Trivalent Salts Research Articles

Studies of the Sorption-Desorption of Pesticides from Cellulose-Based Derivative Nanocomposite Hydrogels

This study analyzed the effect of cellulose derivatives, namely methylcellulose (MC) and carboxymethylcellulose (CMC), on the stability of zeolite in a polymeric solution that would synthesize a three-dimensional network of poly(methacrylic acid)-co-polyacrylamide (PMAA-co-PAAm). Additionally, it investigated the effect of pH on the release of paraquat (PQ) and difenzoquat (DFZ) herbicides. Similar to previous studies with hydrogels containing CMC, the presence of bi and trivalent salts, such as Ca+2 and Al+3, also drastically reduced their swelling degree from 6.7 g/g in NaCl (0.15 mol·L−1) to 2.1 g/g in an AlCl3 solution (0.15 mol·L−1) for the MC nanocomposite. The viscosity results may suggest that the formation of a polysaccharide-zeolite complex contributed to the zeolite stabilization. As for the adsorption results, all samples adsorbed practically the entire concentration of both herbicides in an aqueous solution. Finally, it was also observed that the valence of the salts and molecular weight of the herbicide affect the release process, where DFZ was the herbicide with the highest concentration released. Both nanostructured hydrogels with CMC and MC exhibited lower release at pH = 7.0. These results demonstrated that a more in-depth evaluation of the phenomena involved in the application of these materials in controlled-release systems could help mitigate the impact caused by pesticides.

Solution and Surface Solvation of Nitrate Anions with Iron(III) and Aluminum(III) in Aqueous Environments: A Raman and Vibrational Sum Frequency Generation Study.

Hydrated trivalent metal nitrate salts, Fe(NO3)3·9H2O and Al(NO3)3·9H2O, in both solid and aqueous phases are investigated. Raman and surface-selective vibrational sum frequency generation (SFG) spectroscopy, are used to shed light on ion-ion interactions and hydration in several spectral regions spanning low frequency (440-550 cm-1) to higher frequency modes of nitrate and water (720, 1050, 1250-1450, and 2800-3750 cm-1). These frequencies span the metal-water mode, nitrate in-plane deformation, nitrate symmetric and asymmetric modes, and the OH stretch of condensed phase water molecules. Comparison to NaNO3, and in some cases KNO3, is also shown, providing insight. Splitting and frequency shifts are observed and discussed for both the solid state and solution phase. The Lewis acidity of Fe3+ and Al3+ ions plays a significant role in the observed spectra, in particular for the nitrate asymmetric band splitting and frequency shift. The spectral response from water solvation for iron and aluminum nitrates is nonlinear as compared to linear for sodium nitrate, suggesting significantly different solvation environments that are limited by water hydration capacity at higher concentrations. Moreover, a non-hydrogen bonded OH, dangling OH, from hydrating water molecules is observed spectroscopically for Al and Fe nitrate solutions. Furthermore, aluminum nitrate perturbs the surface water structure more than iron nitrate despite aluminum being a weaker Lewis acid. The surface water structure is thus found to be unique for the Al(NO3)3 solutions as compared to both Fe(NO3)3 and NaNO3, such that surface solvation is more pronounced. This observation exemplifies the nature of the Fe(III) and Al(III) ions and their substantial influence on the surface water structure.

The ion-activated attractive patchy particle model and its application to the liquid-vapor phase transitions.

Patchy particles are an intriguing subject of study and indeed a model system in the field of soft matter physics. In recent years, patchy particle models have been applied to describe a wide variety of systems, including colloidal crystals, macromolecular interactions, liquid crystals, and nanoparticle assemblies. Given the importance of the topic, rationalizing and capturing the basic features of these models is crucial to their correct application in specific systems. In this study, we extend the ion-activated attractive patchy particles model previously employed to elucidate the phase behavior of protein solutions in the presence of trivalent salts. Our extension incorporates the effect of repulsion between unoccupied and occupied binding sites, depicted as patches. Furthermore, we examine the influence of model parameters on the liquid-vapor coexistence region within the phase diagram, employing numerical methods. A deeper understanding of this model will facilitate a better comprehension of the effects observed in experiments.

