Charged Complexes Research Articles

Synthesis and structure of Americium(III) diglycolate oxalate Trihydrate, Am(ODA)(C2O4)(H2O)3

Improving f-element separations is important for actinide(III) (An3+) and lanthanide(III) (Ln3+) based technologies. Unfortunately, An3+ and Ln3+ ions are difficult to separate from one another because they have similar chemical characteristics. One successful separation method utilizes anion exchange chromatography. This approach exploits differences in An3+ and Ln3+ Lewis acidities and their varying abilities to attract anionic complexing agents, like oxalates (C2O42–) and diglycolates (ODA2–). The resulting negatively charged complexes are then separated using an anion exchange resin. To better understand how this anion exchange separation works, we reacted Am3+(aq) (aq designates Am3+ dissolved in water) with the anion exchange complexing agents (H2C2O4 and H2ODA). The resulting Am(ODA)(C2O4)(H2O)3 product was characterized using single crystal X-ray diffraction and UV-Vis-NIR spectroscopy. The Am(ODA)(C2O4)(H2O)3 structure was similar to that established previously for Ln3+ analogues, namely Ln(ODA)(C2O4)(H2O)x. These compounds were all isomorphous, had bridging C2O42– and ODA2– ligands, and crystallized as 2-dimensional extended solids. In addition, the Am3+–O bond distances could be predicted based on relative differences in Am3+ and Ln3+ 9-coordinate metal ionic radii. Overall, isolation of Am(ODA)(C2O4)(H2O)3 showcased similarities in complexation and crystallization chemistry for Am3+ and Ln3+.

High-order exciton complexes induced by an interlayer carrier transfer in 2D van der Waals heterostructures.

High-order correlated excitonic states, such as biexciton, charged biexciton, and polaron, hold a promising platform in contemporary quantum and nonlinear optics due to their large Bohr radii and thus strong nonlinear interactions. The recently found 2D TMDs further give such excitonic states additional valley properties, with bound state of excitons in opposite valleys in momentum spaces. Despite great efforts that have been made on emission properties of excitonic states, their absorption features, especially the ultrafast absorption dynamics, are rarely reported. Here, we reported the enhanced optical absorption of the high-order charged-excitonic states in monolayer WS2, including singlet, triplet, and semidark trions (3-particle state), and charged biexcitons (5-particle state), by utilizing the interlayer charge transfer-induced photo-doping effect in the graphene-WS2 heterostructure. Depending on recombination rates of doping electrons, absorption intensities of charged complexes exhibit ultrafast decay dynamics, with lifetimes of several picoseconds. Due to many-body interaction, both increasing pump intensity and lattice temperature can broaden these fine excitonic absorption peaks and even reverse the shape of the transient absorption spectrum.

Preparation, structural analysis, efficient photocatalytic degradation mechanism and pathway for p-nitrophenol of Ag-deposited Co-coordination polymer composites

This study addressed the problem of photogenerated charge complexation in coordination polymers (CPs), a considerable barrier to stable, high-performance photocatalysts, by hydrothermally preparing a novel cobalt coordination polymer, [Co(DDB)0.5(PTP)(DMA) (H2O)2]·H2O (Co-CP) using the mixed ligands 1,4-di(3,5-dicarboylphenoxy) benzene (H4DDB) and 4′-(4′′-pyridyl)-2,4′,6′,4′′-terpyridine (PTP). Theoretical calculations have demonstrated that the metal-to-ligand charge transfer (MLCT) in Co-CP is crucial in enhancing charge separation efficiency. Additionally, a silver-deposited composite (Ag@Co-CP) was synthesized through photoreduction. With 1.65wt% Ag, the Ag@Co-CP-2 composites exhibited optimal photocatalytic degradation of various organic pollutants, including nitroaromatic, rhodamine B, methylene blue, basic magenta, and methyl orange. Using charge-coupled devices, scanning electron microscopy, transmission electron microscopy, X-ray diffraction, fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, density functional theory, electron spin resonance measurements, and liquid chromatography-mass spectrometry, we extensively examined the morphology, structure, and photoelectric properties of the developed materials. Our exploration of the structural-activity relationship was supported by results from these structural and optoelectronic analyses. Free radical capture tests and analyses of electron spin resonance led us to pinpoint ·O2−, h+, and ·OH as significant contributors to the reaction system. Finally, we outlined the degradation process, reaction mechanism, and potential pathways. This study contributes to the critical task of designing interfaces between noble metals and semiconductors for improved photocatalytic performance.

