving high flame retardant properties, struggle to balance environmental sustainability and resource utilization. This work delves into the green synthesis and mechanism of action of ceramizable flame retardants. Using phytic acid (PA) and urea (U) as raw materials, ionic complexation assembly in water, employing polydopamine (PDA) as an adhesive, to develop an environmentally friendly, bio-based synergistic flame retardant (PAU) is conducted. Building upon this groundwork, the addition of the ceramic filler kaolin (KL) and the fluxing agent sodium carbonate (Na2CO3) physically modifies the PAU, resulting in a novel eco-friendly, bio-based, ceramifiable flame retardant (PAUK). Employing the prepared PAUK through an effective surface coating technique, a lightweight and scratch-resistant flame-retardant expanded polystyrene insulation board (EPS-PAUK) is created. The best EPS-PAUK composite in our study exhibits an oxygen index of 52.5, achieves a V-0 UL-94 rating, and features excellent smoke suppression and compression strength up to 67.8 kPa, while nearly maintaining the lightweight characteristics of the EPS insulation boards. This bio-based, ceramifiable flame retardant system offers a new approach for producing lightweight, highly efficient flame-retardant and high-performance polymers.

Synthesis, crystal Structure, theoretical calculation and luminescence properties of Cu(Ⅱ), Co(Ⅱ), Ni(Ⅱ) and Zn(Ⅱ) quinolinyl benzimidazole complexes with multiple coordination number induced by proton

The innovative ligand H2L, featuring a benzimidazole structure substituted with 8-hydroxyquinoline and equipped with N,O donor sites, underwent successful synthesis and meticulous characterization. Notably, this ligand was exclusively synthesized through catalysis under protonated conditions, accompanied by an in-depth exploration of the catalytic mechanism. Employing single-crystal X-ray diffraction, we acquired and authenticated four distinct asymmetric double-decker sandwich mononuclear transition metal complexes: [Cu(HL)2]·2H2O, [Co(HL)2]·CH3OH, [Ni(HL)2] and [Zn(HL)2]·CH2Cl2. Among these, complex 1 revealed an intriguing five-coordinate Cu(II) center adopting a distorted square pyramidal geometry, whereas the central metal ions in complexes 2–4 exhibited a six-coordinate configuration, characterized by a distorted octahedral geometry. Noteworthy is the observation that the dihedral angles within the crystal structures of complexes 2–4 approached approximately 90° to a significant extent. To delve deeper into the electronic properties and transitions, meticulous DFT and TD-DFT calculations were performed on both the ligand H2L and complexes 1–4. Furthermore, a comprehensive investigation into the luminescence properties of both H2L and its complexes was conducted, revealing a pronounced luminescence quenching effect in the complexes compared to the ligand. Through thorough analysis utilizing Hirshfeld surface examination and IRI analysis, various weak intermolecular interactions within the system were elucidated.

Electronic Properties of [Ru(NH3)6][M(CN)6] Double-Complex Crystals and Their Thermal Decomposition to Prussian Blue Analogs

The complex ions, [Ru(NH3)6]2+/3+ and [Fe(CN)6]3-/4-, are well known redox couples exhibiting fast interfacial and homogeneous electron transfer rates in aqueous solution. Here we show that when mixed together, they form insoluble double-complex Ax[Ru(NH3)6][Fe(CN)6] crystals with rhombohedral symmetry, where A is a cationic species and 0≤x≤2. The analogous interactions of [Ru(NH3)6]2+/3+ with [Ru(CN)6]3-/4- produces Ax[Ru(NH3)6][Fe(CN)6] crystals. Electrical measurements of these single crystals exhibit ohmic current-voltage responses, with corresponding conductivities on the order of 0.1 mS/m. We propose a solid-state charge transport mechanism based on Marcus theory for homogeneous outer-sphere electron transfer.Thermal decomposition at mild temperatures removes ammine ligands and transforms these crystals into nanopolycrystalline Prussian blue analogs (PBAs) that retain the macroscopic geometry of the double-complex crystals but adopt the familiar highly defected porous crystal structure and intervalence charge transfer characteristics of PBAs.