Single-bubble sonoluminescence of itterbium(II or III) and thulium(II or III) chloride nanoparticles colloidal suspensions in dodecane

Colloidal suspensions of nanoparticles of di- and trivalent ytterbium and thulium chloride crystals in dodecane were prepared by ultrasonic dispersion. The average nanoparticle size in the suspensions was 20–35 nm. During single-bubble sonolysis with the bubble moving at the standing wave antinode, identical bands with a maximum at 550 nm appeared in the sonoluminescence spectra with spectral resolution Δλ = 15 nm for suspensions of both Yb(II) and Yb(III) salts. Bands with a maximum at 600 nm were found for suspensions of Tm(II) and Tm(III) salts. These sonoluminescence bands coincide with the photoluminescence bands of Yb(II) (550 nm) or Tm(II) (600 nm) salts, respectively. For suspensions of divalent lanthanide salts, these sonoluminescence bands appear when nanoparticles get into a moving bubble, because of collisional excitation of Yb(II) or Tm(II) in the bubble plasma, which periodically appears during acoustic oscillations: [Ln(II)]suspension → [Ln(II)]bubble → [Ln(II)]plasma → [Ln(II)*]plasma → Ln(II) + hνLn(II). The presence of analogous bands for suspensions of trivalent lanthanide salts is caused, in particular, by also their reduction in the plasma after they get into a bubble: [Ln(III)]suspension → [Ln(III)]bubble → [Ln(III)]plasma → [Ln(II), Ln(II)*]plasma → [Ln(II)*]plasma → Ln(II) + hνLn(II). The reduction of lanthanide ions in the bubble plasma is not limited to the reaction Ln(III) → Ln(II), Ln(II)*, but can proceed further giving singly charged lanthanide cations and lanthanide atoms: Ln(II) → Ln(I), Ln(I)* → Ln(0), Ln(0)*. The single-bubble sonoluminescence spectra with Δλ = 1.5 nm for a suspension of Yb(III) salt showed characteristic lines of Yb(I) and Yb(0). These characteristic lines and bands for ytterbium and thulium atoms and ions are suitable for sonoluminescent spectroscopic analysis, that is, identification and quantification of ions in solutions and suspensions and determination of electronic temperature in bubble plasma.

Highly active organocatalyst from a trivalent phosphazenium salt for ring-opening copolymerization of epoxides and cyclic anhydrides enhanced by hydrogen bonding interactions

Highly active organocatalyst from a trivalent phosphazenium salt for ring-opening copolymerization of epoxides and cyclic anhydrides enhanced by hydrogen bonding interactions

From adsorption to crystallization of proteins: Evidence for interface-assisted nucleation

Protein crystallization is among the key processes in biomolecular research, but the underlying mechanisms are still elusive. Here, we address the role of inevitable interfaces for the nucleation process. Quartz crystal microbalance with dissipation monitoring (QCM-D) with simultaneously optical microscopy, confocal microscopy, and grazing-incidence small angle X-rays scattering (GISAXS) were employed to investigate the temporal behavior from the initial stage of protein adsorption to crystallization. Here we studied the crystallization of the Human Serum Albumin (HSA), the most abundant blood protein, in the presence of a charged surface and a trivalent salt. We found evidence for interface-assisted nucleation of crystals. The kinetic stages involved are initial adsorption followed by enhanced adsorption after longer times, subsequent nucleation, and finally crystal growth. The results highlight the importance of interfaces for protein phase behavior and in particular for nucleation.

TEMPLATE-ENGINEERED TRIVALENT IRON AND CHROMIUM CONTAINING MACROCYCLIC COMPLEXES: CHARACTERIZATION AND IN VITRO STUDIES

A novel series of tetraaza macrocyclic complexes of biological importance was synthesized by “in situ” template reaction between triethylenetetramine and dibenzoylmethane in the presence of trivalent Fe and Cr metal salts in 1:1:1 molar ratio. These complexes are represented by molecular formula [M(C[Formula: see text]H[Formula: see text]N[Formula: see text]X]X2; [Formula: see text](III) and Cr(III); [Formula: see text], NO[Formula: see text], −OAc; C[Formula: see text]H[Formula: see text]N[Formula: see text] ligand. The reported complexes were characterized by using various physicochemical and spectroscopic techniques including elemental analyses, molar conductance, thermo-gravimetric analysis, FTIR, UV–Visible and mass spectral studies. The results obtained from analytical techniques and spectroscopic techniques together suggested the complexes have a square pyramidal geometry. Various computational studies were performed including molecular docking and modeling. Further, macrocyclic complexes were also screened for their “in vitro” antimicrobial activity against selected bacterial and fungal strains. The antioxidant activity of these complexes was also evaluated. Some of the complexes were found to possess remarkable antimicrobial activity and antioxidant activity. However, complex [Fe(C[Formula: see text]H[Formula: see text]N[Formula: see text](NO[Formula: see text]](NO[Formula: see text] was found to be most potent against selected bacterial and fungal strains. On the other hand, complex [Cr(C[Formula: see text]H[Formula: see text]N[Formula: see text](NO[Formula: see text]](NO[Formula: see text] was found to show best antioxidant activity with lowest value of IC[Formula: see text].