Complexation of lanthanide ions with citric acid in aqueous solutions

The stability constants of triply charged lanthanide ions complexes with citric acid of 1:2 stoichiometry weremeasured by potentiometric titration in a wide pH range, and the relationship between the constants and the lanthanide type was analyzed. A mathematical model for the equilibrium in studied solutions was proposed.

Ag2O-Containing Biocidal Interpolyelectrolyte Complexes on Glass Surfaces-Adhesive Properties of the Coatings.

Biocidal coatings are of great interest to the healthcare system. In this work, the biocidal activity of coatings based on a complex biocide containing polymer and inorganic active antibacterial components was studied. Silver oxide was distributed in a matrix of a positively charged interpolyelectrolyte complex (IPEC) of polydiallyldimethylammonium chloride (PDADMAC) and sodium polystyrene sulfonate (PSS) using ultrasonic dispersion, forming nanoparticles with an average size of 5-6 nm. The formed nanoparticles in the matrix are not subject to agglomeration and changes in morphology during storage. It was found that the inclusion of silver oxide in a positively charged IPEC allows a more than 4-fold increase in the effectiveness of the complex biocide against E. coli K12 in comparison with the biocidal effect of PDADMAC and IPEC. Polycation, IPEC, and the IPEC/Ag2O ternary complex form coatings on the glass surface due to electrostatic adsorption. Adhesive and cohesive forces in the resulting coatings were studied with micron-scale coatings using dynamometry. It was found that the stability of the coating is determined primarily by adhesive interactions. At the macro level, it is not possible to reliably identify the role of IPEC formation in adhesion. On the other hand, use of the optical tweezers method makes it possible to analyze macromolecules at the submicron scale and to evaluate the multiple increase in adhesive forces when forming a coating from IPEC compared to coatings from PDADMAC. Thus, the application of ternary IPEC/Ag2O complexes makes it possible to obtain coatings with increased antibacterial action and improved adhesive characteristics.

Optimized condition for pei-based transient transfection of lifeact-gfp/nls-mcherry expressing plasmid used as cell barcode for syncytia live cell imaging

The transfection efficiency positively affects the successful plasmid DNA transfer into cells, with the highlight on the amount of plasmid DNA and its ratio to the transfection reagent. Polyethyleneimine (PEI) is a cost-effective transfection reagent that facilitates DNA transfer by forming positively charged DNA complexes. It allows DNA to interact with negatively charged cell surfaces and enter the cells by endocytosis. In this study, we optimized the condition for transient transfection of life act-GFP/NLS-mCherry-expressing plasmid in BHK-21 and 293T cells using PEI. This plasmid is helpful as a biosensor of the cytoskeleton and nucleus that enables live imaging observation using a fluorescence microscope, for instance, in the observation of syncytium. Here, we optimized two independent variables: the amount of DNA (0.5 and 1 µg) and the ratio of DNA-PEI (1:3 and 1:4). GFP and mCherry expressions were observed at 24, 48, and 72 h post-transfection. As a result, transfection efficiency achieved by using PEI in 293T cells is higher than in BHK-21 cells, which are ~90% and ~50%, respectively. Moreover, amongst four different transfection conditions, in both cell lines, 1 µg of plasmid DNA with a 1:3 DNA-PEI ratio yields the most efficiency with the least amount of toxicity. We used this condition for the syncytia observation in 293T cells as a model of the cell-to-cell transmission of SARS-CoV-2. Syncytia formation was successfully observed by detecting the giant cells expressing GFP/mCherry with multiple nuclei.