Thiourea-Induced Cocrystallization of Mixed-Halide Perovskite Thin Films for High-Performance Pure Blue Perovskite Light Emitting Diodes

Metal halide perovskite light-emitting diodes (PeLEDs) are gaining significant attention towards next-generation display materials owing to their advantageous properties, including color tunability, exceptionally narrow bandwidth, and high luminescence. Recent studies have successfully achieved over 20% external quantum efficiencies (EQE) in green and red PeLEDs. However, the blue PeLEDs lag far behind those of green or red PeLEDs because unstable phase stability in mixed halide perovskite thin films under high turn-on voltage (Von). In specific, the blue emission usually possesses halide ions with smaller ionic radius (Cl- or Br-), which easily migrates under high operative bias generating significant halogen vacancies and phase-transformation. In this context, we suggest thiourea as a promising additive for stabilizing defective perovskite thin films. Thiourea is a well-known hydrogen bond donor to halogens, which allows potential coordination complex of thiourea-halide ions to encompass well-dispersed mixed halides in co-crystallized perovskite lattices. In addition, the strong coordination of the C=S···Pb2+ was also demonstrated the thiourea-incorporated perovskite films, which effectively passivated undercoordinated Pb2+ antisites. Consequently, the thiourea-incorporated perovskite films exhibited stable deep-blue emission within 460 nm, demonstrating excellent luminance and quantum efficiency in pure blue PeLEDs. Moreover, the addition of thiourea achieved decreased Von and excellent spectral stability of pure blue PeLEDs at high applied bias, leading to significant advancements in pure blue perovskite display technology.

(Invited) Advances in Modeling Ion Transport in Micropores and Charging Behavior of Porous Electrodes: Merging Molecular Insights with Machine Learning for Energy Storage

Electric double layer (EDL) charging is a complex process coupling electro-osmotic flow, surface reactions, and ion concentration gradients. The charging dynamics depends on the properties of electrolyte and electrode structure, as well as initial and boundary conditions. While molecular dynamics (MD) simulations and first-principles calculations can encompass all factors, their computational demands are substantial even for simple electrochemical systems such as electrolytes near a planar surface. This presentation explores recent advancements in modeling ion transport in micropores and the charging behavior of porous electrodes with different theoretical and simulation methods. Illustrative examples will be discussed on the integration of molecular modeling and machine-learning techniques to enhance our understanding of complex electrochemical processes and improve the design of energy storage devices.

(Invited) Experimentally Measuring the Role of Ion-Phonon and Ion-Electron Correlations in Solid-State Li Ion Conductors

In superionic conductors, ion hopping involves a complex interplay of ion-phonon, ion-electron, and ion-ion correlations that is challenging to measure experimentally. In this presentation, we present a new experimental technique that can directly measure ultrafast ion hopping on its inherent picosecond and longer timescale. The technique works by measuring the time-resolved perturbation to a GHz impedance signal when potential ion-coupling interactions are driven with UV to THz irradiation. High-bandwidth, real-time electronics allow synchronization of the impedance measurement to ultrafast laser pulses for varying carrier frequencies. The result of the measurement is the relative strength of different correlations in the many-body ion hopping Hamiltonian. We demonstrate the technique on Li0.5La0.5TiO3 (LLTO) and single crystalline Li7La3Zr2O12 (LLZO), both solid-state Li+ conductors. The ultrafast laser-driven impedance measurements reveal that the dominant ion hopping mechanism in LLTO is through a coupled phonon-ion THz rocking mode. Although this higher frequency mode is less than one-quarter of the overall phonon density of states, it leads to the majority of ion hops as compared to other optical and acoustic phonon modes. Metastable states lasting tens of minutes were also measured for ion-electron perturbations. Further work on extending the technique to measure ion-ion correlations is currently underway. In general, the new technique applies to any complex ion conducting system such as polymers, fuel cells, supercapacitors, and membranes.

