Degree Of Hydroxylation Research Articles

Water dissociation on mixed Co–Fe oxide bilayer nanoislands on Au(111)

We investigate the hydroxylation behaviour of mixed Co–Fe oxide nanoislands synthesized on a Au(111) surface under exposure to water vapour at vacuum conditions. The pure Co and Fe bilayer oxides both become hydroxylated by water exposure in vacuum conditions, albeit to a very different extent. It is however an open question how mixed oxides, exposing sites with a mixed coordination to Fe and Co, behave. By forming surface O species with a mixed Fe/Co coordination, we can investigate the nature of such sites. By means of scanning tunnelling microscopy and x-ray photoelectron spectroscopy, we characterize a series of Co–Fe oxides samples with different Fe contents at the atomic scale and observe a scaling of the hydroxylation degree with the amount of Fe inside the Co–Fe oxides. Our results indicate that the Fe dopants within the Co–Fe oxides have opposing effects on edge and basal plane sites modifying the maximum hydroxylation degree of pure cobalt oxide, perturbing the original binding sites of H, releasing the absorbed H or blocking the diffusion pathway of H.

Hematite as an Electrocatalytic Marker for the Study of Archaeological Ceramic Clay bodies: A VIMP and SECM Study**

AbstractThe electrocatalytic effect exerted by hematite, a ubiquitous component of clay bodies, on the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) can be used to acquire information on archaeological ceramics. The solid‐state voltammetric response of different hematite and ochre specimens, accompanied by SECM analysis in contact with 0.10 M HCl aqueous solution, is described. In air‐saturated solutions, catalytic effects on the ORR and OER are accompanied by Fe(III)/Fe(II) and Fe(IV)/Fe(III) redox reactions. Such processes are conditioned by a variety of factors, the hydroxylation degree of the mineral surfaces being particularly influential, and exhibit significant variations upon heating the specimens between 300 and 900 °C. Voltammetric measurements carried out on a set of archaeological samples of Apulian red‐figured pottery dated back within 5th and 4th centuries BCE permit to obtain site‐characteristic voltammetric profiles.

Laser Desorption/Ionization Mass Spectrometry as a Potential Tool for Evaluation of Hydroxylation Degree of Various Types of Titanium Dioxide Materials.

For many applications, TiO2 must have a unique surface structure responsible for its desirable physicochemical properties. Therefore the fast and easy methods of TiO2 surface characterization are of great interest. Heated TiO2 samples and dye-modified TiO2 samples were analyzed by laser desorption/ionization mass spectrometry. In the negative ion mode, two types of ions were detected, namely (TiO2)n− and (TiO2)nOH−. It has been established that the samples can be differentiated based on the relative ion abundances, especially with respect to the free hydroxyl group population. It indicates that laser desorption ionization mass spectrometry has the potential for the investigation of the surface properties of various TiO2 materials.

Study on the chemical potential of apigenin, luteolin, quercetin, and myricetin using the molecular modeling

In the present paper, the chemical potential of four flavonoids i.e. apigenin, luteolin, quercetin, and myricetin, of interest in the pharmaceutical industry was investigated using molecular modelling. The equilibrium geometry of molecular structures was calculated in the gas phase and ground state by using B3LYP hybrid functional in conjunction with a 6-311G(d,p) basis set. In order to assess the chemical potential of investigated flavonoids, the main quantum molecular descriptors, such as the dipole moment, the energy of the highest/lowest occupied/unoccupied molecular orbital, the gap energy, the electronegativity, the chemical hardness/softness, and the electrophilicity index have been computed. Also, the influence of the hydroxylation degree of chemical compounds on the chemical potential is discussed.

Adsorption of Epoxy Oligomers on Iron Oxide Surfaces: The Importance of Surface Treatment and the Role of Entropy.

Epoxy-based coatings are widely used in a range of industries as protective coatings. The performance of the final solid-polymer system is dependent on the physicochemical properties of the interface and the interaction between the polymer and the solid substrate. In this study, we perform atomistic molecular dynamics simulations to investigate the binding of a common component in epoxy resins, diglycidyl ether of bisphenol A (DGEBA), on two iron oxide surfaces, hematite (0001) and magnetite (100), and investigate the effect of surface hydroxylation on the binding energy. We show that adsorption of DGEBA on hematite is more favorable than on magnetite and that the adsorbed molecules are highly localized on the pristine hematite surface but mobile on highly hydroxylated hematite surfaces and magnetite surfaces irregardless of surface hydroxylation fraction. A high degree of hydroxylation significantly reduces the binding energy of DGEBA on hematite but not on magnetite. The free-energy calculations confirm the trends observed upon hydroxylation, but the magnitude of the potential of mean force is lower than the binding energy due to the entropic contributions. Therefore, it can be suggested that DGEBA will adsorb more strongly on a surface containing a higher content of hematite than magnetite and that the presence of hydroxyl groups will weaken this adsorption. The presence of hydroxyl groups increases mobility of the chains, which can affect the coating rigidity.