Ag nanorod@PEI-Ag nanohybrid as an excellent signal label for sensitive and rapid detection of serum HER2

The accurate detection of Human epidermal growth factor receptor-2 (HER2) as a critical breast cancer biomarker can be essential for the early selection of therapeutic approaches. HER2 is a prominent component of a signaling network. Overexpression of the HER2 protein due to amplification of its gene leads to the development of an aggressive subtype of breast cancer. Patients with tumors that overexpress HER2 are eligible for treatment that significantly reduces mortality rates. Herein, we present a fast and simple method for detecting serum HER2. A new electrochemical label has been developed using charged Ag nanorod@ polyethylenimine-Ag (Ag NR@ PEI-Ag) nanohybrid. The synthesized Ag NR@PEI-Ag nanohybrid simultaneously has the electroactive property of silver and the large surface area of the PEI, which results in the enhancement of the detection signal. So, using Ag NR@PEI-Ag nanohybrid as the electrochemical label, a simple, fast, and sensitive electrochemical biosensor was designed to detect HER2. This way, after immobilizing HER2 aptamer on the Au electrode surface, HER2 or human serum was exposed to the aptamer. Then, the positively charged Ag NR@PEI-Ag nanohybrid was adsorbed onto the negatively charged aptamer-HER2 complex, and the current that was produced due to the Ag/AgCl reaction was measured as the electrochemical signal. The aptasensor shows a broad linear response from 10–12 to 10–7 g, a low detection limit (LOD) of 10 pg, and a total assay time of ~ 30 min.

High‐Performance Near‐Infrared Organic Photodetectors Enabled by Fabricating an Interdigital Heterojunction

AbstractNear‐infrared organic photodetectors (NIR‐OPDs) are of significant applications in optical communication, medical monitoring, and bioimaging, and have become a centerpiece of organic photodetector (OPD) research. To overcome the well‐known challenge of high dark current in NIR‐OPDs, researchers have investigated and introduced the sequential deposition method to prepare photosensitive layers of gradient heterojunction structure. However, this photosensitive layer suffers from the issue of insufficient exciton diffusion length, which in turn limits the photoresponse performance of devices. To address this issue, an interdigital heterojunction (IHJ) structure is designed, forming the adjustable large‐area bicontinuous phase, and constructing rich donor/acceptor interfaces and straightforward carrier transport channels. In this structure, the film shows enhanced crystallinity, which effectively reduces the trap density and suppresses the dark current. In addition, efficient exciton dissociation and charge extraction along with suppressed charge complexation promote the enhanced photoresponse of IHJ devices. Consequently, the IHJ NIR‐OPD achieves a high detectivity of 7.35 × 1013 Jones at 805 nm at −0.2 V, which is one of the highest values at 800–900 nm among reported NIR‐OPDs. Further, the IHJ devices are successfully applied to arterial pulse monitoring and transmission‐based bioimaging. This study provides new insights for realizing high‐performance NIP‐OPDs.

Site-Specific Polymerization-Induced Electrostatic Self-Assembly: Synthesis of Highly Charged Salt-Tolerant Polyion Complex Nanoreactors

Site-Specific Polymerization-Induced Electrostatic Self-Assembly: Synthesis of Highly Charged Salt-Tolerant Polyion Complex Nanoreactors

Rotational Transitions of COH+ and He: New Interaction Potential, Bound States, Scattering and Pressure Broadening Cross‐sections**

AbstractWe present new calculations of a metastable isomer of HCO+, i. e., COH+ in collision with He. The COH+ has been suggested as an alternative molecular hydrogen tracer, which makes it of great interest for astrophysical studies. COH+ was first observed in astronomical space towards SgrB2 with the observation of J=1→0, J=2→1 and J=3→2 lines. Calculations are based on new ab initio potential energy surfaces (PES) of charged complex COH+‐He using the CCSD(T) in conjunction with aug‐cc‐pVQZ basis set. The PES has a well depth of −836.5 cm−1 towards H‐end at the COH+‐He distance (R) of 2.9 Å in linear orientation. To test the new PES, the calculations of the bound‐state are carried out and pressure broadening cross‐sections of COH+ with He collisions are computed for kinetic energies up to 150 cm−1 using the accurate close‐coupling method. Further, the pressure broadening and shift coefficients have been calculated from the corresponding real and imaginary parts of cross‐sections for the first six rotational transitions. The data obtained is found to be in the same order as the HCO+‐He system. Further, the results of rate coefficients are compared with the reported COH+‐He and HCO+‐He data. The results generated by this study are believed to be useful for both laboratory and future astrophysical research.

