High-pressure synthesis of ε-FeOOH from β-FeOOH and its application to the water oxidation catalyst

Research on materials under extreme conditions such as high pressures provides new insights into the evolution and dynamics of the earth and space sciences, but recently, this research has focused on applications as functional materials. In this contribution, we examined high-pressure/high-temperature phases of β-FeO_1−x(OH)_1+xCl_x with x = 0.12 (β-FeOOH) and their catalytic activities of water oxidation, i.e., oxygen evolution reaction (OER). Under pressures above 6 GPa and temperatures of 100–700 °C, β-FeOOH transformed into ε-FeOOH, as in the case of α-FeOOH. However, the established pressure–temperature phase diagram of β-FeOOH differs from that of α-FeOOH, probably owing to its open framework structure and partial occupation of Cl⁻ ions. The OER activities of ε-FeOOH strongly depended on the FeOOH sources, synthesis conditions, and composite electrodes. Nevertheless, one of the ε-FeOOH samples exhibited a low OER overpotential compared with α-FeOOH and its parent β-FeOOH, which are widely used as OER catalysts. Hence, ε-FeOOH is a potential candidate as a next-generation earth-abundant OER catalyst.

Research on materials under extreme conditions such as high pressures provides new insights into the evolution and dynamics of the earth and space sciences, but recently, this research has focused on applications as functional materials.     

Fe(ii) and Mn(ii) removal by Ca(ii)–manganite (γ-MnOOH)-modified red mud granules in water

In this study, a material (DLRMG) was synthesized by modifying Ca²⁺ and manganite (γ-MnOOH) on red mud granules (RMG), which were the main raw materials derived from industrial alumina. Moreover, a series of experiments were conducted on the adsorption of Fe²⁺ and Mn²⁺ in underground water. The prepared samples were analyzed by X-ray diffraction (XRD), thermogravimetric analysis-differential thermal analysis (TG-DTA), zeta potential analysis, BET and scanning electron microscopy (SEM); the concentration of the effluent was found to be of acceptable standard after the treatment. DLRMG continued to treat fluoride wastewater even after the saturated adsorption of Fe²⁺ and Mn²⁺, and the results clearly showed that the treatment was effective. Overall, the problems of red mud stockpile and pollution in China would be effectively controlled by DLRMG.

The use of the waste of aluminum industry to prepare effective polluted materials for the treatment of underground water.     

Oxygen Equilibrium Characteristics of Abnormal Hemoglobins: Hirose (α2β237Ser), L Ferrara (α247Glyβ2), Broussais (α290Asnβ2), and Dhofar (α2β258Arg)

The oxygen equilibrium characteristics of four structural variants of hemoglobin A were correlated with their amino acid substitutions.Hemoglobin Dhofar, in which the proline at E2(58)beta is replaced by arginine, had normal oxygen equilibrium characteristics.Hemoglobin L Ferrara. in which the aspartic acid at CD5(47)alpha is replaced by glycine, and hemoglobin Broussais, in which the lysine at FG2(90)alpha is replaced by asparagine, both showed a slightly elevated oxygen affinity; nevertheless both demonstrated a normal heme-heme interaction and a normal Bohr effect.Hemoglobin Hirose, in which the tryptophan at C3 (37)beta is replaced by serine, showed abnormalities of all oxygen equilibrium characteristics; i.e., increased oxygen affinity, diminished heme-heme interaction, and reduced Bohr effect.These results suggest that aspartic acid at CD5(47)alpha and lysine at FG2(90)alpha are involved in the function of the hemoglobin molecule, despite the fact that these positions are not located directly in the heme or the alpha-beta-contact regions.Tryptophan at C3(37)beta is located at contact between alpha(1)- and beta(2)-subunits. It is suggested that the substitution by serine might disturb the quarternary structure of the mutant hemoglobin molecule during transition from oxy-form to deoxy-form resulting in an alteration of the heme function.     

Visible light-induced oxidative α-hydroxylation of β-dicarbonyl compounds catalyzed by ethylenediamine–copper(ii)

We have developed an efficient oxidative α-hydroxylation of β-keto esters with firstly using the structurally simple ethylenediamine–copper(ii) as a catalyst for β-keto esters activation and using visible light as the driving force for generating more active singlet oxygen (¹O₂) from triplet state oxygen (³O₂) in the air, providing a series of α-hydroxy β-keto esters in excellent yields (up to 99%) under extremely low photosensitizer loading (0.01 mol%) and catalyst loading (1 mol%) within a short time. Moreover, the gram-scale synthesis showed the practical utility of this protocol.

