Preparation and in vitro apatite-forming ability of hydroxyapatite and β-wollastonite composite materials

This paper provides a one-step method of preparation of the ceramic powders, containing various amounts of hydroxyapatite (HA) and β-wollastonite (WT), based on the salt coprecipitation and subsequent thermal treatment of the synthesis products at 1000?°C. Aqueous solutions of Ca(OH)₂, H₃PO₄ and Na₂SiO₃ were used as precursors of Ca₁₀(PO₄)₆(OH)₂ and β-CaSiO₃, as a minimal amount of by-product is formed during such an interaction of reagents. Variation of the concentration of the initial reagents allows the preparation of ceramic powders containing from 0 to 100?wt% of apatite. All composites were examined by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), laser diffraction analysis and an adsorption method (BET). Degradability of composite powders was analyzed in the Tris-HCl buffer solution. The apatite-forming ability of synthetic composites was investigated by soaking composite ceramics in a simulated body fluid (SBF). The results that were obtained reveal an increase in the dissolution rate of powders with wollastonite addition. Soaking of the composite ceramics in SBF leads to the formation of a bone-like apatite spherical particle layer on their surfaces, which become thicker while the content of β-СаSiO₃ in the samples increases.     

Characterization of silica-coated silver nanoparticles prepared by a reverse micelle and hydrolysis–condensation process

Described herein is the synthesis of individually silica-coated silver nanoparticles using a reverse micelle method followed by hydrolysis and condensation of tetraethoxysilane (TEOS). The size of a silica-coated silver nanoparticle can be controlled by changing the reaction time and the concentration of TEOS. By maintaining the size of a silver nanoparticle as a core particle at around 7 nm, the size of a silica-coated silver nanoparticle increased from 13 to 28 nm as the reaction time increased from 1 to 9 h due to an increase in silica thickness. The size of silica-coated silver nanoparticles also increased from 15 to 22 nm as the TEOS concentration increased from 7.8 to 40 mM. The size of a silica-coated silver nanoparticle can be accurately predicted using the rate of the hydrolysis reaction for TEOS. Neither the dispersion nor the film of silica-coated silver nanoparticles exhibited any peak shifting during surface plasmon resonance (SPR) at around 410 nm, whereas, without silica coating, the SPR peak of Ag film shifted to 466 nm.     

The effect of magnesium content on in vitro bioactivity,biological behavior and antibacterial activity of sol–gel derived 58S bioactive glass

Bioactive glasses (BGs) have a great potential for bone replacement and regeneration in bone tissue engineering applications. In this research, first, sol–gel derived magnesium substituted 58?S BGs (MBGs) series composed of 60SiO₂–4P₂O₅-(36-x) CaO- xMgO, (x = 0; 1; 3; 5; 8 and 10?mol.%) were synthesized and stabilized at 700?°C to eliminate the nitrates and prevent the crystallization of MBGs. MgO was substituted for CaO in the BG formula up to 10?mol% and the effect of Mg concentration on in vitro bioactivity and cellular properties of the MBGs were investigated by immersing them in simulated body fluid (SBF) followed by structural characterization using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) techniques. The effects Mg on proliferation and differentiation of osteoblastic MC3T3-E1 cells were also evaluated by 3-(4,5dimethylthiazol-2-yl)??2,5-diphenyltetrazolium bromide (MTT) and alkaline phosphate (ALP) activity.Results revealed that magnesium-substituted 58?S BG with 5?mol% MgO (BG-5) had the highest formation rate of hydroxyapatite (HA) while substitution of 8?mol% and10 mol% MgO (BG-8 and BG-10) lowered the bioactivity. MTT and ALP results confirmed that the substitution of the MgO up to 5?mol% increased both proliferation and differentiation of MC3T3-E1 cells, while more substitution had a negative effect and resulted in a decrease of proliferation and differentiation in BG-8 and BG-10. The result of antibacterial test showed that MBGs exhibited antibacterial effect against methicillin-resistant Staphylococcus aureus (MRSA) bacteria. Taken together, results suggest that, among all the synthesized MBGs, sample BG-5 is a promising candidate as multifunctional biomaterial for bone tissue engineering with maximum cell proliferation and ALP activity, good bioactivity and high antibacterial efficiency against MRSA bacteria. Eventually, the BG-5 is suggested to be used in segmental defects in rat model in vivo.     