In-situ poly(hexahydrotriazine) gels temporary plugging agent suitable for high-temperature reservoirs: Regulation by inorganic chloride salts

A new acid-soluble in-situ temporary plugging agent suitable for high-temperature reservoirs was developed. By regulating the aldehyde-amine condensation reaction using inorganic chlorine salts, the poly(hexahydrotriazine) gels (PHT gels) exhibit good plugging performance and high-temperature resistance and can be degraded in weak acid solutions without residue. Results show that inorganic chlorine salts have a regulating effect on the gelling time of the gelant. Without the salt or the addition of monovalent chlorine salt, the gelant gels at room temperature but does not form a gel at high temperatures. After adding divalent or trivalent inorganic salts, PHT gels are formed at high temperatures, and their gelling time increases with the increase in salt content. Mechanical compression experiments show that the compression resistance of PHT gels is almost unchanged after exposure to high temperature (140 °C) and high salt (200 g/L NaCl and 10 g/L CaCl2). Displacement experiments show that PHT gels have excellent plugging performance with a plugging rate of more than 98.50% and a maximum plugging pressure of 5.34 MPa under the high temperature and high-salt conditions mentioned above. In addition, a hydrochloric acid solution with pH ≤ 5 can achieve residue-free breakage of PHT gels. The gel-breaking fluid has a high surface activity to facilitate flowback and a core unblocking rate of more than 100% after gel-breaking, making the reservoir permeability recoverable. The plugging and acidolysis ability of PHT gels make them excellent in-situ temporary plugging agents. This study aims to provide insights into the preparation of PHT gels and their use in high-temperature reservoirs.

Acetic acid as a protic solvent for reducing sulphuric acid concentrations in the production of cellulose nanocrystals alongside transition metal co-catalysts

Cellulose nanocrystals (CNC) conventionally involve highly concentrated sulphuric acid, which typically resulted in the formation of undesirable by-products. Although less corrosive mineral acids have been explored as alternatives, high concentrations are still required. In this study, CNC was successfully isolated from Leucaena leucocephala wood using mild sulphuric acid with acetic acid as protic solvent, and it was further studied with the addition of Lewis acids in the form of multivalent transition metal salts as co-catalyst. Selected divalent and trivalent transition metal salts including (Cr(NO3)3, Fe(NO3)3, Co(NO3)2, and Ni(NO3)2) were investigated. The morphology, chemical structure, particle size, and physicochemical properties of the CNCs were determined. Controlled depolymerization of cellulose was observed using transmission electron microscopy (TEM). Rod-like morphology for all CNCs was obtained during the hydrolysis process with the smallest CNC particles found at an average length of 278.1 ± 35.1 nm and a diameter of 13.4 ± 3.0 nm. The results showed that higher valence state metal ions resulted in better cellulose hydrolysis efficiency. In addition, the use of transition metal salt as a co-catalyst improved production efficiency and minimised carbonization of CNC while maintaining desired crystallinity and thermal properties.

Performance of ionic liquid functionalized metal organic frameworks in the adsorption process of phenol derivatives.