An efficient visible light-induced oxidative α-hydroxylation of β-dicarbonyl compounds has been developed using structurally simple ethylenediamine–copper(ii) as a catalyst.     

Cationic palladium(ii)-catalyzed synthesis of substituted pyridines from α,β-unsaturated oxime ethers

An efficient method for the synthesis of multi-substituted pyridines from β-aryl-substituted α,β-unsaturated oxime ethers and alkenes via Pd-catalyzed C–H activation has been developed. The method, using Pd(OAc)₂ and a sterically hindered pyridine ligand, provides access to various multi-substituted pyridines with complete regioselectivity. Mechanistic studies suggest that the pyridine products are formed by Pd-catalyzed electrophilic C–H alkenylation of α,β-unsaturated oxime followed by aza-6π-electrocyclization. The utility of this method is showcased by the synthesis of 4-aryl-substituted pyridine derivatives, which are difficult to synthesize efficiently using previously reported Rh-catalyzed strategies with alkenes.

An efficient method for the synthesis of multi-substituted pyridines from α,β-unsaturated oxime ethers via cationic Pd(ii)-catalyzed C–H activation has been developed.     

Thermal stability and oxidation characteristics of α-pinene, β-pinene and α-pinene/β-pinene mixture

Turpentine is a renewable resource, has good combustion performance, and is considered to be a fuel or promising additive to diesel fuel. This is very important for the investigation of thermal stability and energy oxidation characteristics, because evaluation of energy or fuel quality assurance and use safety are necessary. The main components of turpentine are α-pinene and β-pinene, which have unsaturated double bonds and high chemical activity. By investigating their thermal stability and oxidation reaction characteristics, we know the chemical thermal properties and thermal explosion hazard of turpentine. In this present study, the thermal stability and oxidation characteristics of α-pinene, β-pinene and α-pinene/β-pinene mixture were investigated using a high sensitivity accelerating rate calorimeter (ARC) and C80 calorimeter. The important parameters of oxidation reaction and thermal stability were obtained from the temperature, pressure and exothermic behavior in chemical reaction. The results show that α-pinene and β-pinene are thermally stable without chemical reaction under a nitrogen atmosphere even when the temperature reaches 473 K. The initial exothermic temperature of the two pinenes and their mixture is 333–338 K, and the heat release (−ΔH) of their oxidation is 2745–2973 J g⁻¹. The oxidation activation energy (E_a) of α-pinene, β-pinene and α-pinene/β-pinene mixture is 116.25 kJ mol⁻¹, 121.85 kJ mol⁻¹, and 115.95 kJ mol⁻¹, respectively. There are three steps in the oxidation of pinenes: the first is the induction period of the oxidation reaction; the second is the main oxidation stage, and the pressure is reduced; the third is thermal decomposition to produce gas.

Turpentine is a renewable resource, has good combustion performance, and is considered to be a fuel or promising additive to diesel fuel.     

Recyclable iron(ii) caffeine-derived ionic salt catalyst in the Diels–Alder reaction of cyclopentadiene and α,β-unsaturated N-acyl-oxazolidinones in dimethyl carbonate

Iron(ii) triflate was used in combination with caffeine-derived salts as recyclable catalysts for the Diels–Alder reaction run in dimethyl carbonate (DMC) as a green solvent. The catalyst was prepared as an ionic salt from a xanthinium salt and Fe(OTf)₂. Various substrates including α,β-unsaturated carbonyl and N-acyloxazolidinone derivatives were reacted with cyclopentadiene using this recyclable catalyst. The use of a low catalyst loading (1 mol%) afforded high yields (up to 99%) of the corresponding cycloadducts. The recycling and the efficiency of the catalyst were demonstrated for several runs.

Iron(ii) triflate was used in combination with caffeine-derived salts as recyclable catalysts for the Diels–Alder reaction run in dimethyl carbonate (DMC) as a green solvent.     