Beyond Purple Tomatoes: Combined Strategies Targeting Anthocyanins to Generate Crimson, Magenta, and Indigo Fruit

The range of colours of many flowers and fruits is largely due to variations in the types of anthocyanins produced. The degree of hydroxylation on the B-ring affects the hue of these pigments, causing a shift from the orange end of the visible spectrum to the blue end. Besides colour, this modification can also affect other properties of anthocyanins, including the ability to protect the plant against different stresses or, when included in the human diet, to provide benefits for disease prevention. The level of hydroxylation of the B-ring is determined by the activity of two key hydroxylases, F3′H and F3′5′H, and by the substrate preference of DFR, an enzyme acting downstream in the biosynthetic pathway. We show that, in tomato, a strategy based on fruit-specific engineering of three regulatory genes (AmDel, AmRos1, AtMYB12) and a single biosynthetic gene (AmDFR), together with the availability of a specific mutation (f3′5′h), results in the generation of three different varieties producing high levels of anthocyanins with different levels of hydroxylation. These tomatoes show distinctive colours and mimic the classes of anthocyanins found in natural berries, thus providing unique near-isogenic material for different studies.

Initial hydration process of calcium silicates in Portland cement: A comprehensive comparison from molecular dynamics simulations

As the main components of Portland cement, calcium silicates show substantial differences in their hydration reactivity which have not been fully explained. A comprehensive comparison of the initial hydration process of calcium silicates, namely dicalcium silicate (C2S) and tricalcium silicate (C3S), was conducted using molecular dynamics simulations. The initial hydration process was divided into three stages using cut-off times of 0.001 ns and 3 ns. The hydration of M3-C3S (010) was more evident than that of β-C2S (100), supported by the hydroxylation degree, radial distribution function, atomic density profile, etc. The coordination number of the surface Ca atoms might be the underlying reason for such a difference. Interactions between cement surfaces and water molecules were mainly characterised by solid OH bonding and Ca-water O bonding. Dissolution of Ca atoms was observed, although quite scarce, while no dissolution of Si atoms was observed.

Synthesis and biological activity of N6-mannopyranosyladenines

In this work, potentially bioactive condensation products of adenine with D-mannose and 6-deoxy-L-mannose (L-rhamnose) were synthesized in water and ethanol solutions. According to FTIR spectroscopy and elemental analysis, mono-N6-glycosylated adenines were isolated from water systems in satisfactory yields, while ethanol solutions contained mixtures of N6 and N9-products, as well as complexes of the latter with copper ions. A detailed analysis of the vibrational spectra of N6-glycosyladenines confirmed the structure of carbohydrate fragments in the form of pyranose rings, while some part of the product was obtained in the form of deoxyaminoketosis. N-rhamnosyladenine was formed with a more than double yield because of a higher stability of rhamnose with regard to side reactions. The reflection spectra of model solutions of glycosyladenines, recorded 4 days after preparation, showed no bands characteristic of free adenine in the range of 1250-1110 cm-1, which indicates a sufficient resistance of the synthesized products towards hydrolytic cleavage under experimental conditions. The conducted biotesting of the isolated products on wheat seeds (Triticum aestivum L.) showed an increase in the content of chlorophylls in seedlings for both mannosilade-nines compared to the control. A decrease in the concentration of synthesized products in germination solutions from 0.1 to 0.001% led to an increase in the accumulation of photosynthetic pigments, while this effect was more pronounced for rhamnosyladenine. The latter can be connected with the structural features of car-bohydrate fragments, in particular, the differences in the hydroxylation degree of glucoside fragments. Future research will investigate the mechanisms of transformation and action of N6-substituted adenines.