Detection of Pb(II) and Cr(III) Using Dy(III) Ion with Pyrazoline Derivatives Ligand

Exposure to heavy metal ions Pb2+ and Cr3+ in Indonesia is getting more attention, especially in various industries and transportation. The sensor complex compound Dy3+ with fluorescence-based pyrazoline-derived ligands (fluorosensor) has the potential to detect heavy metal ions Pb2+ and Cr2+. This research was initiated by synthesizing the pyrazoline derivative ligand and then reacting it with Dy3+ metal ion. The formed Dy3+ complex compounds was then characterized using spectroscopic methods. The results of scanning complex compounds using a UV-Vis spectrophotometer obtained two maximum wavelengths namely at 255 and 359 nm are indicating the presence of a transition type n→π* and π→π*. The results of fluorescence spectrophotometer analysis obtained maximum fluorescence intensity of Dy3+ complex compound was in the wavelength at 370 nm with fluorescence intensity of 4273 a.u. Fluorescence based sensor studies of the Dy complex when Pb2+ and Cr3+ metal ions were added showed changes in fluorescence intensity so that the fluorosensor type was obtained for the Dy3+ metal ion complex compound with Pb2+ and Cr3+, namely "turn-on-off" and "turn-off" respectively.

Spectral Hole-Burning Studies of a Mononuclear Eu(III) Complex Reveal Narrow Optical Linewidths of the 5D0→7F0 Transition and Seconds Long Nuclear Spin Lifetimes.

Coordination complexes of rare-earth ions (REI) show optical transitions with narrow linewidths enabling the creation of coherent light-matter interfaces for quantum information processing (QIP) applications. Among the REI-based complexes, Eu(III) complexes showing the 5D0→7F0 transition are of interest for QIP applications due to the narrow linewidths associated with the transition. Herein, we report on the synthesis, structure, and optical properties of a novel Eu(III) complex and its Gd(III) analogue composed of 2,9-bis(pyrazol-1-yl)-1,10-phenanthroline (dpphen) and three nitrate (NO3) ligands. The Eu(III) complex-[Eu(dpphen)(NO3)3]-showed sensitized metal-centred emission (5D0→7FJ; J=0,1,2,3, 4, 5, or 6) in the visible region, upon irradiation of the ligand-centred band at 369 nm, with the 5D0→7F0 transition centred at 580.9 nm. Spectral hole-burning (SHB) studies of the complex with stoichiometric Eu(III) concentration revealed a narrow homogeneous linewidth (Γh) of 1.55 MHz corresponding to a 0.205 μs long optical coherence lifetime (T2opt). Remarkably, long nuclear spin lifetimes (T1spin) of up to 41 s have been observed for the complex. The narrow optical linewidths and long T1spin lifetimes obtained for the Eu(III) complex showcase the utility of Eu(III) complexes as tuneable, following molecular engineering principles, coherent light-matter interfaces for QIP applications.

Bioinspired Self-Growing Layered Hydrogel Enabled by Catechol Chemistry-Mediated Interfacial Catalytic System.

Tissue-inspired layered structural hydrogel has attracted increasing attention in artificial muscle, wound healing, wearable electronics, and soft robots. Despite numerous efforts being devoted to developing various layered hydrogels, the rapid and efficient preparation of layered hydrogels remains challenging. Herein, inspired by the self-growth concept of living organisms, an interfacial catalytic self-growth strategy based on catechol chemistry-mediated self-catalytic system of preparing layered hydrogels is demonstrated. Typically, the tannic acid-metal ion (e.g., TA-Fe3+) complex embedded in the hydrogel substrate would catalytically trigger rapid solid-liquid interfacial polymerization to grow the hydrogel layer without bulk solution polymerization. The self-growth process can be finely controlled by changing the growth time, the molar ratio of Fe3+/TA, and so on. The strategy is applicable to prepare various layered hydrogels as well as complex layered hydrogel patterns, allowing the customization of the physicochemical properties of the hydrogel. In addition, the self-adhesive layered hydrogel was prepared and can be utilized as a wearable strain sensor to monitor physiological activities and human motions. The demonstrated interfacial catalytic self-growth strategy will provide a route to design and fabricate layered hydrogel materials.

Eu3+-functionalized covalent organic framework for ratiometric fluorescence detection and adsorption of tetracycline and information steganography.