Facile synthesis,antibacterial mechanisms and cytocompatibility of Ag–MnFe2O4 magnetic nanoparticles

Magnetic MnFe₂O₄ nanoparticles containing 0, 1 and 3 at.% silver, respectively were synthesized by one-pot sol-gel method for antibacterial applications in biomedical fields. Material characterizations indicate that MnFe₂O₄ begins crystallization at 134 °C and oxidation at 450 °C, the grain size and agglomeration degree increase with the silver content and silver exists as metallic state for the particles. The saturation magnetization decreases with the sintering temperature and slightly increases with the silver content, with the maximum of 50.0 emu/g obtained. Antibacterial tests by plate counting and PI-Hoechst 33342 staining suggest that the antibacterial activity of Ag–MnFe₂O₄ nanoparticles is silver content-dependent. Silver ions concentration measurement, β-galactosidase activity assay and transmission electron microscopic observation show that the antibacterial activity is dominated by the actions of the released silver ions, rather than the membrane cell impairment or reactive oxygen species-induced oxidative stress mechanism. MC3T3-E1 cell test demonstrates the best cytocompatibility of the nanoparticles with 3 at.% silver, which is likely related to the reduced cell endocytosis of the aggregated particles. The combination of magnetism, antibacterial activity and biocompatibility would make Ag–MnFe₂O₄ nanoparticles a potential multi-functional material in various biomedical applications.     

Sol–gel synthesis,characterization, and neurotoxicity effect of zinc oxide nanoparticles using gum tragacanth

The use of plant extract in the synthesis of nanomaterials can be a cost effective and eco-friendly approach. In this work we report the “green” and biosynthesis of zinc oxide nanoparticles (ZnO-NPs) using gum tragacanth. Spherical ZnO-NPs were synthesized at different calcination temperatures. Transmission electron microscopy (TEM) imaging showed the formation most of nanoparticles in the size range of below 50 nm. The powder X-ray diffraction (PXRD) analysis revealed wurtzite hexagonal ZnO with preferential orientation in (101) reflection plane. In vitro cytotoxicity studies on neuro2A cells showed a dose dependent toxicity with non-toxic effect of concentration below 2 µg/mL. The synthesized ZnO-NPs using gum tragacanth were found to be comparable to those obtained from conventional reduction methods using hazardous polymers or surfactants and this method can be an excellent alternative for the synthesis of ZnO-NPs using biomaterials.     

PLLA–silver nanoparticles bionanocomposite membranes: Preparation,antibacterial activity,and in vitro hydrolytic degradation assessment

Silver nanoparticles (AgNp) were synthesized in aqueous phase and transferred to chloroform using a fatty amine as phase transfer agent. Poly(l -lactic acid) (PLLA) membranes were prepared using the “functionalized” chloroform. The amount of AgNp in the chloroform was determined by atomic absorption spectroscopy. Thermogravimetric analysis, differential scanning calorimetry, and field emission scanning electron microscopy were used to characterize the membranes. A decrease of the thermal stability of the membranes was observed upon the addition of AgNp; meanwhile, the polymer crystallinity degree increased, making the membranes more fragile and brittle. The in vitro degradation assessments of the membranes in artificial saliva suggested that the time necessary to degrade the PLLA reduced by raising the concentration of the nanostructures. Additionally, the antibacterial assays demonstrated that the addition of only 13 ppm of AgNp were enough to inhibit the formation of biofilm over the bionanocomposite membranes. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47998.     

Structural and thermal analysis of in situ synthesized C–WC nanocomposites

Nanostructure of carbon encapsulated tungsten carbide (WC@C) has been prepared using reaction between metallic magnesium (Mg), acetone (C₃H₆O) and tungsten trioxide (WO₃) in an autoclave at 600 °C. The resultant powders were characterized by X-ray diffraction (XRD), differential thermal analysis/thermal gravimetric analysis and transmission electron microscopy (TEM). The XRD results showed that the optimization of the reaction time facilitates the reduction as well as carburization of the tungsten source. The apparent activation energy for decarburization of carbide phase was also evaluated from the data of thermal analysis to find the thermal stability of carbide phase. TEM image showed that the synthesized sample consisted of particles with an average size of 35 nm.     

