Hydroxide Complexes Research Articles

Physicochemical, structural, digestive properties, and interaction mechanism of Tartary buckwheat starch-Rutin-calcium hydroxide complex

Tartary buckwheat is rich in starch and rutin, with Ca(OH)2 often used to improve the quality of buckwheat-extruded noodles. This study investigated the properties of a system combining tartary buckwheat starch (TBS), fixed Ca(OH)2 (0.6 %), and varying rutin addition (R, 2–10 %) to understand their interactions. Rutin addition in the presence of Ca(OH)2 significantly affected the structural and physicochemical properties of TBS in a dose-dependent manner. Microscopy showed that rutin particles precipitated on the gel walls of the TBS-R-Ca complexes at high rutin doses, more noticeably without Ca(OH)2. Rutin decreased gelatinization viscosity, whereas Ca(OH)2 alleviated this reduction in viscosity and gel structure. Ca(OH)2 and 2 % rutin significantly reduced the gelatinization and retrogradation enthalpies, relative crystallinity, short-range order degree, and TBS digestion rate. 1H NMR spectroscopy revealed interaction sites between rutin and TBS. Molecular dynamics results indicated that rutin and TBS can form effective hydrogen bonds and hydrophobic interactions, with Ca(OH)2 helping to maintain system stability.

Isothermal conversion of methane to methanol over Cu-CHA using different oxidants

Methane oxidation to methanol in cyclic processes using CuO-zeolites has traditionally employed O2 and N2O as oxidants. This study explores the use of Cu-CHA zeolite, demonstrating that CO2 can substitute O2 in an isothermal reaction at 400 °C, analogous to previous findings using Cu-MAZ. The use of in situ UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS) and density functional theory (DFT) theoretical calculations identified the formation of a binuclear copper hydroxide complex, Z-[CuOH-HOCu]2+-Z, on the Cu-CHA. Initial treatment using CO2 led to marginally superior catalytic activity, compared to the use of O2 alone, indicating the stability of the Z-[CuOH-HOCu]2+-Z complex against self-reduction at 400 °C. In subsequent cycles, activation with O2 facilitated the oxidation of adsorbed methanol, yielding water and reconstituting the active sites. Conversely, activation with CO2 led to the partial desorption of methanol, precluding water production and subsequent catalyst regeneration. The findings suggested that both O2 and CO2 activations necessitated a post-reaction water extraction step, followed by thermal treatment to replenish the active sites. Importantly, the results indicated that CO2 could be used as a viable alternative oxidant to O2 in this catalytic process, potentially enhancing the sustainability of industrial methanol production.

Influence of the second coordination sphere on O2 activation by a nonheme iron(II) thiolate complex

The synthesis and characterization of a new ligand, 1-(bis(pyridin-2-ylmethyl) amino)-2-methylpropane-2-thiolate (BPAMe2S−) and its nonheme iron complex, FeII(BPAMe2S)Br (1), is reported. Reaction of 1 with O2 at −20 °C generates a high-spin iron(III)-hydroxide complex, [FeIII(OH)(BPAMe2S)(Br)] (2), that was characterized by UV–vis, 57Fe Mössbauer, and electron paramagnetic resonance (EPR) spectroscopies, and electrospray ionization mass spectrometry (ESI-MS). Density functional theory (DFT) calculations were employed to support the spectroscopic assignments. In a previous report (J. Am. Chem. Soc.2024, 146, 7915–7921), the related iron(II) complex, FeII(BNPAMe2S)Br (BNPAMe2S− = bis((6-(neopentylamino)pyridinyl) methyl)amino)-2-methylpropane-2-thiolate) was reported and shown to react with O2 at low temperature to give a rare (η2-superoxo)‑iron(III) intermediate, which then converts to an S‑oxygenated sulfinate as seen for the nonheme iron thiol dioxygenases. This complex includes two hydrogen bonding neopentylamino groups in the second coordination sphere. Complex 1 does not include these H-bonding groups, and its reactivity with O2 does not yield a stabilized Fe/O2 intermediate or S‑oxygenated products, although the data suggest an inner-sphere mechanism and formation of an iron‑oxygen species that is capable of abstracting hydrogen atoms from solvent or weak CH bond substrates. This study indicates that the H-bond donors are critical for stabilizing the FeIII(O2-•) intermediate with the BNPAMe2S− ligand, which in turn leads to S‑oxygenation, as opposed to H-atom abstraction, following O2 activation by the nonheme iron center.