Characterization and adsorption properties of cross-linked yeast/β-cyclodextrin polymers for Pb(ii) and Cd(ii) adsorption

In this study, a crosslinked yeast/β-cyclodextrin polymer (Y–β-CDP), for use as an effective adsorbent for removal Pb(ii) and Cd(ii) ions from aqueous solution, has been innovatively prepared by grafting β-cyclodextrin (β-CD) onto the surface of baker''s yeast (BY) and thiomalic acid as a crosslinker. Several characterization techniques, such as SEM equipped with an EDS analyzer, FTIR, XRD, and XPS were employed characterize the Y–β-CDP. The impact of various operating parameters, such as pH, adsorbent dosage, initial concentration of metal ions, contact time and solution temperature, as well as adsorption kinetics, isotherms and thermodynamics were systematically investigated. The adsorption of Pb(ii) and Cd(ii) on Y–β-CDP reached equilibrium in 25 min, and the kinetic process conforms to the pseudo-second order model. The Langmuir model was used to describe the adsorption isotherm data better than the Freundlich model. The predicted maximum adsorption capacity at 25 °C for Pb(ii) and Cd(ii) was 150.08 and 102.80 mg g⁻¹, respectively, when the initial concentration of metal ions was 120 mg L⁻¹. The thermodynamic analysis revealed that the adsorption procedure of Pb(ii) and Cd(ii) onto Y–β-CDP was spontaneous and endothermic. Furthermore, regeneration experiments demonstrated that Y–β-CDP had excellent recyclability. Together, all results suggested that Y–β-CDP could potentially be a promising adsorbent in the purification of water contaminated with heavy metal ions.

A cross-linked yeast/β-cyclodextrin polymer (Y–β-CDP) was synthesized to remove Pb(ii) and Cd(ii) from aqueous solution.     

LiCl-promoted amination of β-methoxy amides (γ-lactones)

An efficient and mild method has been developed for the amination of β-methoxy amides (γ-lactones) including natural products michelolide, costunolide and parthenolide derivatives by using lithium chloride in good yields. This reaction is applicable to a wide range of substrates with good functional group tolerance. Mechanism studies show that the reactions undergo a LiCl promoted MeOH elimination from the substrates to form the corresponding α,β-unsaturated intermediates followed by the Michael addition of amines.

The amination of β-methoxy amides (γ-lactones) including natural products michelolide, costunolide and parthenolide derivatives were first developed by using lithium chloride.

The formation of carbon–nitrogen bonds remains one of the most fundamental and widely practiced reactions in organic synthesis, due to the prevalence of this functionality in the preparations of functional molecules in pharmaceutical chemistry, biochemistry and material sciences.¹ Various synthetic methodologies have been developed to form C(sp²)-N bonds, including the Goldberg reaction,² Buchwald–Hartwig reaction,³ imine reduction⁴ and the nucleophilic addition of carbon-nucleophiles to imine derivatives.⁵ Meanwhile, the formations of C(sp³)-N bonds can be achieved by reductive amination, which involves the conversion of a carbonyl group to an amine via an imine intermediate, such as Eschweiler–Clarke reaction⁶ and Borch reductive amination.⁷ Nucleophilic substitution of alkyl(pseudo)halides with amines (amine alkylation) serves as one direct strategy for the preparation of alkylamines, while the necessity of pre-installation of the halogen atoms and the production of stoichiometric inorganic salt wastes are considered as two main drawbacks for its application in large scale industrial synthesis.⁸Methoxy as the leaving group in the amination reactions has recently attracted the attention of organic chemists. For instance, Chiba and coworkers reported a method for the nucleophilic amination of methoxy arenes,⁹ which was achieved by using sodium hydride (NaH) in the presence of lithium iodide (LiI) through a concerted nucleophilic aromatic substitution pathway (Fig. 1a).¹⁰ Kondo and coworkers demonstrated that the organic superbase t-Bu-P4 efficiently catalyzes the amination of methoxy(hetero)arenes with the amine nucleophiles (Fig. 1b).¹¹ The t-Bu-P4 is also suitable to catalyze the amination of β-(hetero)arylethyl ethers with amines to synthesize β-(hetero)arylethylamines (Fig. 1c).¹² Sun and coworkers reported that C–S bond cleavage to access N-substituted acrylamide and β-aminopropanamide(Fig. 1d).¹³Open in a separate windowFig. 1Amination reactions of methyl ethers.Recently, we described the application of a CuBr–LiCl composite for the short-chain alkoxylation of aryl bromides.¹⁴ During that course of study, the single-shell lithium ion was found to embrace a unique affinity for oxygen and can be used as an additive to activate C–O bond and facilitate the nucleophilic reaction. On the basis of this study, we herein present the synthesis of β-amino amides (γ-lactones) via the elimination of methoxy group followed by Michael addition of an amine, that was promoted by LiCl in good yields under conventional conditions.We initiated our study with the reaction of 3-methoxy-N-phenylpropanamide 1a and piperidine 2a in the presence of lithium salts (