The growth of industrial activities has produced a significant increase in the release of toxic organic pollutants (OPs) to the environment from industrial wastewater. On this premise, this study reports the use of metal organic frameworks (MOFs) impregnated with various ionic liquids (ILs) in the adsorption of phenol derivatives, i.e., 2,6-dimethylphenol and 4,4'-dihydroxybiphenyl. MOFs were prepared starting from 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) with divalent (Co, Ni, Cu) and trivalent (Ce) metal salts in mild hydrothermal conditions using water as a green solvent. Imidazolium base ionic liquids, namely 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium nitrate, 1-butyl-3-methylimidazolium chloride, and 1-hexyl-3-methyl-imidazolium chloride, were used to modify MOFs, leading to composite materials (IL@MOF), which show the structural characteristics of MOFs, and complement the advantages of ILs. SEM, EDX images, and TG data indicate that the IL is just attached on the surface of the adsorbent material, with no changes in crystal size or morphology, but with slightly altered thermal stabilities of IL@MOF composites compared to the original ILs and MOFs, pointing to some interionic interaction between IL and MOF. This research consists of equilibrium experiments, studying the effect of the initial concentration of OPs on the adsorption efficiency of the as-prepared MOFs and IL@MOF, in order to determine the influence of the nature of the adsorbent on its developed adsorption capacity and to investigate the performance of both ILs and MOFs. To determine the maximum adsorption capacity, several empirical isotherms were used: Langmuir, Freundlich, Redlich-Peterson, and Dubinin-Radushkevich. The characteristic parameters for each isotherm and the correlation coefficient (R2) were identified. The IL modification of MOFs increased the adsorption capacity of IL@MOF for the removal of phenol derivatives from aqueous solution. The adsorption capacity function of the MOF structure follows the trend CeHEDP > CoHEDP > NiHEDP > CuHEDP. The best performance was achieved by adsorbent materials based on Ce.

Влияние катодного внедрения хрома в цинковое покрытие на его защитную способность

The influence of cathodic introduction of chromium into the surface layers of a zinc coating on the change in its corrosion resistance has been determined. Electrodeposition of zinc from electrolytes of various compositions was carried out on electrodes made of St3 steel. TsO grade zinc was used as an anode. Preliminary steel electrode was preparated treating the steel surface of in the potentiostatic mode of pre-phase deposition (DPD) at a potential 50 mV more positive than the equilibrium potential of zinc (Ep) in the working electrolyte for 5 minutes. The zinc coating was applied in potentiostatic mode at a potential of –1.20 V relative to the silver chloride reference electrode. The introduction of chromium into the electrodeposited zinc coating was carried out in the potential range from –0.97 to –1.15 V from electrolytes containing trivalent chromium salt. The results of X-ray fluorescence analysis of the component composition of working electrodes after cathodic introduction of chromium, the morphology of the formed surface obtained using scanning electron microscopy, indicate the presence of chromium in the coating composition and its effect on the structure of the deposit. The corrosion resistance of modified zinc coatings by cathodic introduction of chromium at potentials of –1.05 V and –1.10 V for 5 minutes exceeds this characteristic of chromated zinc.

Исследование физико-химических свойств препаратов протеин сукцинилат железа (III) и гидроксид полимальтозат железа (III)

The variety of dosage forms of iron-containing drugs and the complex metabolism of iron in the body cause certain difficulties in prescribing the drug and analyzing its effectiveness. There are numerous clinical studies on the benefits of various oral iron preparations, however, there is no convincing clinical data to suggest the superiority of one particular iron preparation over another. When analyzing the literature on clinical studies of iron deficiency therapy with preparations based on iron (II) sulfate and complex salts of iron (III) polymaltose hydroxide ("Maltofer") and iron (III) succinylate protein ("Ferlatum"), there are conflicting data. As a rule, existing publications do not focus on the relationship between the physico-chemical properties of drugs and side effects, bioavailability. From the analysis of the literature data on clinical trials, it is advisable to note that side effects and bioavailability depend on the following physico-chemical properties of the preparations: – ability to hydrolyze Fe (II) and (III); – strength of the iron-containing compound; – redox and surface-active properties of Fe (II) and (III). In this work, for the first time, two preparations of trivalent complex iron salts were compared according to their physico-chemical properties. The objects of the study were the drugs "Maltofer" (iron (III) hydroxydopolymaltosate) and "Ferlatum" (iron (III) protein succinylate). The physicochemical properties were studied by methods of trilonometry, conductometry, stalagmometry, potentiometry, and iodometric titration. According to the results of the study, the following conclusions were obtained: – complex compounds that are part of the medicines "Maltofer" and "Ferlatum" are hydrolyzed. This suggests that the probability of a side effect in the form of constipation will be less when using the drug "Maltofer". – aqueous solutions of "Ferlatum" have lower values of surface tension, which will contribute to better penetration of the drug through the cell membrane. – complex compounds of iron (III) hydroxydopolymaltosate and iron (III) protein succinylate are durable. The strength of the complex can lead to a slow release of iron ions during assimilation, and affect redox properties. The strength decreases when diluted to lower concentrations of the drug in aqueous systems, therefore, it is advisable to take this property into account when prescribing doses of drugs for their effective assimilation. – the reduction of Fe3+ to Fe2+ in the composition of drugs is possible only at a concentration of 10 mg/l in an aqueous system in an acidic environment at pH = 1-2. At higher concentrations, the oxidation state of Fe3+ is stable. Therefore, it is necessary to additionally introduce a reducing agent for the effective absorption of medicines. The obtained data on the physico-chemical properties of the drugs "Maltofer" and "Ferlatum" explain some of the results of clinical studies published in the scientific literature, and can be a criterion for clinical evaluation of their effectiveness.