Investigating solvent effects on synthesizing novel cobalt hydroxide and fluoride complex from Co(BF4)2 as active materials of the battery supercapacitor hybrid

Metal-organic framework (MOF) derivatives with tunable pore structure and improved conductivity are intensively designed as electroactive materials. Incorporating structure directing agents (SDA) is beneficial for designing MOF derivatives with excellent electrochemical performances. Ammonium fluoroborate has been reported as an effective SDA, coupled with cobalt salt and 2-methylimidazole, to synthesize zeolitic imidazolate framework-67 (ZIF-67) derivatives for charge storage. However, the synthetic environment for growing cobalt-based active materials is relatively complex. In this study, cobalt tetrafluoroborate (Co(BF4)2) is proposed as a novel cobalt precursor, supplementing cobalt ions and acting as the SDA in a single chemical, to synthesize the cobalt-based electroactive material of energy storage electrodes. Interactions between solvent molecules and solutes play significant roles on the morphology, composition, and electrochemical performance of active materials. Deionized water, methanol and ethanol are used as precursor solvents to understand their effects on material and electrochemical properties. The optimal electrode presents a specific capacitance of 608.3 F/g at 20 mV/s, attributed to the highest electrochemical surface area and evident compositions of cobalt fluoride and hydroxide. A battery supercapacitor hybrid achieves the maximum energy density of 45 Wh/kg at 429 W/kg. The CF retention of 100% and Coulombic efficiency of 99% are achieved after 10,000 cycles.

Gold in sulfide fluids revisited

Gold solubility was measured at temperatures of 350, 400, 450, and 490 °C and pressures of 500 and 1000 bar in an ’oxidized sulfide’ system, as a function of pHT (2 – 10) and sulfur concentration (m(Stotal) = 0.03 – 1.2 [mol·(kg H2O)-1]). In this system, sulfur primarily exists as H2S, H2SO3, H2SO4, their dissociation products, and radical species such as S2- and S3-. The complexes Au(HS)2-, Au2S22-, AuHS(aq), AuHS(H2S)3(aq), and AuOH(aq) were identified as the primary gold species in the experimental fluids, varying with pH and m(Stotal). The solubility constants for Au(HS)2-, a critical (hydro)sulfide complex, align excellently with literature for ’reduced sulfide’ fluids, where sulfur predominantly exists in the 2- oxidation state. New experimental data from the ’oxidized sulfide’ system were regressed along with reliable literature data from ’reduced sulfide’ systems to calculate standard thermodynamic properties and parameters of the Helgeson-Kirkham-Flowers (HKF) model. The solubility constants for charged complexes, Au(HS)2- and Au2S22-, increase sharply with temperature, whereas those for neutral species, AuHS(aq) and AuHS(H2S)3(aq), show a pronounced peak near 300 °C. These (hydro)sulfide complexes account for gold solubility ranging from a few tens of ppb to a few tens of ppm in natural sulfide fluids, depending on the fluid pH. Thermodynamic calculations also indicate that, in addition to (hydro)sulfide species and the hydroxide complex, AuCl2- significantly contributes to Au mobility in high-temperature acidic chloride fluids. Based on new experimental data and prior studies using solubility and X-ray absorption spectroscopy methods, other gold complexes including mixed Au-HS-Cl, Au-HS-S3- species, and complexes with alkali metal cations, are deemed redundant. Above 250 °C, the influence of chloride salts on gold solubility can be accurately modeled using a simple extended Debye-Hückel equation with the term bγ·I = 0. The Setchenov coefficient bn = 0 suffices for calculating the activity coefficients of neutral species. This streamlined thermodynamic model aligns closely with earlier experimental work by Terry Seward and his team, effectively describing the state of Au in all types of natural fluids where Au exists in the 1+ oxidation state, under any set of P-T-f(O2)-f(S2)-compositional parameters.