Catalyst-free chemoselective α-sulfenylation/β-thiolation for α,β-unsaturated carbonyl compounds

A novel, efficient, catalyst-free and product-controllable strategy has been developed for the chemoselective α-sulfenylation/β-thiolation of α,β-unsaturated carbonyl compounds. An aromatic sulfur group could be chemoselectively introduced at α- or β-position of carbonyls with different sulfur reagents under slightly changed reaction conditions. A series of desired products were obtained in moderate to excellent yields. Mechanistic studies revealed that B₂pin₂ played the key role in activating the transformation towards the β-thiolation of α,β-unsaturated carbonyl compounds. This transition-metal-catalyst-free method provides a convenient and efficient tool for the highly chemoselective preparation of α-thiolation or β-sulfenylation products of α,β-unsaturated carbonyl compounds.

This catalyst-free method provides a useful and efficient tool for the highly chemoselective preparation of α-thiolation or β-sulfenylation products of α,β-unsaturated carbonyl compounds.     

Intermolecular interactions between β-cyclodextrin and water

This study focused on demonstrating the intermolecular interactions between β-cyclodextrin and water, with the aim to better understand the transfer of small molecules to β-cyclodextrin. The intermolecular interaction strength between β-cyclodextrin and water was analyzed using different methods such as the dynamic adsorption of water, the TG-DSC of β-cyclodextrin and molecular modeling employing MM2 force field calculations. The experiments for the adsorption of water on β-cyclodextrin was aimed to systematically investigate the adsorption characteristics, such as adsorption capacity, adsorption rate, adsorption heat and activation energy, influenced by the adsorption temperature and vapor pressure of water. The results indicated that the water adsorption on β-cyclodextrin is an exothermic process. The hysteresis loop type in the adsorption isotherms at multiple temperatures indicated that water adsorption is not purely a traditional physical adsorption due to the existence of structure effects such as the cavity effect and hydrogen bonding. The activation energy during water adsorption was 7.4 kJ mol⁻¹. However, the activation energy during water desorption was in the range of 35–45 kJ mol⁻¹, which decreased with an increase in the amount of water adsorbed. This indicated that water adsorption is much easier than water desorption from β-cyclodextrin and that water desorption is more difficult with a small amount of adsorbed water compared with a large amount of adsorbed water. Subsequently, the obtained average intermolecular interaction strength between β-cyclodextrin and water under the experimental conditions was 67.5 kJ mol⁻¹ (water), which was verified by DSC.

This study focused on demonstrating the intermolecular interactions between β-cyclodextrin and water, with the aim to better understand the transfer of small molecules to β-cyclodextrin.     

Electrophilic halogenations of propargyl alcohols: paths to α-haloenones, β-haloenones and mixed β,β-dihaloenones

The Meyer–Schuster rearrangement of propargyl alcohols or alkynols leading to α,β-unsaturated carbonyl compounds is well known. Yet, electrophilic halogenations of the same alkynols and their alkoxy, ester and halo derivatives are inconspicuous. This review on the halogenation reactions of propargyl alcohols and derivatives intends to give a perspective from its humble direct halogenation beginning to the present involving metal catalysis. The halogenation products of propargyl alcohols include α-fluoroenones, α-chloroenones, α-bromoenones and α-iodoenones, as well as β-haloenones and symmetrical and mixed β,β-dihaloenones. They are, in essence, tri and tetrasubstituted alkenes carrying halo-functionalization at the α- or β-carbon. This is a potential stepping stone for further construction towards challenging substituted alkenones via Pd-catalysed coupling reactions.

This review highlights the development of α-haloenone, β-haloenone and mixed β,β-dihaloenone formations from propargyl alcohols via direct electrophilic halogenations and metal catalysed-halonium interception rearrangements.     