Functional materials with organic/inorganic composites as the main matrix and rare earth ion complexes as the guest have shown a very broad application prospect for antibiotic sensors. However, Eu3+-complex often relies on a single fluorescence response signal, which is susceptible to changes in the detection environment and cannot simultaneously detect and remove tetracycline (TC). Herein, green fluorescent covalent two-dimensionalorganic framework (COF-TD) is synthesized, followed by modification of Eu3+ to synthesize COF-TD@Eu3+. In the ratiometric sensor, Eu3+ serves as the recognition site and specific response probe for TC, while COF-TD is the fluorescence reference and carrier for Eu3+. Due to the antenna effect, TC enhances the red fluorescence of Eu3+, while the green fluorescence of COF-TD remainsalmost stable. Based on the change of fluorescence intensity and fluorescence color from green to red, the efficient ratiometric sensing can be finished in 1min. The developed method shows high sensitivitywith a detection limit of 0.3μM and highselectivity to TC which makes the methodapplicableto detect TC in traditional Chinese medicine preparations. In addition, due to the high specific surface area of COFs and specific adsorption sites, COF-TD@Eu3+ also shows good performance for TC removal. The findings show that the maximum adsorption capacity is 137.3mgg-1 and the adsorption equilibrium is reached in 30min. Smartphone assisted COF-TD@Eu3+ for both ratiometric fluorescence detection and detecting the absorption ofTC is proposed for the first time. The molecular cryptosteganography that transforms the selective response of COF-TD@Eu3+ to binary strings is anticipated to advance utilization of nanomaterials in logic sensing and information safety.

Synthesis, X-ray Crystallography, Spectroscopic Characterizations, Density Functional Theory, and Hirshfeld Surface Analyses of a Novel (Carbonato) Picket Fence Iron(III) Complex.

An Fe(III)-carbonato six-coordinate picket fence porphyrin complex with the formula [K(2,2,2-crypt)][FeIII(TpivPP)(CO3)]·C6H5Cl·3H2O (I) has been synthesized and characterized by UV-Vis and FT-IR spectra. The structure of (carbonato)(α,α,α,α-tetrakis(o-pivalamidophenyl)porphinato)ferrate(III) was also established by XRD. The iron atom is hexa-coordinated by the four nitrogen atoms of the pyrrol rings and the two oxygen atoms of the CO32- group. Complex I, characterized as a ferric high-spin complex (S = 5/2), presented higher Fe-Np (2.105(6) Å) and Fe-PC (0.654(2) Å) distances. Both X-ray molecular structure and Hirshfeld surface analysis results show that the crystal packing of I is made by C-H⋯O and C-H⋯Cg weak intermolecular hydrogen interactions involving neighboring [FeIII(TpivPP)(CO3)]- ion complexes. Computational studies were carried out at DFT/B3LYP-D3/LanL2DZ to investigate the HOMO and LUMO molecular frontier orbitals and the reactivity within the studied compound. The stability of compound I was investigated by analyzing both intra- and inter-molecular interactions using the 2D and 3DHirshfeld surface (HS) analyses. Additionally, the frontier molecular orbital (FMO) calculations and the molecular electronic potential (MEP) analyses were conducted to determine the electron localizations, electrophilic, and nucleophilic regions, as well as charge transfer (ECT) within the studied system.

Surface Ammonium Ions Assisted Decoration of Monodisperse Cobalt Nanoparticles on Molybdenum Oxide Films as Efficient Electrocatalysts for Hydrogen Evolution Reaction.

The high expense associated with electrocatalysts poses a challenge to the advancement of a hydrogen-based energy economy. The utilization of nonprecious metal-based electrocatalysts that are easily prepared and cost-effective is imperative for the future sustainability of a hydrogen society. The semiconductive MoO3-x has been identified as a promising nonprecious electrocatalyst for the hydrogen evolution reaction (HER). Nevertheless, enhancing its relatively low electrocatalytic activity toward HER remains a top priority. This study illustrates the manipulation of surface ammonium ions (NH4+) to produce uniform and distinct cobalt nanoparticles (Co NPs) on active MoO3-x supports, resulting in a more effective heterostructured composite electrocatalyst for HER. The presence of NH4+ ions in the MoO3-x film was extensively examined using infrared spectroscopy, X-ray photoelectron spectroscopy, and UV-visible colorimetric techniques. Additionally, the firmly attached NH4+ ions were employed as binding sites to precipitate Co-containing complex ions. Due to the monolayer-like adsorption of NH4+ ions, only a small quantity of Co precipitate was formed, which was subsequently electrochemically transformed into Co atoms that diffused and created well-separated uniform metallic Co nanoparticles (with an average size of less than 10 nm) on the MoO3-x film. The resulting heterostructure displays a 4.5-fold increase in current density for HER compared to the MoO3-x electrocatalyst through electrochemical assessments. The enhanced catalytic activity was ascribed to the optimized adsorption/desorption of the species involved in water reduction at the heterointerfaces and improved charge transfer rates. These nanoheterostructures hold great promise for a variety of applications in heterogeneous electrocatalysis, while the novel approach could potentially direct the creation of more heterostructures.