Anemia of chronic diseases in the early stages of chronic kidney disease as a risk factor for cardiovascular complications in patients with glomerulonephritis

To determine biomarkers of anemia of chronic disease (ACD) in patients with glomerulonephritis (GN) in the early stages of CKD, to assess their role as risk factors for cardiovascular complications (CVС). Seventy nine patients with GN were studied, among them: 40 with primary сhronic GN (CGN), 39 with secondary forms:19 - GN with ANCA-associated systemic vasculitis, 20 - GN with systemic lupus erythematosus (SLE) at early (all I-II) CKD stages. In all patients, the level of serum C-reactive protein (CRP), hepcidin, interferon γ, and the circulating form of protein Klotho (s-Klotho) were determined. When a relative iron deficiency was detected [transferrin iron saturation coefficient (TSAT) <20%], patients were administered parenterally iron [III] sucrose hydroxide complex (Venofer). The frequency of anemia among patients with systemic diseases is 3.2 times higher than among patients with primary CGN. Patients with anemia (group I; n=43) had higher rates of daily proteinuria (p<0.001), systolic blood pressure (p<0.05), serum levels of interferon γ (p<0.001) and hepcidin (p<0.001) and lower values of eGFR (p<0.05) than patients without anemia (group II; n=36). A strong inverse correlation was noted between the level of hepcidin and the content of iron in serum (r=-0.856; p<0.001), between the level of hemoglobin and the level of interferon γ (r=-0.447; p<0.05), hepcidin (r=-0.459; p<0.05) and CRP (r=-0.453; p<0.05). A significant inverse correlation was found between the level of hemoglobin and CVC risk factors - the value of systolic blood pressure (r=-0.512; p<0.05) and the mass index of the left ventricular myocardium (r=-0.619; p<0.01). At the same time, the contribution of 2 from 6 analyzed factors, hepcidin and eGFR, to the development of ACD was 92.5%, of which 86.6% accounted for hepcidin. A strong direct correlation was also found between a decrease in hemoglobin level and a decrease in the level of s-Klotho protein (r=0.645; p<0.001), a decrease in the level of s-Klotho and an increase in the level of serum hepcidin (r=-0.541; p<0.05). The leading value of anemia (beta -0,29; p=0,04) and depression of the s-Klotho level (beta -0,44; p=0,02) as independent cardiovascular risk factors in this group of patients was confirmed by multivariate analysis. In patients with identified deficiency of iron (n=40), after 3-4 weeks of intravenous administration of venofer, the target level of hemoglobin (Нb>120 g/l) and transferrin saturation with iron (TSAT>20%) were achieved. Among the biomarkers of ACD in patients with immunoinflammatory diseases of the kidneys (primary and secondary СGN), the increase in the serum level of hepcidin is greatest importance. The concomitant to anemia decrease in s-Klotho is a leading risk factor for CVС in CKD. Early correction of ACD with iron supplements makes it possible to achieve target levels of Hb and TSAT and have subsequently a positive effect on the production of s-Klotho and the severity of left ventricular hypertrophia.

Prediction of the pKa's of Hydrated Metal Carbonates and Bicarbonates for Mg, Ca, Mn, Fe, Co, Ni, Cu, and Zn Dications.