Effect of Pulsed Currents on Oxygen and Carbon Contents of Trivalent Chromium Based Deposits

Hexavalent chromium salts have been identified as toxic for both humans and the environment by Health authorities, which led the authorities to take measures such as the implementation of strict rules, such as the REACH regulation. While some applications may be substituted by other processes, the thick hard chromium plating used for its functional properties in friction and wear lacks of alternatives. Among them, trivalent chromium salts have been extensively studied [1], but this kind of electrolytes presents typical difficulties, leading to more fragile coatings with through-cracks, and a typical increase of hardness up to very high values after annealing. This change in the chromium coating behavior is often attributed to a significant increase in carbon and oxygen contents [2].If temperature as well as current density have shown a great influence on both carbon and oxygen, their effects are reversed, with for example a decrease in oxygen content with temperature (due to a high solubility of hydroxides) accompanied by an increase in carbon content that leads to amorphous deposits. It is however very difficult to reduce both carbon and oxygen. The present work is built on a parallel study carried-out in the IRT M2P project CRONOS 2024, which discover the possibilities to limit the pH increase at the interface by inserting long-time toff during electrodeposition [3].Various parameters (ton times, toff times, peak current density) have been scanned for chromium deposition on a copper tip (to make the oxygen and carbon analysis easier). It has been showed that a possible control of oxygen and carbon is possible, leading to very low values and changes in deposits properties (hardness, behavior after annealing, roughness ...). The best sequence was studied for various temperatures, and the combination of parameters extensively described.Finally, 15CDV6 steel samples were coated and fully characterized.[1] P. Benaben, « An Overview of Hard Chromium Plating Using Trivalent Chromium Solutions », Plating and Surface Finishing, p. 8, 2011.[2] A. Baral et R. Engelken, « Modeling, Optimization, and Comparative Analysis of Trivalent Chromium Electrodeposition from Aqueous Glycine and Formic Acid Baths », J. Electrochem. Soc., vol. 152, no 7, p. C504, 2005, doi: 10.1149/1.1933688.[3] M. Marcelet et al., « Influence of Pulse-Current Parameters on pH Measured By Local Method », Meet. Abstr., vol. MA2019-02, no 21, p. 1046, sept. 2019, doi: 10.1149/MA2019-02/21/1046.

Use of Pulsed Currents with Long Off-Times to Increase Proprieties of Trivalent Chromium Based Deposits