Radiometal Complexes as Pharmacokinetic Modifiers: A Potent 68Ga-Labeled Gastrin-Releasing Peptide Receptor Antagonist Based on the Macrocyclic Metal Chelator NODIA-Me.

The gastrin-releasing peptide receptor (GRPr) is overexpressed in various cancer types including prostate and breast carcinomas, making it an attractive target for molecular imaging and therapy. In this work, we designed a novel GRPr antagonistic probe comprising metal chelator NODIA-Me. This 1,4,7-triazacyclononane-based chelator forms positively charged metal complexes due to its neutral methylimidazole arms. Because a positive charge at the N-terminus of GRPr conjugates is responsible for high receptor affinity as exemplified by the current gold standard DOTA-RM2, we investigated if a positively charged radiometal complex can be used as a pharmacokinetic modifier to also produce high-affinity GRPr conjugates. In this respect, the bioconjugate NODIA-Me-Ahx-JMV594 was prepared by a combination of solid-phase peptide synthesis and solution-based reactions in a 94% yield. Radiolabeling provided the 68Ga-labeled conjugate in radiochemical yields of >95% and radiochemical purities of >98% with mean molar activities of Am ∼17 MBq nmol-1. The competitive GRPr affinity of the metal-free and 69/71Ga-labeled conjugate was determined to be IC50 = 0.41 ± 0.06 and 1.45 ± 0.06 nM, respectively. The metal-free GRPr antagonist DOTA-RM2 and its corresponding 69/71Ga complex had IC50 values of 1.42 ± 0.07 and 0.98 ± 0.19 nM, respectively. Small-animal PET imaging of mice bearing GRPr(+) PC-3 tumors revealed high radioactivity accumulation in the tumors and in the pancreas as an organ with high levels of GRPr expression. These findings were corroborated by the corresponding ex vivo biodistribution data, in which the tumors and the pancreas exhibited the highest radioactivity accumulation. By coinjection of an excess of NODIA-Me-Ahx-JMV594, uptake in the tumors and GRPr(+) organs was significantly reduced, confirming specific receptor-mediated uptake. The estrogen receptor-positive tumor of a female breast cancer patient was clearly visualized by PET imaging using 68Ga-labeled NODIA-Me-Ahx-JMV594. To summarize, the positive charge at the N-terminus of the conjugate induced by the Ga(NODIA-Me) complex resulted in high GRPr affinity comparable to that of the potent antagonist DOTA-RM2. The conjugate NODIA-Me-Ahx-JMV594 is a promising probe for imaging of GRPr tumors that warrants further evaluation in larger patient cohorts as well as in combination with other radiometals.

Enabling Nucleophilic Reactivity in High-Spin Fe(II) Imido Complexes: From Elementary Steps to Cooperative Catalysis.

ConspectusTransition metal complexes featuring an M═NR bond have received great attention as critical intermediates in the synthesis of nitrogen-containing compounds. In general, the properties of the imido ligand in these complexes are dependent on the nature of the metal center. Thus, the imido ligand tends to be nucleophilic in early transition metal complexes and electrophilic in late transition metal complexes. Nonetheless, the supporting ligand can have a dramatic effect on its reactivity. For example, there are sporadic examples of nucleophilic late transition metal imido complexes, often based on strongly donating supporting ligands. Building on these earlier works, in this Article, we show that the imido ligand in a low-coordinate high-spin bis(carbene)borate Fe(II) complex is able to access previously unknown reaction pathways, ultimately leading to new catalytic transformations. We first focus on the synthesis, characterization, and stoichiometric reactivity of a highly nucleophilic Fe(II) imido complex. The entry point for this system is the intermediate-spin three-coordinate Fe(III) imido complex, which is generated from the reaction of an Fe(I) synthon with an organic azide. Alkali metal reduction leads to a series of M+ (M = Li, Na, K) coordinated and charge-separated (M = K(18-C-6)) high-spin Fe(II) imido complexes, all of which have been isolated and fully characterized. Combined with the electronic structure calculations, these results reveal that the alkali ions moderately polarize the Fe═N bond according to K+ ≈ Na+ < Li+. As a result, the basicity of the imido ligand increases from the charged separated complex to K+, Na+, and Li+ coordinated complexes, as validated by intermolecular proton transfer equilibria. The impact of the counterion on imido ligand reactivity is demonstrated through protonation, alkylation, and hydrogen atom abstraction reactions. The counterion also directs the outcome of [2 + 2] reactions with benzophenone, where alkali coordination facilitates double bond metathesis. Building from here, we describe how the unusual nucleophilicity of the high-spin Fe(II) imido complex revealed in stoichiometric reactions can be extended to new catalytic transformations. For example, a [2 + 2] cycloaddition reaction serves as the basis for the catalytic guanylation of carbodiimides under mild conditions. More interestingly, this complex also exhibits the first ene-like reactivity of an M═NR bond in reactions with alkynes, nitriles, and alkenes. These transformations form the basis of catalytic alkyne and nitrile α-deuteration and pKa-dictated alkene transposition reactions, respectively. Mechanistic studies reveal the critical role of metal-ligand cooperativity in facilitating these catalytic transformations and suggest the new avenues for transition metal imido complexes in catalysis that extend beyond classical nitrene transfer chemistry.