The gas- and aqueous-phase acidities of hydrated metal dication carbonates, bicarbonates, and hydroxide complexes M(CO3)(H2O)n for n = 1 to 3, M(HCO3)2, M(HCO3)2(H2O)2, M(HCO3)(OH), and M(HCO3)(H2O)2(OH) for M = Mg, Ca, Mn, Fe, Co, Ni, Cu, and Zn were calculated at the CCSD(T)/aug-cc-pwCVDZ/cc-pwCVDZ level in the gas phase and at the B3LYP/aug-cc-pVTZ/cc-pVTZ(-PP) level with the COSMO self-consistent reaction field (SCRF) method in the aqueous phase. The composite correlated molecular orbital theory G3(MP2) and G3(MP2)B3 methods were used to predict the pKa's of the Mg structures and cis-cis carbonic acid to provide additional benchmarks. Using values scaled to experiment for H2CO3, the pKa's of bicarbonate ligands in group 2 and transition-metal complexes were compared to carbonic acid to gauge the effect of the metal complex on the bicarbonate. The group 2 metal complexes M(HCO3)2 and M(HCO3)(OH) decreased the acidity of the bicarbonate ligands, whereas their dihydrates were even less acidic. The transition-metal di-bicarbonate and bicarbonate hydroxide complexes generally made the bicarbonate more acidic especially when reduction of the metal occurs consistent with electron donation from the ligands; this is accompanied by spin transfer which typically increases in the order Mn < Fe < Co < Ni < Cu. The transition-metal dihydrates were less acidic than carbonic acid. Using values scaled to experiment for hydrated metal dications, the pKa's of water coordinated to group 2 and transition-metal complexes were generally more acidic than the hydrated metal dications, with the exception of Ca bicarbonate dihydrate, Co carbonate, Ni di-bicarbonate dihydrate, and Cu bicarbonate hydroxide di-bicarbonate.

Synthesis, characterization and reactivity of a Mn(III)–hydroxido complex as a biomimetic model for lipoxygenase

Manganese hydroxido (Mn–OH) complexes supported by a tripodal N,N′,N″-[nitrilotris(ethane-2,1-diyl)]tris(P,P-diphenylphosphinic amido) ([poat]3−) ligand have been synthesized and characterized by spectroscopic techniques including UV–vis and electron paramagnetic resonance (EPR) spectroscopies. X-ray diffraction (XRD) methods were used to confirm the solid-state molecular structures of {Na2[MnIIpoat(OH)]}2 and {Na[MnIIIpoat(OH)]}2 as clusters that are linked by the electrostatic interactions between the sodium counterions and the oxygen atom of the ligated hydroxido unit and the phosphinic (P=O) amide groups of [poat]3−. Both clusters feature two independent monoanionic fragments in which each contains a trigonal bipyramidal Mn center that is comprised of three equatorial deprotonated amide nitrogen atoms, an apical tertiary amine, and an axial hydroxido ligand. XRD analyses of {Na[MnIIIpoat(OH)]}2 also showed an intramolecular hydrogen bonding interaction between the MnIII–OH unit and P=O group of [poat]3−. Crystalline {Na[MnIIIpoat(OH)]}2 remains as clusters with Na+---O interactions in solution and is unreactive toward external substrates. However, conductivity studies indicated that [MnIIIpoat(OH)]− generated in situ is monomeric and reactivity studies found that it is capable of cleaving C-H bonds, illustrating the importance of solution-phase speciation and its direct effect on chemical reactivity.Synopsis: Manganese–hydroxido complexes were synthesized to study the influence of H-bonds in the secondary coordination sphere and their effects on the oxidative cleavage of substrates containing C-H bonds.