Pyridine-2-thione and pyrimidine-2-thione derivatives of silver(I): Synthesis and structures of unusual dinuclear and polynuclear coordination compounds, [Ag2Cl2(pytH)2(dppm)], [Ag2Br2(pymtH)(PPh3)3] and {AgCl(pytH)2}n

The chemical reactivity of heterocyclic-2-thiones towards silver halides in presence of donor ligands, such as tertiary phosphines, is poorly explored relative to that with other anions (such as NO3, OAc etc). It was observed in a research report that chemical reactivity of silver(I) chloride/bromide with pyridine-2-thione (pytH) in the presence of a tertiary phosphine, was different in terms of nuclearity. In this manuscript some unusual products from reactions of silver(I) halides with pyridine-2-thione (pytH)/pyrimidine-2-thione (pymtH) in presence of tertiary phosphines are reported. In one case, reaction of a bis(diphenylphosphino)methane (dppm) with silver(I) chloride yielded a crystalline product of stoichiometry, [Ag2Cl2)(pytH)2(µ-P,P-Ph2PCH2PPh2)] 1. Silver(I) chloride with pytH in the presence of tri-p-tolylphosphine ligand did not form the expected, AgCl(pytH)(p-tolyl3P)2 complex, rather it has formed a compound of stoichiometry, {AgCl(pytH)2} 2. The crystal structures of these compounds revealed the formation of a triply bridged di-nuclear compound, [(κ1Cl)Ag(µ-Cl)(µ-P,P-Ph2PCH2PPh2)(µ-S-pytH)Ag(κ1S-pytH)] 1, and a polymeric product, {AgCl(κ1S-pytH)(µ-S-pytH)-}n,2, respectively. The chemical reactivity of pyrimidine-2-thione (pymtH) is found to be different. A reaction of silver(I) bromide with PPh3 and pymtH, yielded a bromo-bridged unsymmetrical dinuclear compound, [(PPh3)2Ag(µ-Br)2Ag(PPh3)(κ1S-pymtH)] 3. Reaction of AgNO3 with pytH and PPh3 in the presence of Et3N base did not yield the expected [Ag(κ1S-pyt)(PPh3)3] compound, rather it formed the ionic complex, [Ag(κ1S-pytH)(PPh3)3](NO3)·CH3OH·0.25H2O 4. In compound 1, there is a short Ag···Ag distance of 3.1127(3) Å, suggesting possibility of argentophillic interaction.

Porous red mud ceramsite for aquatic phosphorus removal: Application in constructed wetlands

Red mud (RM) and spent oyster mushroom substrate (SOMS), by-products of industrial and agricultural production, can be recycled for polluted freshwater purification, bringing about a win-win situation. In this study, unacidified RM and RM acidified with oxalic acid (O-RM) and hydrochloric acid (H-RM), respectively, were mixed with SOMS to produce a porous ceramsite as a potential constructed wetlands (CWs) substrate. The results showed that the O-RM, H-RM, and RM ceramsites displayed fine compressive strengths of 7.75 ± 1.14, 8.40 ± 1.30, and 8.84 ± 0.69 MPa after calcining at 950 °C for 30 min, respectively. The phosphorus adsorption capacities of H-RM, O-RM, and RM ceramsite at a solid-liquid ratio of 25 g/L were 1.18 mg/g, 0.88 mg/g, and 1.06 mg/g, respectively. Toxicity release experiments showed that the ceramsites did not cause secondary environmental pollution, except for arsenic (ranging from 0.210 to 0.238 mg/L). The H-RM ceramsite was tested in a tidal flow-vertical flow CW (TF-VFCW) with Iris pseudacorus L. and Canna indica L plants. In the TF-VFCW, the average chemical oxygen demand (COD), ammonia nitrogen (NH4+-N), total nitrogen (TN), and total phosphorus (TP) removal rates were 81.01, 90.25, 66.90, and 77.32 %, respectively. Plant growth had less impact on COD and NH4-N removal but had greater limited TN and TP removal. Scanning electron microscopy, Fourier-transform infrared spectroscopy, and X-ray diffraction analysis confirmed that acid pretreatment and the incorporation of SOMS significantly increased the surface and interior porous structures of the ceramsite and enhanced phosphate adsorption by the polyhydroxyl aluminum-iron complex ions. Bacteroides and Campylobacter used the energy produced during polyhydroxyalkanoic acid (PHA) catabolism to absorb phosphorus. Therefore, the synergistic effect of the substrate, plants, and microorganisms achieved the removal of phosphorus from CWs and offered effective and environmentally friendly recycling of RM and SOMS.