Synthesis of Fe–Pr co-doped ZnO nanoparticles: Structural,optical and antibacterial properties

In the present work, we studied the role of Fe and Pr addition on the structural, optical and antibacterial properties of spherical ZnO nanoparticles synthesized via sol gel method. The lattice constants values increased, while the average crystallite size decreases as the Pr concentration varies from 0.00 to 0.04. The Fe and Pr cations insertion in the Wurtzite structure were also confirmed by the changes in Zn–O bond length (1.9763 Å to 1.9793 Å for 0.00 ≤ y ≤ 0.04). Raman and FTIR spectroscopies validated the ZnO single-phase formation, and the analysis suggests the existence of oxygen vacancies. The samples showed agglomerated spherical morphology and formation of nanoplate homogeneously organized, while the textural properties were affected by the Fe inclusion. All samples presented band gap values lower than expected for bulk ZnO and the lowest values were obtained for samples containing Fe and Pr. The analysis and deconvolution of photoluminescence spectra confirmed the structural defects formation, caused by the synthesis conditions used and dopants ions inclusion. The antimicrobial activity against Escherichia coli and Staphylococcus aureus using the direct contact method showed superior activity for S. aureus due to the nanoparticles-bacteria interactions. The synergistic effect of dopants may have contributed to the better performance observed against S. aureus, while the Pr concentration directly influenced the inhibitory effect of E. coli. Therefore, the synthesized materials are promising to eliminate pathogenic microorganisms.     

Characterization of doped tin dioxide anodes prepared by a sol–gel technique and their application in an SPE-reactor

Anodes for the electrocatalytic oxidation of organic pollutants in water have been prepared by depositing novel Sb-doped SnO₂ material on Ti supports by the sol–gel technique. Surface analysis of the anodes by nuclear microprobe and XPS-measurements confirmed the formation of a doped film on the substrate. Large scale porous titanium electrodes, up to 50 cm², have been coated with doped SnO₂ for a galvanostatic solid polymer electrolyte (SPE) application, resulting in very low voltage across the stack, even without adding supporting electrolytes to the water. Assessment of the cell performance was carried out using N,N-dimethyl-p-nitrosoaniline (RNO) as a spin trap for ·OH-radicals and phenol as a standard organic contaminant. Kinetic studies were done for the formation of the ·OH-radicals.     

Compressive strength and preliminary in vitro evaluation of gypsum and gypsum–polymer composites in protein-free SBF at 37 °C

Gypsum is a bioresorbable material that has been used in many applications such as tissue regeneration. Mechanical properties of gypsum have limited its applications to non-load bearing sites. The current study aimed at studying the compressive strength and behaviour of gypsum–polymer composites in protein-free simulated body fluids (SBF). Polymers studied were poly(vinyl alcohol) (PVA) and its copolymers with vinyl acetate and itaconic acid in addition to vinyl acetate and vinyl chloride. Composites with the highest compressive strength results were chosen for the preliminary in vitro evaluation in protein-free SBF solutions. Changes in the concentrations of Ca²⁺ and PO₄³⁻ ions, weight loss and morphology of the solid samples were monitored after soaking them in SBF and 1.5 SBF solutions. Results showed resorption of gypsum, concurrently with deposition of apatite in all composites, including polymer-free gypsum. Mechanical integrities of all samples were maintained, suggesting their stabilities when used as bone cements.     

Phase behavior,in vitro drug release,and antibacterial activity of thermoresponsive poloxamer–polyvinyl alcohol hydrogel-loaded mupirocin nanoparticles

This research was designed to develop thermoresponsive poloxamer (P407)–polyvinyl alcohol (PVA) hydrogels to deliver mupirocin nanoparticles for wound healing. The mupirocin nanoparticles containing drug and gelatin or poly (acrylic acid) were prepared by spray drying. The hydrogel phases were evaluated by small-angle X-ray scattering. An in vitro drug release study was performed and the antibacterial activity of mupirocin nanoparticles-loaded hydrogel (MLH) was evaluated. Fourier transform infrared and proton nuclear magnetic resonance spectrum spectra of the mupirocin nanoparticles indicated a weak interaction between mupirocin and the carriers of carbopol and gelatin. The mupirocin molecules were surrounded by the carrier molecules. The MLH appeared to exhibit single diamond (Fd3m) phase behavior similar to P407 and the hydrogel base. The release of MLH in vitro indicated first-order kinetics (R² = .9839–.8868). The MLH showed lower minimum inhibitory concentrations and minimum bactericidal concentrations against Staphylococcus aureus, Staphylococcus epidermidis, Pseudomonas aeruginosa, and Escherichia coli than mupirocin ointment.     