Uranium(VI) hydrolysis up to 250 °C and its geological implications

The hydrolysis of uranium(VI) has been investigated by solubility experiments conducted on sodium uranate (Na2U2O7) over a pHT range of 4.5–8 at 200 and 250 °C. Equilibrium constants for the UO2OH+, UO2OH20, UO2OH3- and UO2OH42- complexes have all been derived at both temperatures. Alongside this investigation a comprehensive literature review has been conducted to document previous investigations into U(VI) hydrolysis at temperatures above 25 °C. Using the new data reported here alongside those available in the literature, modified Ryzhenko-Bryzgalin equation of state parameters have been generated for the UO2OH+, UO2OH20, UO2OH3- and UO2OH42- complexes along with the polynuclear UO22OH22+ and UO23OH5+ complexes. This permits future works to extrapolate thermodynamic properties for these complexes to pressure–temperature conditions beyond those for which experimental data are available. Results reported here highlight the potential inadequacies of using the Ryzhenko-Bryzgalin and revised Helgeson-Kirkham-Flowers equations of state to extrapolate thermodynamic properties solely from room temperature data, with discrepancies ranging over 2–6 orders of magnitude being observed between extrapolations and the equilibrium constants experimentally derived at 200/250 °C. Using the newly derived properties, we report the results of thermodynamic calculations of uranium solubility and aqueous speciation under hydrothermal conditions relevant to a range of geological systems. These calculations suggest that uranyl hydroxide complexes may be responsible for uranium transport in a wide range of crustal fluids potentially obviating the need for high ligand concentrations.

A spectroscopic study of the stability of uranyl-carbonate complexes at 25–150 °C and re-visiting the data available for uranyl-chloride, uranyl-sulfate, and uranyl-hydroxide species

The stabilities of uranyl-carbonate and uranyl-hydroxide aqueous complexes were experimentally determined at temperatures ranging from 25 to 125 °C using in situ UV–vis and Raman spectroscopic techniques. Combined with earlier determinations of the stability of chloride, sulfate, and hydroxide complexes at temperatures up to 250 °C, these data permit to create a consolidated dataset suitable for modeling of U(VI) mobilization in natural systems. The parameters of the Modified Ryzhenko-Bryzgalin and the Helgeson-Kirkham-Flowers (HKF) Equations of State (EoS) were derived based on this dataset and used for thermodynamic modeling different scenarios of U(VI) mobilization. These models suggest that at conditions relevant to natural systems, carbonate-mediated transport of U(VI) is likely suppressed by the high stability of solid UO2(OH)2 and Na2U2O7. In contrast, sulfate-mediated mobilization mechanisms are highly efficient at acidic and near-neutral pH conditions and can lead to effective hydrothermal mobilization of U(VI).

Effects of Ring Size and Steric Encumbrance on Boron-to-Palladium Transmetalation from Arylboronic Esters.

The structure of the diol from which an arylboronic ester is derived dramatically influences the rate of transmetalation in the Suzuki-Miyaura cross-coupling reaction. Some esters undergo transmetalation more than 20 times faster than the parent arylboronic acid. Herein, investigations into the influence of arylboronic ester ring size and steric properties on the mechanism of transmetalation in the Suzuki-Miyaura reaction are described. Both factors impact the propensity of an arylboronic ester to bind to a dimeric palladium hydroxide complex. The reaction of hindered arylboronic esters derived from 1,2-diols (1,3,2-dioxaborolanes) with palladium hydroxide dimers to form a complex incorporating a Pd-O-B linkage is thermodynamically favorable, but the barrier to coordination is often higher than the barrier to arene transfer. In contrast, the analogous reaction between arylboronic esters derived from 1,3-diols (1,3,2-dioxaborinanes) and palladium hydroxide dimers is thermodynamically unfavorable, as 1,3,2-dioxaborinanes exhibit decreased electrophilicity compared to esters derived from 1,2- or 1,4-diols. These factors also influence the barrier of the arene transfer step, and in many cases, arylboronic esters that do not easily form Pd-O-B linked complexes undergo transmetalation faster than those that do because of hyperconjugative stabilization of the arene transfer transition state.

Valence Tautomerism Induced Proton Coupled Electron Transfer:X-H Bond Oxidation with a Dinuclear Au(II) Hydroxide Complex.