Oxide-water interaction and wetting property of ceria surfaces tuned by high-temperature thermal aging

The high transmittance, environmentally robust, and unique interaction with water make lanthanide series rare-earth oxides promising for various applications such as next-generation self-cleaning coatings. However, the underlying mechanism of the anomalous hydrophobicity in lanthanide oxides remains controversial due to the lack of molecular-level studies in a well-controlled environment, which greatly limits the possibility to engineer their wettability for broader technical applications. Here, we systematically studied the mechanism that governs the wetting behaviors of ceria films by in-situ X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, and water contact angle measurements under the environmentally controlled conditions. It was found that the hydrophobicity of ceria was mainly contributed by the adsorbed hydrocarbon, and the wettability could be enhanced on cleaner ceria surfaces with more degree of hydroxylation. Based on the significant dependence of wetting property on surface contamination, we further developed an in-situ annealing method to significantly improve the water-splitting performance of ceria powders by removing hydrocarbon contamination. These results suggest that the removal of surface contamination by high-grade oxidation is the key factor to facilitate the water dissociation of ceria films, providing new insights into the control of their wetting property and design of high-performance devices based on ceria films.

Titanium and Protein Adsorption: An Overview of Mechanisms and Effects of Surface Features.

Titanium and its alloys, specially Ti6Al4V, are among the most employed materials in orthopedic and dental implants. Cells response and osseointegration of implant devices are strongly dependent on the body–biomaterial interface zone. This interface is mainly defined by proteins: They adsorb immediately after implantation from blood and biological fluids, forming a layer on implant surfaces. Therefore, it is of utmost importance to understand which features of biomaterials surfaces influence formation of the protein layer and how to guide it. In this paper, relevant literature of the last 15 years about protein adsorption on titanium-based materials is reviewed. How the surface characteristics affect protein adsorption is investigated, aiming to provide an as comprehensive a picture as possible of adsorption mechanisms and type of chemical bonding with the surface, as well as of the characterization techniques effectively applied to model and real implant surfaces. Surface free energy, charge, microroughness, and hydroxylation degree have been found to be the main surface parameters to affect the amount of adsorbed proteins. On the other hand, the conformation of adsorbed proteins is mainly dictated by the protein structure, surface topography at the nano-scale, and exposed functional groups. Protein adsorption on titanium surfaces still needs further clarification, in particular concerning adsorption from complex protein solutions. In addition, characterization techniques to investigate and compare the different aspects of protein adsorption on different surfaces (in terms of roughness and chemistry) shall be developed.

Poplar MYB117 promotes anthocyanin synthesis and enhances flavonoid B-ring hydroxylation by up-regulating the flavonoid 3',5'-hydroxylase gene.

Flavonoids, such as anthocyanins, proanthocyanidins, and flavonols, are widespread plant secondary metabolites and important for plant adaptation to diverse abiotic and biotic stresses. Flavonoids can be variously hydroxylated and decorated; their biological activity is partly dependent on the degree of hydroxylation of the B-ring. Flavonoid biosynthesis is regulated by MYB transcription factors, which have been identified and characterized in a diversity of plants. Here we characterize a new MYB activator, MYB117, in hybrid poplar (Populus tremula×tremuloides). When overexpressed in transgenic poplar plants, MYB117 enhanced anthocyanin accumulation in all tissues. Transcriptome analysis of MYB117-overexpressing poplars confirmed the up-regulation of flavonoid and anthocyanin biosynthesis genes, as well as two flavonoid 3',5'-hydroxylase (F3'5'H) genes. We also identified up-regulated cytochrome b5 genes, required for full activity of F3'5'H . Phytochemical analysis demonstrated a corresponding increase in B-ring hydroxylation of anthocyanins, proanthocyanidins, and flavonols in these transgenics. Similarly, overexpression of F3'5'H1 directly in hybrid poplar also resulted in increased B-ring hydroxylation, but without affecting overall flavonoid content. However, the overexpression of the cytochrome b5 gene in F3'5'H1-overexpressing plants did not further increase B-ring hydroxylation. Our data indicate that MYB117 regulates the biosynthesis of anthocyanins in poplar, but also enhances B-ring hydroxylation by up-regulating F3'5'H1.

CuWO4 with CuO and Cu(OH)2 Native Surface Layers for H2S Detection under in-Field Conditions.