Health authorities directives, such as the REACH European regulation, are particularly severe with compounds such as hexavalent chromium salts, toxic for both humans and the environment. As a result, trivalent chromium salts have been extensively studied [1] as a promising alternative to the hard chromium process. However, electrolytes containing trivalent chromium ions present challenges, as the proprieties of the deposits are not identical, although they are getting closer. One difference is the high carbon and oxygen contents in trivalent chromium plating [2], mainly caused by the incorporation of organic and hydroxide species, the latest as a result of the increase of the surface pH. This is a direct consequence of the significant current used to reduce protons during the plating process.There are several approaches to limit pH increase [3], such as adjusting the temperature or the bulk pH, or adding specific chemical compounds. This study explores the use of pulsed currents. An initial research did not be able to define pulse parameters (e.g., current density, on and off-times) that could selectively reduce chromium without also reducing hydrogen [4], which can occur with other electrolytes. We consequently decided to focused on near-surface phenomena by measuring local pH [5]. This was possible by implementating a micro-electrode to a few dozen of µm from the interface. Thus, a critical parameter was identified : resting time (toff). It was found that extending off-times maintained optimal pH values at the interface during deposition. The effect of these pulse sequences was evaluated, among other parameters, on internal stresses formed during deposition and the relaxation phase using a device developed at the University of Houston (material science program and electrical and computer engineering) [6]. [1] P. Benaben, « An Overview of Hard Chromium Plating Using Trivalent Chromium Solutions », Plating and Surface Finishing, p. 8, 2011. [2] A. Baral et R. Engelken, « Modeling, Optimization, and Comparative Analysis of Trivalent Chromium Electrodeposition from Aqueous Glycine and Formic Acid Baths », J. Electrochem. Soc., vol. 152, no 7, p. C504, 2005, doi: 10.1149/1.1933688. [3] J. Ji, W. C. Cooper, D. B. Dreisinger, et E. Peters, « Surface pH measurements during nickel electrodeposition », J Appl Electrochem, vol. 25, no 7, p. 642-650, juill. 1995, doi: 10.1007/BF00241925. [4] J. Rolet, « Influence de la forme de l’onde de polarisation sur la microstructure et les propriétés de revêtements électrolytiques élaborés à base de chrome trivalent », PhD thesis, Bourgogne Franche-Comté, 2017. [5] M. Marcelet et al., « Influence of Pulse-Current Parameters on pH Measured By Local Method », Meet. Abstr., vol. MA2019-02, no 21, p. 1046, sept. 2019, doi: 10.1149/MA2019-02/21/1046. [6] K. Ahmadi et al., « Crack Free Cr Coatings from Cr 3+ Electrolyte », J. Electrochem. Soc., vol. 169, no 1, p. 012504, janv. 2022, doi: 10.1149/1945-7111/ac4bfa.

Expanding the Coordination of f-Block Metals with Tris[2-(2-methoxyethoxy)ethyl]amine: From Molecular Complexes to Cage-like Structures.

Low-valent f-block metals have intrinsic luminescence, electrochemical, and magnetic properties that are modulated with ligands, causing the coordination chemistry of these metals to be imperative to generating critical insights needed to impact modern applications. To this end, we synthesized and characterized a series of twenty-seven complexes of f-metal ions including EuII, YbII, SmII, and UIII and hexanuclear clusters of LaIII and CeIII to study the impact of tris[2-(2-methoxyethoxy)ethyl]amine, a flexible acyclic analogue of the extensively studied 2.2.2-cryptand, on the coordination chemistry and photophysical properties of low-valent f-block metals. We demonstrate that the flexibility of the ligand enables luminescence tunability over a greater range than analogous cryptates of EuII in solution. Furthermore, the ligand also displays a variety of binding modes to f-block metals in the solid state that are inaccessible to cryptates of low-valent f-block metals. In addition to serving as a ligand for f-block metals of various sizes and oxidation states, tris[2-(2-methoxyethoxy)ethyl]amine also deprotonates water molecules coordinated to trivalent triflate salts of f-block metal ions, enabling the isolation of hexanuclear clusters containing either LaIII or CeIII. The ligand was also found to bind more tightly to YbII and UIII in the solid state compared to 2.2.2-cryptand, suggesting that it can play a role in the isolation of other low-valent f-block metals such CfII, NpIII, and PuIII. We expect that our findings will inspire applications of tris[2-(2-methoxyethoxy)ethyl]amine in the design of light-emitting diodes and the synthesis of extremely reducing divalent f-block metal complexes that are of interest for a wide range of applications.

A mixed valence decanuclear cerium-oxo cluster CeIII4CeIV6 for efficient photocurrent response

Cerium-oxo clusters with mixed valence exhibit distinctive redox properties due to cerium ions switch between +3/+4 valence states. However, the design and synthesis of these clusters present formidable challenges, resulting in limited availability of such species, often necessitating the use of both CeIII and CeIV reactants. Herein, we successfully obtained a mixed valence cerium-oxo cluster CeIII4CeIV6(µ3-O)4(µ4-O)4(acac)14(CH3O)6(CH3OH)2 (CeIII4CeIV6, Hacac = acetylacetone) through low-temperature crystallization only using the trivalent cerium salt. The coexistence as well as the distribution of Ce ions in different valence states have been determined from a multifaceted analysis. In addition, the stability of the synthesized cluster was confirmed by the HRESI-MS study through redissolution of the single crystal sample in fresh methanol. Importantly, Importantly, this study reveals the mechanism for the generation of +4 valence state. Under alkaline conditions, the presence of trace oxygen and the involvement of acetylacetone ligand facilitated the partial oxidation of CeIII to CeIV. The cluster CeIII4CeIV6 has strong ultraviolet absorption and long visible light absorption. As the electrode precursor, CeIII4CeIV6 showed clear photocurrent response and high photocurrent intensity due to CeIII/CeIV redox reaction.