U(VI) sorption by CTAB/Bent–MOF-74 from various carbonate solutions

CTAB/Bent-MOF-74 was synthesized via hydrothermal method to investigate its U(VI) sorption in carbonate solutions. Generally, CTAB/Bent-MOF-74 (∼87.6 mg·g−1) showed better sorption capacity than CTAB/Bent-MOF-71 (∼64.2 mg·g−1) and CTAB/Bent-CS-35 (∼81.4 mg·g−1) in U(VI)-Cl coexist carbonate solutions when pH = 8.0, [NaHCO3] =2 mmol·L−1, [NaCl] =0.1 mol·L−1 and [U(VI)] =50 mg L−1. The competitive sorption between HCO3−/CO32−, OH−, halide ions and U(VI) complexes ions as well as the weakened electrostatic attraction decreased the composite's uranium sorption efficiency and capacity at high pHinitial, NaHCO3, phosphate, Ca/Mg and halide ions concentrations. The pseudo-second-order kinetics and Langmuir models indicated a monolayer homogeneous chemisorption process. Besides, 0.1mol·L−1 HCl shows the highest desorption efficiency among the selected desorbents, and the sorption rate is still high even after four times of desorption. In particular, the decreasing inhibitory capacity of the halide ions was on the order of I−, F−, Br−, Cl−. Characterization analyzes confirmed the good structural stability and Br anion exchange as well as the -OH/-COOH coordination and electrostatic attraction, which could be the predominant sorption mechanisms of U(VI) by CTAB/Bent-MOF-74. The results provided theoretical references for understanding the uranium sorption in natural uranium-containing water and designing potential uranium-extracting materials.

In-situ complexation of Cu(II) with polyethyleneimine (PEI) triggers the enhanced formation of halonitromethanes, dichloroacetonitrile, and dichloroacetamide during UV/chlorine disinfection: Cu(I) contribution and Cl· sustainable production

The complexation of copper ions (Cu(II)) with coexisting organic ligands (e.g. polyethyleneimine (PEI)) in water may pose a new threat to water quality. This study revealed that the maxima concentrations of HNMs, DCAN, and DCAcAm from Cu(II)-PEI complex during UV/chlorine disinfection were 1.54, 2.00, and 1.25 times higher than those from PEI, and the maxima concentrations of HNMs, DCAN, and DCAcAm from Cu(II)-PEI complex during chlorination disinfection were 1.22, 1.31, and 1.10 times higher than those from PEI. Meanwhile, specific Cu(II) concentration (0.25 ∼ 3.0 mg L−1) and alkaline pH were more favorable for forming HNMs, DCAN, and DCAcAm during UV/chlorine disinfection, which were highly dependent on the involvement of HO· and Cl·. Cu(II)-PEI, an in-situ formed stable complex that permitted an efficient interconversion cycle of Cu(II)/Cu(I) via concurrent metal-to-ligand charge transfer and ligand-to-metal charge transfer. The analysis and comparison of extensive products provided solid evidence for the primary role of Cu(I) and the enhanced production of Cl· in increasing HNMs, DCAN, and DCAcAm productions, rather than only Cu(II) catalysis similar to that during chlorination. The new findings broaden the knowledge of the influence of in-situ formed Cu(II)-organic complexes on forming HNMs, DCAN, and DCAcAm during UV/chlorine disinfection.