The paper presents the possibility of detecting low H2S concentrations using CuWO4. The applicative challenge was to obtain sensitivity, selectivity, short response time, and full recovery at a low operating temperature under in-field atmosphere, which means variable relative humidity (%RH). Three different chemical synthesis routes were used for obtaining the samples labeled as: CuW1, CuW2, and CuW3. The materials have been fully characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). While CuWO4 is the common main phase with triclinic symmetry, different native layers of CuO and Cu(OH)2 have been identified on top of the surfaces. The differences induced into their structural, morphological, and surface chemistry revealed different degrees of surface hydroxylation. Knowing the poisonous effect of H2S, the sensing properties evaluation allowed the CuW2 selection based on its specific surface recovery upon gas exposure. Simultaneous electrical resistance and work function measurements confirmed the weak influence of moisture over the sensing properties of CuW2, due to the pronounced Cu(OH)2 native surface layer, as shown by XPS investigations. Moreover, the experimental results obtained at 150 °C highlight the linear sensor signal for CuW2 in the range of 1 to 10 ppm H2S concentrations and a pronounced selectivity towards CO, CH4, NH3, SO2, and NO2. Therefore, the applicative potential deserves to be noted. The study has been completed by a theoretical approach aiming to link the experimental findings with the CuW2 intrinsic properties.

Synthetic Biology Driven Biosynthesis of Unnatural Tropolone Sesquiterpenoids.

Tropolone sesquiterpenoids (TS) are an intriguing family of biologically active fungal meroterpenoids that arise through a unique intermolecular hetero Diels–Alder (hDA) reaction between humulene and tropolones. Here, we report on the combinatorial biosynthesis of a series of unprecedented analogs of the TS pycnidione 1 and xenovulene A 2. In a systematic synthetic biology driven approach, we recombined genes from three TS biosynthetic gene clusters (pycnidione 1, xenovulene A 2 and eupenifeldin 3) in the fungal host Aspergillus oryzae NSAR1. Rational design of the reconstituted pathways granted control over the number of hDA reactions taking place, the chemical nature of the fused polyketide moiety (tropolono‐ vs. monobenzo‐pyranyl) and the degree of hydroxylation. Formation of unexpected monobenzopyranyl sesquiterpenoids was investigated using isotope‐feeding studies to reveal a new and highly unusual oxidative ring contraction rearrangement.

Down-Regulation of Collagen Hydroxylation in Colorectal Liver Metastasis.

Collagen is significantly upregulated in colorectal liver metastasis (CRLM) compared to liver tissue. Expression levels of specific collagen types in CRLM resemble those in colorectal cancer (CRC) and colon tissue. We investigated whether the collagen hydroxylation pattern from the primary tumor also migrates with the metastatic tumor. The degree of collagen alpha-1(I) hydroxylation in colon, CRC, liver, and CRLM tissue of the same individuals (n = 14) was studied with mass spectrometry. The degree of hydroxylation was investigated in 36 collagen alpha-1(I) peptides, covering 54% of the triple helical region. The degree of hydroxylation in liver tissue was similar to that in colon tissue. The overall degree of hydroxylation was significantly lower (9 ± 14%) in CRC tissue and also significantly lower (12 ± 22%) in CRLM tissue compared to colon. Furthermore, eleven peptides with a specific number of hydroxylations are significantly different between CRLM and liver tissue; these peptides could be candidates for the detection of CRLM. For one of these eleven peptides, a matching naturally occurring peptide in urine has been identified as being significantly different between patients suffering from CRLM and healthy controls. The hydroxylation pattern in CRLM resembles partly the pattern in liver, primary colorectal cancer and colon.

Features of the Formation of Adsorption Centers of Thermally Modified High-Silica Porous Glasses

The results are presented on studies of the content of Lewis and Bronsted centers on the internal surface of high-silica porous glass (PG) obtained by the through chemical etching of alkali-borosilicate glass with the two-frame structure, including the one modified by an isothermal treatment in an electric furnace in air in the temperature range from 120 to 750°C. The content of the active surface centers is determined by the adsorption of the acid-base indicators with different рKа values. For all samples under investigation, the predominance of hydroxyl groups over siloxane ones is established, which indicates a high degree of surface hydroxylation; and the extreme dependence of the content of surface centers on the heat treatment temperature with the pronounced maximum at 650°C is found.

Studies of Dynamic Binding of Amino Acids to TiO2 Nanoparticle Surfaces by Solution NMR and Molecular Dynamics Simulations.