Biomolecule-entrapped SiO2 nanoparticles for ultrafast green synthesis of silver nanoparticle–decorated hybrid nanostructures as effective catalysts

Noble-metal hybrid nanostructures have gained tremendous attention due to their potential roles in biomedical and catalytic applications. In this study, for the synthesis of silver nanoparticles (Ag NPs)–silica (SiO₂) NPs, a novel green chemistry approach was employed, in which green tea biomolecule–encapsulated SiO₂ nanostructures were used for the reduction of silver ions to produce hybrid nanostructures within 300?s. The high-resolution transmission electron microscopy (HrTEM) revealed the formation of uniform ultrafine spherical Ag NPs that were evenly distributed in the nanostructures. The formed nanohybrid structures showed efficient catalytic activity for the formation of derivatives of dihydroquinoline, and retained 91% of their reusability capacity, even after 5 repeated cycles. Hence, this work provides a novel synthesis method not only for the synthesis of biomolecule-entrapped SiO₂ nanostructures, but also for the rapid formation of catalytically active hybrid nanostructures.     

Comparison of PdCo/SBA-15 prepared by co-impregnation and sequential impregnation for Fischer–Tropsch synthesis

Properties and catalytic performance of bimetallic Pd–Co/SBA-15 prepared by co-impregnation (0.2Pd–10Co-CIP) and sequential impregnation (0.2Pd–10Co-SIP) for Fischer–Tropsch synthesis (FTS) were investigated. After calcination, Co₃O₄ was formed and located inside the channels of SBA-15 and on external surface. Compared to 0.2Pd–10Co-SIP, 0.2Pd–10Co-CIP had a smaller surface area, pore size, lower reduction temperature and less active sites due to larger particle sizes of Co₃O₄. From FTS testing, 0.2Pd–10Co-SIP provided higher and steadier conversions of CO and H₂ as well as higher yield of C₅–C₉ products.     

Morphological,structural and ellipsometric investigations of Cr doped TiO2 thin films prepared by sol–gel and spin coating

Pure and chromium doped titanium dioxide (TiO₂) thin films at different atomic percentages (0.5%, 1.3% and 2.9%) have been elaborated on ITO/Glass substrates by sol–gel and spin–coating methods using titanium (IV) isopropoxide as a precursor. The surface morphology of films was investigated by scanning electron microscopy (SEM) and Atomic Force Microscopy (AFM), the structure was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and high resolution transmission microscopy (HRTEM). SEM and HRTEM show homogenous and polycrystalline films. XRD patterns indicate a phase transition from anatase to anatase-rutile leading to expand the absorption band of TiO₂ molecules around 520 cm⁻¹ in FTIR spectra. The optical constants such as the refractive index (n), the extinction coefficient (K) and the band gap (E_g) as well as the film thickness are determined using spectroscopic ellipsometry technique and Fourouhi–Blommer dispersion model. Results show three major changes; (i) the thickness of pure TiO₂ layer is 54 nm, which linearly decreases when the layer is doped with chromium and reaches 33 nm for a doping concentration of 2.9%, (ii) the band gap energy (E_g) is also linearly reduced from 3.24 eV to 2.80 eV when the Cr-doping agent increases, and, (iii) a phase transition from anatase to anatase-rutile is observed causing an increase in values of n(λ) for wavelength greater than 350 nm.     