THE CELLULAR ORIGIN OF HUMAN IMMUNOGLOBULINS (γ2, γ1M, γ1A)

A study was made of the cellular origin of human immunoglobulins (γ₂, γ_1M, γ_1A). The results indicated that two closely related families of cells form immunoglobulins in human lymphoid tissue: germinal (reticular) centers and plasma cells. Thus their cellular origin in addition to their known antigenic relations further justifies placing the immunoglobulins in one family of proteins. Immunoglobulins were also formed to a small extent in primitive reticular cells which resembled those of germinal centers but were separated from them. Possibly such cells were undergoing transition to the much more numerous plasma cells with which they were commonly associated. The mantles of small lymphocytes which surrounded germinal centers did not contain detectable quantities of immunoglobulins. While in general only one type of immunoglobulin was present in an individual cell or germinal center, γ₂- and γ_1M-globulin were identified on occasion in the same plasma cell and germinal center. A peculiarity of the fetal thymus gland was the presence of immunoglobulin, mainly γ_1M, in a small number of cells of small and intermediate size and primitive reticular appearance and in Hassall's corpuscles.     

Synthesis of α,β-unsaturated esters of perfluoropolyalkylethers (PFPAEs) based on hexafluoropropylene oxide units for photopolymerization

α,β-unsaturated esters are usually synthesized for polymer applications. However, the addition of maleate (cis-configuration) to a fluorinated moiety is challenging due to its potential isomerization during esterification. Various synthetic routes were attempted and led to very low conversion or side-products. The immiscibility of both reagents combined with an easy isomerization or attack on the double bond were potential explanations. In this paper, the synthesis of maleates oligo(hexafluoropropylene oxide) is reported by Steglich esterification and the reaction conditions are discussed depending on the molecular weight of the fluorinated moieties. After UV-curing, hydrophobic polymers were obtained by copolymerization with vinyl ethers by electron acceptor–donor systems.

Hydrophobic macromonomers synthesized by Steglich esterification to generate UV-curable materials.     

Nanomagnetic macrocyclic Schiff-base–Mn(ii) complex: an efficient heterogeneous catalyst for click approach synthesis of novel β-substitued-1,2,3-triazoles

In the present work, a novel symmetrical 15-membered macrocyclic Schiff base complex of manganese was prepared using the reaction of the synthetic 2,6-diacetylpyridine functionalized Fe₃O₄ MNPs with 2,2-(piperazine-1,4-diyl)dianiline and Mn(ii) bromide salt via a template approach. The resulting [Fe₃O₄@PAM–Schiff-base–Mn][ClO₄] heterogenized complex was characterized using FT-IR, XRD, BET, TGA, EDX, Xray-mapping, SEM, TEM and VSM analysis. To demonstrate proof of concept, Huisgen 1,3-dipolar cycloaddition synthesis of 1,2,3-triazoles was selected to evaluate the activity and reusability of the catalyst. The ethanol as a green solvent proved to be an excellent reaction medium for this synthesis. Yields of up to 100% were obtained in some cases. Significantly, as demonstrated, [Fe₃O₄@PAM–Schiff-base–Mn][ClO₄] catalyst was recycled for 8 cycles without losing catalytic activity under the optimized reaction conditions. The hot filtration and ICP-OES tests ratified that there was no leaching of metal during the catalytic reaction, indicating the heterogeneous manner of the catalyst.

A 15-membered macrocyclic Schiff base complex of manganese catalyzed the Huisgen 1,3-dipolar cycloaddition reactions has been developed and yielding a wide variety of 1,2,3-triazoles derivatives in good to excellent yields.     

Counterselection against Dμ Is Mediated through Immunoglobulin (Ig)α-Igβ

The pre-B cell receptor is a key checkpoint regulator in developing B cells. Early events that are controlled by the pre-B cell receptor include positive selection for cells express membrane immunoglobulin heavy chains and negative selection against cells expressing truncated immunoglobulins that lack a complete variable region (Dμ). Positive selection is known to be mediated by membrane immunoglobulin heavy chains through Igα-Igβ, whereas the mechanism for counterselection against Dμ has not been determined. We have examined the role of the Igα-Igβ signal transducers in counterselection against Dμ using mice that lack Igβ. We found that Dμ expression is not selected against in developing B cells in Igβ mutant mice. Thus, the molecular mechanism for counterselection against Dμ in pre-B cells resembles positive selection in that it requires interaction between mDμ and Igα-Igβ.     