Influence of the Charge Ratio of Guanine-Quadruplex Structure-Based CpG Oligodeoxynucleotides and Cationic DOTAP Liposomes on Cytokine Induction Profiles.

Cationic liposomes, specifically 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP) liposomes, serve as successful carriers for guanine-quadruplex (G4) structure-based cytosine-guanine oligodeoxynucleotides (CpG ODNs). The combined benefits of CpG ODNs forming a G4 structure and a non-viral vector carrier endow the ensuing complex with promising adjuvant properties. Although G4-CpG ODN-DOTAP complexes show a higher immunostimulatory effect than naked G4-CpG ODNs, the effects of the complex composition, especially charge ratios, on the production of the pro-inflammatory cytokines interleukin (IL)-6 and interferon (IFN)-α remain unclear. Here, we examined whether charge ratios drive the bifurcation of cytokine inductions in human peripheral blood mononuclear cells. Linear CpG ODN-DOTAP liposome complexes formed micrometer-sized positively charged agglomerates; G4-CpG ODN-DOTAP liposome complexes with low charge ratios (0.5 and 1.5) formed ~250 nm-sized negatively charged complexes. Notably, low-charge-ratio (0.5 and 1.5) complexes induced significantly higher IL-6 and IFN-α levels simultaneously than high-charge-ratio (2 and 2.5) complexes. Moreover, confocal microscopy indicated a positive correlation between the cellular uptake of the complex and amount of cytokine induced. The observed effects of charge ratios on complex size, surface charge, and affinity for factors that modify cellular-uptake, intracellular-activity, and cytokine-production efficiency highlight the importance of a rational complex design for delivering and controlling G4-CpG ODN activity.

O-16 - The chelate makes the difference: Positively charged copper complexes favor receptor affinity and cell internalization of gastrin-releasing peptide receptor agonists and antagonists

O-16 - The chelate makes the difference: Positively charged copper complexes favor receptor affinity and cell internalization of gastrin-releasing peptide receptor agonists and antagonists

Novel family of [RuCp(N,N)(P)]+ compounds with simultaneous anticancer and antibacterial activity: Biological evaluation and solution chemistry studies