Effect of Zn substitution on the AC induction heating properties of ZnxMn1-xFe2O4 (x = 0.1–0.9) nanoparticles prepared using microwave assisted synthesis

Zn_xMn_1-xFe₂O₄ (x = 0.1–0.9) magnetic nanoparticles (MNPs) were prepared using a microwave-assisted coprecipitation method, and the effect of Zn substitution on the AC induction heating properties of the MNPs was investigated. With increasing Zn substitution, owing to the lower solubility product of Zn²⁺ ions, the formation of new nuclei was preferred over grain growth, which reduced the average crystallite size. The saturation magnetization initially increased with Zn substitution, attained the maximum value at x = 0.5, and decreased beyond that due to Yafet-Kittel type triangular spin ordering. The prepared MNPs exhibited superparamagnetic behaviour at ～ 300 K. AC induction heating studies of the MNPs indicated a specific absorption rate of ～ 130 ± 4 W/g_Fe at x = 0.1. The AC induction heating efficiency did not exhibit any non-monotonic variation at x = 0.5, and progressively decreased with increasing Zn concentration. This was attributed to the reduction in the MNP size and anisotropy energy density at higher Zn concentration that caused the relaxation dynamics to be Nèel dominated with lower effective relaxation time. AC induction heating studies on the agar-immobilized samples confirmed the Brownian relaxation mediated magneto-thermal energy conversion at lower Zn concentration. The obtained results demonstrated that saturation magnetization alone does not influence the AC induction heating efficiency and relaxation dynamics play a significant role.     

Natural fuel assisted synthesis of Mg–Cu ferrite nanoparticles: Evaluation of structural,dielectric, magnetic and humidity sensing properties

The effects of lemon juice and annealing treatment on phase composition, vibrational modes, microstructural and dielectric behavior of Mg doped copper ferrite nanoparticles have been synthesized and analyzed in detail in this present work. The various characterization techniques are used to examine the phase, microstructural, vibrational and dielectric nature of the samples at different annealing temperatures (600 °C and 900 °C). The phase and microstructure of Mg substituted CuFe₂O₄ nanoparticles have been analyzed by XRD, SEM and TEM. The secondary phase peaks free XRD spectra revealed that the as burst and the annealed Mg–CuFe₂O₄ nanoparticles have single phase cubic spinel structure. The average crystallite size of the as burnt, annealed 600 °C and annealed 900 °C of as prepared nanoparticles are calculated as 8.9 nm, 12.8 nm and 31.6 nm respectively. Another verification of the spherical shaped particle's size was confirmed by TEM analysis and it found as average size of 28.7 nm, this result is well matched with XRD analysis. The effect of size with impact of annealing treatment on magnetic and dielectric properties also analyzed. The size-dependent Mg–CuFe₂O₄ nanostructures exhibit promising sensing properties which ensure them as a potential candidate for humidity sensor applications. The as-burnt and annealed samples both show a humidity response over the humid range of 10–95 %RH. The sample annealed at 900 °C has the highest average sensor response (6.02 MΩ/%RH) among the as-burnt sample (6.38 MΩ/%RH) and annealed sample at 600 °C (7.11 MΩ/%RH).     

A study on the catalytic performance of Pd/γ-Al2O3, prepared by microwave calcination, in the direct synthesis of dimethylether

A series of Pd/γ-Al₂O₃ hybrid catalysts were prepared by impregnation and subsequent calcination under microwave irradiation. The catalysts were used for direct synthesis of dimethylether (DME) from syngas. The results show that calcination under microwave irradiation improved both the activity and selectivity of the catalysts for DME synthesis. The optimum power of the microwave was determined to be 420 W. Under such optimum conditions, CO conversion, DME selectivity and time space yield of DME were 60.1%, 67.0%, and 21.5 mmol·mL⁻¹·h⁻¹, respectively. Based on various characterizations such as nitrogen physisorption, X-ray diffraction, CO-temperature- programmed desorption, and Fourier transform infrared spectral analysis, the promotional effect of the microwave irradiation on the catalytic property was mainly attributed to both the higher dispersion of Pd and the significant increase in the adsorption on the CO-bridge of Pd. Microwave irradiation with very high power led to the increase in CO-bridge adsorption and thereby decreased the catalytic activity, whereas the coverage by metallic Pd of the active sites on acidic γ-Al₂O₃ significantly occurred under microwave irradiation with very low power, resulting in a decrease in the selectivity to DME.     