We report the preparation and characterization of the dinuclear AuII hydroxide complex AuII 2(L)2(OH)2 (L=N,N'-bis (2,6-dimethyl) phenylformamidinate) and study its reactivity towards weak X-H bonds. Through the interplay of kinetic analysis and computational studies, we demonstrate that the oxidation of cyclohexadiene follows a concerted proton-coupled electron transfer (cPCET) mechanism, a rare type of reactivity for Au complexes. We find that the Au-Au σ-bond undergoes polarization in the PCET event leading to an adjustment of oxidation levels for both Au centers prior to C(sp3)-H bond cleavage. We thus describe the oxidation event as a valence tautomerism-induced PCET where the basicity of one reduced Au-OH unit provides a proton acceptor and the second more oxidized Au center serves as an electron acceptor. The coordination of these events allows for unprecedented radical-type reactivity by a closed shell AuII complex.

Valence Tautomerism Induced Proton Coupled Electron Transfer:X−H Bond Oxidation with a Dinuclear Au(II) Hydroxide Complex

AbstractWe report the preparation and characterization of the dinuclear AuII hydroxide complex AuII2(L)2(OH)2 (L=N,N′‐bis (2,6‐dimethyl) phenylformamidinate) and study its reactivity towards weak X−H bonds. Through the interplay of kinetic analysis and computational studies, we demonstrate that the oxidation of cyclohexadiene follows a concerted proton‐coupled electron transfer (cPCET) mechanism, a rare type of reactivity for Au complexes. We find that the Au−Au σ‐bond undergoes polarization in the PCET event leading to an adjustment of oxidation levels for both Au centers prior to C(sp3)−H bond cleavage. We thus describe the oxidation event as a valence tautomerism‐induced PCET where the basicity of one reduced Au−OH unit provides a proton acceptor and the second more oxidized Au center serves as an electron acceptor. The coordination of these events allows for unprecedented radical‐type reactivity by a closed shell AuII complex.

A mesoionic carbene stabilized nickel(II) hydroxide complex: a facile precursor for C-H activation chemistry.

We report the synthesis of a new nickel(II) hydroxide complex 2 supported by a rigid, tridentate triazolylidene-carbazolid ligand. The complex can be accessed in high yields following a simple and stepwise extraction protocol using dichloromethane and aqueous ammonium chloride followed by aqeous sodium hydroxide solution. We found that complex 2 is highly basic, undergoing various deprotonation/desilylation reactions with E-H and C-H acidic and silylated compounds. In this context we synthesized a variety of novel, functionalized nickel(II) complexes with trimethylsilylolate (3), trityl sulfide (4), tosyl amide (5), azido (6), pyridine (7), acetylide (8, 9), fluoroarene (10 & 11) and enolate (12) ligands. We furthermore found that 2 reacts with malonic acid dimethyl ester in a knoevennagel-type condensation reaction, giving access to a new enolate ligand in complex 13, consisting of two malonic acid units. Furthermore, complex 2 reacts with acetonitrile to form the cyanido complex 14. The formation of complexes 13 and 14 is particularly interesting, as they underline the potential of complex 2 in both C-C bond formation and cleavage reactions.

Corrosion effect of acid/alkali on cementitious red mud-fly ash materials containing heavy metal residues