A family of ten novel ruthenium(II)-cyclopentadienyl organometallics of general formula [Ru(η5-C5H5)(N,N)(PPh2(C6H4COOR)][CF3SO3] (1–10) in which (N,N) = 4,4′-R′-2,2′-bipyridyl (R = –H or –CH2CH2OH; R’ = –H, –CH3, –OCH3, –CH2OH, and –CH2-biotin) was prepared from [Ru(η5-C5H5)(PPh2(C6H4COOH))2Cl]. All compounds were fully characterized by means of several spectroscopic and analytical techniques, and the molecular structures of [Ru(η5-C5H5)(PPh2(C6H4COOH))2Cl], 1, 3 and 4 have been additionally studied by single-crystal X-ray diffraction. The anticancer activity of all compounds was evaluated in sensitive and multidrug-resistant counterpart cell lines from human colorectal cancer (Colo 205 and Colo 320) and non-small cell lung cancer NSCLC (A549, NCI–H460 versus NCI–H460/R) as well. Notably, compounds 6 and 7 (R CH2CH2OH and (N,N) = bipy or Me2bipy, respectively) showed antiproliferative effect against both cell lines with high intrinsic selectivity towards cancer cells. The antibacterial activity of all compounds was also evaluated against both Gram negative and Gram positive strains, and some compounds in the series showed potent antibacterial activity against Staphylococcus aureus strains, including the methicillin-resistant MRSA strains.Solution speciation studies revealed that the complexes bearing the PPh2(C6H4COO−) ligand are neutral at physiological pH (7.4) in contrast with their ethylene glycol derivatives that have a permanent positive charge. While all compounds are lipophilic, the difference in the distribution coefficient for neutral and charged complexes is around one order of magnitude. Complexes 6 and 7 exhibited excellent biological activity and were selected for further studies. Spectrofluorometric methods were used to investigate their interaction with biomolecules such as human serum albumin (HSA) and calf thymus DNA (ct-DNA). For these complexes, binding site II of HSA is a possible binding pocket through non-covalent interactions. The release of ethidium from the DNA adduct by the charged complexes proves their interaction with DNA in contrast to the neutral ones.In conclusion, Ru(II)-cyclopentadienyl complexes with 2,2′-bipyridyl-derivatives and an ethylene glycol moiety tethered to the phenylphosphane co-ligand are very promising from a therapeutic perspective, in particular complexes 6 and 7 that display remarkable antibacterial activity with a high anti-proliferative effect against colon and non-small cell lung cancers, both clinically challenging neoplasias in need of effective solutions.

Seasonal controls on stream metal(loid) signatures in mountainous discontinuous permafrost

We assess physical and chemical processes driving seasonal fluctuations in dissolved (<0.45 μm) trace metal(loid) concentrations in subarctic streams in discontinuous permafrost. Our analysis integrates multiple years of stream hydrometric and geochemical data with geochemical analyses of bedrock, permafrost, and active-layer samples. Three principal flow regimes govern stream hydrology: winter baseflow, spring freshet, and summer high flows. Metal(oid) concentrations in streams respond seasonally to these flow regimes. Baseflows are dominated by discharge of circumneutral-pH groundwater draining fractured bedrock. This discharge acts as a source of metals found as oxyanions or neutrally charged complexes, such as uranium and molybdenum. High stream flows are associated with peak concentrations of aluminium, cobalt, copper, iron, nickel, titanium, and vanadium. Concentrations of the metal cations aluminium, cobalt, copper, nickel, and titanium peak during freshet, when infiltration of snowmelt through organic-rich and moderately acidic soils favors their complexation with dissolved organic carbon. Concentrations of vanadium peak during summer high flows, likely reflecting flow through mineral soils in the active layer and involving reductive dissolution of iron(III)-(oxyhydr)oxides. The seasonal variation of arsenic concentrations is complex; at the majority of catchments it is sourced from shallow flowpaths in the active layer, but it can also be locally associated with discharge of deeper bedrock groundwater, which is spatially constrained by the presence of permafrost. Based on our analysis, we present a conceptual model that describes the flowpaths and processes governing metal(loid) release to streams in discontinuous permafrost. This model provides a framework upon which we consider changes in metal(loid) export into water resources in the context of thawing permafrost.

Tuning nanofiltration membrane performance: OH–MoS2 nanosheet engineering and divalent cation influence on fouling and organic removal

Natural organic matter (NOM) present in surface water causes severe organic fouling of nanofiltration (NF) membranes employed for the production of potable water. Calcium (Ca2+) and magnesium (Mg2+) are alkaline earth metals present in natural surface water and severely exacerbate organic fouling owing to their ability to cause charge neutralization, complexation, and bridging of NOM and the membrane surface. Hence, it is of practical significance to engineer membranes with properties suitable for addressing organic fouling in the presence of these cations. This study employed OH-functionalized molybdenum disulphide (OH–MoS2) nanosheets as nanofillers via the interfacial polymerization reaction to engineer NF membranes for enhanced removal of NOM and fouling mitigation performance. At an optimized concentration of 0.010 wt.% of OH–MoS2 nanosheet, the membrane was endowed with higher hydrophilicity, negative charge and rougher membrane morphology which enhanced the pure water permeance by 46.33% from 11.2 to 16.39 L m−2 h−1 bar−1 while bridging the trade-off between permeance and salt selectivity. The fouling performance was evaluated using humic acid (HA) and sodium alginate (SA), which represent the hydrophobic and hydrophilic components of NOM in the presence of 0, 0.5, and 1 mM Ca2+ and Mg2+, respectively, and the performance was benchmarked with control and commercial membranes. The modified membrane exhibited normalized fluxes of 95.09% and 93.26% for HA and SA, respectively, at the end of the 6 h filtration experiments, compared to the control membrane at 89.71% and 74.25%, respectively. This study also revealed that Ca2+ has a more detrimental effect than Mg2+ on organic fouling and NOM removal. The engineered membrane outperformed the commercial and the pristine membranes during fouling tests in the presence of 1 mM Ca2+ and Mg2+ in the feed solution. In summary, this study has shown that incorporating OH–MoS2 nanosheets into membranes is a promising strategy for producing potable water from alternative water sources with high salt and NOM contents.