Non‐monotonic salt concentration dependence of inverted electrokinetic flow

AbstractModeling of electrokinetic flows is crucial to understand numerous phenomena associated with electrochemistry, biophysics, and colloidal science. Here, we incorporate the modified Gaussian renormalized fluctuation theory into transport equations for electrolyte solutions to study the ion‐correlation‐induced inversion of electrokinetic flows, also known as charge inversion. We are able to capture the non‐monotonic dependence of inverted streaming current and reversed electrophoretic mobility on salt concentration. By analyzing the double‐layer structure, we elucidate that this non‐monotonicity is a consequence of the competition between spatially varying ion correlations and the translational entropy of the ions. We find that for practical values of surface charge densities, the excluded volume effect does not play any significant role. In a significant improvement over existing theories, our theoretical predictions are in quantitative agreement with experimental measurements for charge inversion in trivalent salts.

The effect of cations and epigallocatechin gallate on in vitro salivary lubrication

Ionic valency influences oral processing by changing salivary behavior and merits more attention since little is known. In this study, the influence of three ionic valences (monovalent, divalent and trivalent), ionic strength and epigallocatechin gallate (EGCG) on lubricating properties of saliva were investigated. Tribological measurements were used to characterize the lubrication response of KCl, MgCl2, FeCl3, and AlCl3 in combination with EGCG to the ex vivo salivary pellicle. KCl at 150 mM ionic strength provided extra lubrication via hydration lubrication. Contrarily, trivalent salts aggregated together with the salivary mucins via ionic cross-link interactions, which led to a decrease in salivary lubrication. FeCl3 and AlCl3 affected the salivary lubrication differently, which was attributed to changes in the pH. Finally, in presence of EGCG, FeCl3 interacted with EGCG via chelating interactions, preventing salivary protein aggregation. This resulted in less desorption of the salivary film, retaining the lubrication ability of salivary proteins.

Metal Ion-induced Gelation of High-concentration Graphite-like Crystalline Nanosheet Aqueous Suspensions.

The stability and transformation of nanomaterial aqueous suspensions are essential for their applications. Preparation of high-concentration carbon nanomaterials suspensions remains challenging due to their nonpolar nature. Herein, 200mgmL-1 carbon nanomaterial aqueous suspensions are achieved by using graphite-like crystalline nanosheets (GCNs) with high hydrophilicity. Furthermore, these high-concentration GCN aqueous suspensions spontaneously transform into gels when induced by mono-, di-, and trivalent metal salt electrolytes at room temperature. Theoretical calculation of potential energy by DLVO theory reveals that the gelatinized GCNs is a new and metastable state between two usual forms of solution and coagulation. It is shown that the gelation of GCNs is due to the preferential orientation of nanosheets in an edge-edge arrangement, which differs from the case of solution and coagulation. High-temperature treatment of GCN gels produces metal/carbon materials with pore structures. This work provides a promising opportunity to create various metal/carbon functional materials.

Synthesis of magnetite-silica-carbon quantum dot nanocomposites for melatonin drug delivery

In targeted drug delivery, the drug is released at a specific and desired point and condition. In this research, magnetite cores (high saturation magnetization property (emu.g-159) were used to target the drug system. First, magnetite nanoparticles were synthesized by coprecipitation method from divalent and trivalent chloride salts of iron (FeCl2 and FeCl3), then mesoporous silicas (with a pore diameter of 13 nm) were formed by Stöber's method from the tetraethylorthosilicate (TEOS) silica source on magnetite cores in spheres form. After that, the carbon quantum dots were synthesized by hydrothermal method from citric acid and their surface was immobilized by dimethylamine which were placed in silica cavities by physical adsorption method.
 The effective drug melatonin (6.46 mg of melatonin per 100 mg of the drug system) was also loaded on this system by physical absorption method and the release of this drug was carefully determined by the release from the dialysis bag in the simulated environment of blood and cancer tissue. the quantum gain of the system was determined to be about 40%. The results showed that the loading of melatonin drug and carbon quantum dots was done well on silica nanoparticles with magnetite cores, and this system releases 30% of the drug even under temperature conditions.