High-strength cementitious red mud-fly ash materials (RFMs) were formed from sodium hydroxide and water glass mixed solutions, and their abilities to solidify heavy metal ions (HMs, e.g., copper and cadmium) were assessed. The mechanism for precipitation of the HMs by corrosive acid/alkali solutions was explored via toxicity leaching tests, as well as SEM, XRD, FT-IR and XPS. The results showed that when the added alkaline activator was not fully consumed, the presence of small amounts of HMs consumed the excess alkaline ions to form hydroxide precipitates that filled the pores of the RFM, so the compressive strength of the RFM increased. Otherwise, the presence of excess HMs reduced the compactness of the RFM and eventually resulted in a highly porous structure, leading to weakening of the material. Additionally, small amounts of anhydrite phases were produced in the RFM. In neutral and alkaline environments, the HMs formed precipitates or coordination complexes with hydroxyl groups, and the solidification efficiencies exceeded 99%. In acidic environments, the HMs converted from their original precipitated forms or ion–hydroxide complexes to free cations. As a result, the HMs were more likely to be separated from the RFMs. Moreover, the RFMs were more prone to disaggregation under acidic conditions, which led to destruction of the RFM microstructure and rerelease of the HMs fixed in the microstructure.

THE ROLE OF SCANDIUM CHLORIDE AND HYDROXIDE COMPLEXES IN THE FORMATION OF SCANDIUM DEPOSITS: INSIGHTS FROM EXPERIMENTS AND MODELING

Abstract Although scandium is commonly concentrated to economic levels by magmatic processes, hydrothermal fluids also play an important role in its concentration. Indeed, the most important source of scandium is currently the Bayan Obo deposit in China, where scandium is extracted from hydrothermally produced aegirine. To know how and why scandium is concentrated by hydrothermal fluids, it is necessary to understand the speciation of scandium in hydrothermal fluids. In a recently published study, we showed that scandium forms stable species with fluoride ions and proposed that such species may have been responsible for the hydrothermal transport of scandium in deposits like Bayan Obo. Chloride ions, which have been shown to form stable complexes with the other rare earth elements (REEs), however, are much more abundant in most hydrothermal fluids than fluoride ions, as are hydroxide ions, particularly at high pH. We, therefore, conducted solubility experiments designed to investigate the stability of scandium chloride and hydroxide complexes in hydrothermal fluids. The experiments investigating the role of chloride species considered the solubility of Sc2O3(s) in the H2O-NaCl-HCl system at 100°, 150°, 300°, and 350°C and saturated water vapor pressure. These experiments showed that scandium concentration is independent of chloride concentration over the range of chlorinity investigated, i.e., up to 3.6 mol Cl– and that scandium, therefore, does not form stable complexes with chloride ions. To evaluate the role of hydroxide species in scandium transport and avoid the effect of chloride ions in the complexation, a second set of experiments was conducted that determined the solubility of Sc2O3(s) in H2O-NaClO4-HClO4 solutions at 100°, 150°, 200°, and 250°C, and saturated water vapor pressure. The results of these experiments showed that the solubility of Sc2O3(s) depends on pH and temperature. Based on the former dependence, two scandium hydroxide complexes, Sc(OH)2+ and Sc(OH)3°, were identified at low and higher pH, respectively. The formation constant (log β) determined for Sc(OH)2+ is 10.29 ± 0.07, 10.32 ± 0.07, 10.35 ± 0.19, and 10.91 ± 0.20 at 100°, 150°, 200°, and 250°C, respectively. That of Sc(OH)3° is 27.22 ± 0.68, 26.66 ± 1.35, 27.04 ± 0.13, and 28.02 ± 0.14 at the same temperatures, respectively. These results demonstrate that, unlike the case for the other rare earth elements, chloride plays a negligible role in transporting scandium in hydrothermal fluids. Instead, they show that scandium hydroxide complexes can be important in the transport of scandium and could have contributed significantly to the formation of deposits like those at Bayan Obo.