Trace Water Changes Metal Ion Speciation in Deep Eutectic Solvents: Ce3+ Solvation and Nanoscale Water Clustering in Choline Chloride-Urea-Water Mixtures.

Eutectic mixtures of choline chloride, urea, and water in deep eutectic solvent (DES)/water molar hydration ratios (w) of 2, 5, and 10, with dissolved cerium salt, were measured using neutron diffraction with isotopic substitution. Structures were modeled using empirical potential structure refinement (EPSR). Ce3+ was found to form highly charged complexes with a mean coordination number between 7 and 8, with the shell containing mostly chloride, followed by water. The shell composition is strongly affected by the molar ratio of dilution, as opposed to the mass or volume fraction, due to the high affinity of Cl- and H2O ligands that displace less favorable interactions with ligands such as urea and choline. The presence of Ce3+ salt disrupted the bulk DES structure slightly, making it more electrolyte-like. The measured coordination shell of choline showed significant discrepancies from the statistical noninteracting distribution, highlighting the nonideality of the blend. Cluster analysis revealed the trace presence of percolating water clusters (25 ≥ n ≥ 2) in solvent compositions of 5 and 10w for the first time.

Determining gas-phase chelation of zinc, cadmium, and copper cations with HisHis dipeptide using action spectroscopy and theoretical calculations

Using light generated by an infrared free electron laser, action spectroscopy was performed on doubly charged complexes of the metalated dipeptide histidyl-histidine (HisHis). Metal cations used were zinc, cadmium, and copper. Molecular dynamics and quantum-chemical calculations were used to screen a large number of conformers, whose theoretical infrared spectra were compared to the recorded action spectra of these metalated complexes. The zinc and cadmium spectra display dominant features associated with an iminol binding motif of the HisHis ligand, where the metal ion coordinates with both pros (π) nitrogens of the imidazole sidechains, the terminal carbonyl oxygen, and the backbone nitrogen for which the hydrogen ordinarily bound here has migrated to a carbonyl. The copper complex was difficult to assign to a single species, because a few predicted bands are absent from the experimental spectrum. The theoretical single point energies were also calculated for all structures examined, and DFT methods were found to describe the ion conformer populations in the case of the zinc and cadmium chelates better than the MP2 prediction.

Strain‐Free GaSb Quantum Dots as Single‐Photon Sources in the Telecom S‐Band

AbstractGenerating single photons in the telecommunication wavelength range from semiconductor quantum dots (QDs) and interfacing them with spins of electrons or holes is of high interest in recent years, with research mainly focusing on indium‐based QDs. However, there is not much data on the optical and spin properties of gallium antimonide (GaSb) QDs, despite it being a physically rich system with an indirect to direct bandgap crossover in the telecom wavelength range. This work investigates the (quantum‐) optical properties of GaSb QDs, which are fabricated by filling droplet‐etched nanoholes in an aluminum gallium antimonide (AlGaSb) matrix. Photoluminescence (PL) features from isolated and highly symmetric QDs are observed that exhibit narrow linewidth in the telecom S‐band and show an excitonic fine structure splitting of up to µeV. Moreover, time‐resolved measurements of the decay characteristics of an exciton are performed and the second‐order photon autocorrelation function of the charge complex is measured to , revealing clear antibunching and thus proving the capability of this material platform to generate non‐classical light.