Nickel-foam-supported β-Ni(OH)2 as a green anodic catalyst for energy efficient electrooxidative degradation of azo-dye wastewater

Electrochemical oxidative degradation (EOD) is a particularly promising technique for removing organic pollutants from wastewater. However, due to the high overpotential of EOD in conventional anode materials, the energy cost of EOD is usually very high, which greatly promotes the search for highly active, stable, and energy-efficient anodic catalysts. Herein, we demonstrated that nickel-foam-supported (NF-supported) β-Ni(OH)₂ (NF/β-Ni(OH)₂) prepared via a facile hydrothermal method could be used as an energy efficient anode for EOD. The as-prepared 3D porous NF/β-Ni(OH)₂ exhibited high activity toward the electrochemical oxidation of methyl orange (MO) in the low potential region (<1.07 V vs. SCE). This property differs greatly from those of the conventional anode materials that require a high positive potential to keep them active for EOD, making NF/β-Ni(OH)₂ an energy-efficient and active anode material for EOD. With an oxidation current density of 0.25 mA cm⁻², the decolorization of MO was completed within 30 min, and the COD removal after 3h of reaction was 63.0%. The normalized energy consumption for the 3 h degradation of MO was 22.2 kW h (kg COD)⁻¹, which is only a fraction of (or even one tenth of) the values reported in the literature. Moreover, NF/β-Ni(OH)₂ had a good stability and recyclability for EOD. No activity decay was observed during 10 h of EOD and the COD removal remained almost unchanged after four consecutive reaction cycles. We demonstrated experimentally that the NF/β-Ni(OH)₂ anode could generate large amounts of hydroxyl radicals and that the oxidation of MO by hydroxyl radicals was the main mechanism during EOD. We believe that this work opens a new avenue for developing highly active and energy-efficient anode materials that can work in the low potential region for EOD.

A novel NF/β-Ni(OH)₂ catalyst for energy efficient electrochemical degradation of methyl orange was fabricated via a facile hydrothermal method.     

Hemoglobin Hasharon (α247 his(CD5)β2): a hemoglobin found in low concentration

Hemoglobin Hasharon (alpha(2) (47 his)(CD5)beta(2)) was found to comprise only 16-19% of hemolysates of carriers. These heterozygotes appeared to have mild, compensated, hemolytic anemia. Hb Hasharon was more heat-labile than hemoglobins A, S, or C. Its specific activity was higher than that of Hb A after administration of (59)Fe to two carriers. When hemoglobin synthesis by bone marrow cells was studied in vitro, about 18% of incorporated leucine appeared in the Hb Hasharon fraction. It is suggested that Hb Hasharon is unstable in vivo, and that mild hemolytic anemia and a relatively small decrease in its concentration in hemolysates result from its denaturation within red cells. Decreased synthesis, which appears to be the major cause of the small amount of abnormal hemoglobin, may protect heterozygotes from clinically significant hemolytic anemia.     

Synthesis,structural characterization and Cu(ii) adsorption behavior of manganite (γ-MnOOH) nanorods

New alternatives for the removal of transition metal ions that present an environmental risk are required. The chemical adsorption of these ions on surfaces with chemisorbent properties represents a promising area of research. In this work, manganite (γ-MnOOH) nanorods were synthesized, with a surface area of 20.22 m² g⁻¹, pore size of 32.18 nm and pore volume of 0.1627 cm³ g⁻¹. After chemical and structural characterization of the manganite sample, it was evaluated as an adsorbent of Cu(ii) from aqueous solution. The equilibrium adsorption data were well fitted by the Langmuir isotherm, and the results indicated that the maximum adsorption capacity of Cu(ii) was 11.926 mg g⁻¹. Cu(ii) ion adsorption on the manganite surface is a spontaneous and exothermic process (ΔG°< 0 and ΔH°< 0). The negative value of ΔS° suggests the stability of the adsorption process without structural change at the manganite–aqueous solution interface. A scheme for chemisorption of Cu(ii) ions on the hydroxylated surface of manganite is proposed.

Manganite (γ-MnOOH) nanorods were synthesized and Cu(ii) adsorption on their hydroxylated surface was a spontaneous process (ΔG° < 0).