Fully Printed Flexible Zinc Oxide Patch for Wearable UV Light Sensing

AbstractMetal oxide materials are widely adopted in UV sensing due to their advantages of reliability, stability, and high sensitivity. However, the fabrication of metal oxide films on flexible substrates using micro/nano printing techniques still poses challenges. Notably, inks containing oxide nanoparticles often lead to nozzle clogging during the printing process. In addition, methods relying on precursor solutions typically require high post‐processing temperatures that conventional flexible substrates cannot withstand. In this study, a novel precursor ink based on zinc amine hydroxide complexes is proposed, enabling post‐processing at a low temperature of 250 °C. Through a fully printed approach, a wearable UV sensor based on a zinc oxide nanofilm on a flexible substrate is successfully fabricated. The sensor exhibits outstanding sensitivity and rapid response characteristics. By incorporating silver nanoparticles into the ink, the baseline resistance of the sensitive material is adjusted. Furthermore, a smart patch utilizing the NFC communication protocol is developed, allowing for wireless, passive, and wearable UV detection. In this study, a process paradigm for fabricating metal oxide films on flexible substrates using micro/nano printing techniques is introduced, showcasing significant potential in the field of micro/nano sensor fabrication.

A Cavity-Shaped Gold(I) Fragment Enables CO2 Insertion into Au-OH and Au-NH Bonds.

A cavity-shaped linear gold(I) hydroxide complex acts as a platform to access unusual gold monomeric species. Notably, this sterically crowded gold fragment enables the trapping of CO2 via insertion into Au-OH and Au-NH bonds to form unprecedented monomeric gold(I) carbonate and carbamate complexes. In addition, we succeeded in the identification of the first gold(I) terminal hydride bearing a phosphine ligand. The basic nature of the Au(I)-hydroxide moiety is also explored through the reactivity toward other molecules containing acidic protons such as trifluoromethanesulfonic acid and terminal alkynes.

The Leaching Behavior of Zinc Oxide in Medical Waste of Dental Clinics

Zinc Oxide is an indispensable substance in the field of dental treatment. It is used daily and intensively in all governmental and private dental clinics, leading to the disposal of very high concentrations of zinc with waste and eventually in landfill sites as a final destination for solid waste removal. This indicates the urgent need to investigate its behavior upon disposal due to the surrounding conditions. Approximately 4195 g of mixed dental waste samples were collected from (17) healthcare centers in Baghdad Al-Karkh. The leaching behavior of ZnO powder was investigated through batch reactors using makeup dental solid waste samples. The ZnO leaching was tested with 3 conditions; acidic, alkaline, and Ionic Strength (IS). The acidic condition was considered the most hazardous condition compared with basic and salinity due to the increasing tendency of ZnO to release Zn ion within waste leachate. In solutions with low pH, the dissolution of ZnO tends to produce zinc ions due to the attack of the ZnO surface by proton. In solutions of pH more than 9, the degradation of zinc oxide produces hydroxide complexes. Increasing (IS) decreased zinc concentration in leachate samples with time by promoting solids aggregation, decreasing the repulsive forces of ZnO particles, and accumulating in the bottom of reactors.

Facile Construction of Inorganic Phosphorus/Boron-Layered Double Hydroxide Complexes for Highly Efficient Fire-Safety Epoxy Resin

For inorganic flame retardants, facile fabrication and high-efficiency fire safety without compromising the mechanical property of the matrix are still significant challenges. Here, nanolayered double hydroxide containing boron constructed on the surface of ammonium polyphosphate (APP) complexes (B-LDH@APP) is prepared by a simple in situ coprecipitation technology to reduce the fire hazard and improves the mechanical performances of epoxy resin (EP). The as-obtained 4B-LDH@APP/EP achieves the UL-94 V-0 rating and presents superior flame-safety performance. With respect to the 4APP/EP, the fire growth rate (FIGRA), the peak heat release rate (pHRR), and the peak smoke production rate (pSPR) of 4B-LDH@APP/EP decrease by 77.8, 57.3, and 52.6%, respectively. This is mainly attributed to the excellent synergistic flame-retardant effect among boron, LDH, and APP, which can accelerate the generation of compact charring residual with a good microstructure during combustion of B-LDH@APP/EP composites. Furthermore, B-LDH@APP slightly affects the mechanical performances of the EP matrix due to the upgraded interfacial interaction.