Structural,magnetic, and electrical evaluations of rare earth Gd3+ doped in mixed Co–Mn spinel ferrite nanoparticles

The controlled and stable crystal structure, reduction in Curie temperature and semiconducting nature of oxide materials are the key factors for magnetoelectrical applications. Therefore, Co_0.6Mn_0.4Gd_xFe_2-xO₄ where x = 0, 0.033, 0.066 and 0.10 were synthesized to analyse the structural, morphological, magnetic, and electrical properties using a sol-gel autocombustion approach. The X-ray diffraction pattern reveals that the cubic crystallite size decreases with increasing smaller content of Gd³⁺ oxides without any secondary phase. Field emission scanning electron microscopy (FE-SEM) and high-resolution transmission electron microscopy (HR-TEM) study explain the complete morphology, agglomeration and dense structure of rare earth-doped Gd oxide in the mixed Co–Mn spinel ferrite nanoparticles. Fourier transform infrared spectra confirms the formation of a spinel structure with absorption bands below 1000 cm^?1. The magnetic analysis shows that the saturation magnetization (59.20 emu/g - 49.71 emu/g) and coercivity (985.21 Oe – 254.11 Oe) of the synthesized samples decreased with increasing content of Gd³⁺ ions. The increase in DC conductivity with increasing temperature verifies the semiconducting nature of the synthesized samples, and a higher DC conductivity of the Co_0.6Mn_0.4Gd_0.10Fe_1.90O₄(CMGF3) samples was observed at approximately 0.0362 S/cm at 973 K temperature.     

Structural,optical, electrical,dielectric, molecular vibrational and magnetic properties of La3+ doped Mg–Cd–Cu ferrites prepared by Co-precipitation technique

Ferrites are among the most frequently investigated materials mainly due to interesting and practically different properties. Therefore, easily and cost-effective lanthanum doped Mg_0.5Cd_0.25Cu_0.25Fe_2-xLa_xO₄ (x = 0.0, 0.0125, 0.025, 0.0375 and 0.05) ferrites were synthesized by a co-precipitation route, a comprehensive characterisation of their structural, optical, electric, dielectric, molecular vibrational, and magnetic properties were carried out. X-ray diffraction analysis confirmed the formation of a cubic spinel structure. Variations in frequency bands were also observed with amplification in optical band gap energy (2.95 – 3.38 eV) due to La³⁺ ions insertion. The electric resistivity had opposite trends at low and high temperatures with increasing La³⁺ content. The Curie temperature, activation energy, and drift mobility were also determined to have values consistent with the semiconducting behavior of the soft ferrites. The saturation magnetization (M_S) has a maximum value 49.385 emu/g with remanent magnetization (M_r) was 34.928 emu/g and coercivity 661.4 Oe for La³⁺ concentration x = 0.05. The minimum dielectric loss was observed for La³⁺ concentration x = 0.025. Moreover, the resistivity (ρ) has a maximum value of 7.95 × 10⁴ Ω cm for La³⁺ concentration x = 0.025. The calculated frequency range of La³⁺ doped Mg–Cd–Cu ferrites was detected in the microwave range (3.36 – 10.80 GHz), suggesting the potential application of the materials in longitudinal recording media and microwave absorbance.     

The role of zinc oxide in Cu/ZnO catalysts for methanol synthesis and the water–gas shift reaction

All commercial catalysts for methanol synthesis and for the water–gas shift reaction in the low temperature region contain zinc oxide in addition to the main active component, copper. The varied benefits of zinc oxide are analysed here. The formation of zincian malachite and other copper/zinc hydroxy carbonates is essential in the production of small, stable copper crystallites in the final catalyst. Further, the regular distribution of copper crystallites on the zinc oxide phase ensures long catalyst life. Zinc oxide also increases catalyst life in the water–gas shift process by absorbing sulphur poisons but it is not effective against chloride poisons. In methanol synthesis, zinc oxide (as a base) removes acidic sites on the alumina phase which would otherwise convert methanol to dimethyl ether. Although bulk reduction of zinc oxide to metallic zinc does not take place, reduction to copper–zinc alloy (brass) can occur, sometimes as a surface phase only. A new interpretation of conflicting measurements of adsorbed oxygen on the copper surfaces of methanol synthesis catalysts is based on the formation of Cu–O–Zn sites, in addition to oxygen adsorbed on copper alone. The possible role of zinc oxide as well as copper in the mechanisms of methanol synthesis is still the subject of controversy. It is proposed that, only under conditions of deficiency of adsorbed hydrogen on the copper phase, hydrogen dissociation on zinc oxide, followed by hydrogen spillover to copper, is significant. This revised version was published online in June 2006 with corrections to the Cover Date.