Adsorption of biomolecules onto material surfaces involves a potentially complex mechanism where molecular species interact to varying degrees with a heterogeneous material surface. Surface adsorption studies by atomic force microscopy, sum frequency generation spectroscopy, and solid-state NMR detect the structures and interactions of biomolecular species that are bound to material surfaces, which, in the absence of a solid-liquid interface, do not exchange rapidly between surface-bound forms and free molecular species in bulk solution. Solution NMR has the potential to complement these techniques by detecting and studying transiently bound biomolecules at the liquid-solid interface. Herein, we show that dark-state exchange saturation transfer (DEST) NMR experiments on gel-stabilized TiO2 nanoparticle (NP) samples detect several forms of biomolecular adsorption onto titanium(IV) oxide surfaces. Specifically, we use the DEST approach to study the interaction of amino acids arginine (Arg), lysine (Lys), leucine (Leu), alanine (Ala), and aspartic acid (Asp) with TiO2 rutile NP surfaces. Whereas Leu, Ala, and Asp display only a single weakly interacting form in the presence of TiO2 NPs, Arg and Lys displayed at least two distinct bound forms: a species that is surface bound and retains a degree of reorientational motion and a second more tightly bound form characterized by broadened DEST profiles upon the addition of TiO2 NPs. Molecular dynamics simulations indicate different surface bound states for both Lys and Arg depending on the degree of TiO2 surface hydroxylation but only a single bound state for Asp regardless of the degree of surface hydroxylation, in agreement with results obtained from the analysis of DEST profiles.

Structural characterization and in vitro immunogenicity evaluation of amphibian-derived collagen type II from the cartilage of Chinese Giant Salamander (Andrias davidianus)

Collagen type II (CT-II) has unique biological activities and functions, yet the knowledge on amphibian-derived CT-II is rare. Herein, acid-soluble collagen (ASC) and pepsin-soluble collagen (PSC) were successfully isolated and characterized from the cartilage of Chinese Giant Salamander (CGS). The in vitro immunogenicity of collagen was then evaluated and compared with that of the standard bovine CT-II (SCT-II) by T-lymphocyte cell proliferation activity. Results demonstrated that ASC and PSC were predominantly CT-II along with minor collagen type I and maintained intact triple-helical structure of nature collagen. Compared with SCT-II, higher glycine content (337.80 and 339.93 residues/1000 residues) and lower degree of proline hydroxylation (51.81% and 52.52%) were observed in ASC and PSC. Additionally, PSC showed comparable T d (63 °C) and higher T m (109 °C) than SCT-II (64 °C and 103 °C, respectively), indicating its high thermal and structural stability. SEM revealed that the lyophilized ASC and PSC had interconnected porous network structures of collagen-based materials. Moreover, different from SCT-II, both ASC and PSC presented no immunogenicity because they did not cause obvious proliferation of murine T-lymphocyte regardless of the induced concentration of collagen increased from 8 to 417 μg/mL. These data suggested that the amphibian-derived CGS cartilage collagens avoid the immunogenic risk of terrestrial animal collagen, and show high thermal stability and potential advantage in biomedical application.

Carboxylate-assisted synthesis of highly-defected monoclinic zirconia nanoparticles

Zirconia (ZrO2) nanoparticles were prepared by hydrothermal route using zirconium oxychloride (ZrOCl2) as a single precursor with different sodium carboxylates as mineralizers. The structure, morphology and defects of the nanoparticles were characterized by XRD, HRTEM and ATR-FTIR spectroscopy. X-ray diffraction studies revealed that the as-synthesized zirconia was pure monoclinic ZrO2 phase. The crystallite sizes were in the range 8.9–19.5 nm. The defects and microstrains of ZrO2 nanoparticles were greatly influenced by the type of sodium carboxylate. Apparently, there was a direct correlation between the stability constant of Zr(IV)-carboxylate complex and the amount of defects in the produced ZrO2. Sodium tartrate produced semicrysalline ZrO2 nanoparticles with microstarin that were 5 times greater than that produced without any carboxylate salt. ZrO2 nanoparticles with increased defects and microstarins were found to be rich with surface hydroxide groups. Designing monoclinic ZrO2 with controlled defects and degree of hydroxylation may have a great impact in heterogonous organic catalysis.

Collagen from Atlantic cod (Gadus morhua) skins extracted using CO2 acidified water with potential application in healthcare

The extraction of collagen from fish skins is being proposed as strategy for valorization of marine origin by-products, being a sustainable alternative to mammal collagen. The method commonly uses solutions of organic acids, but new methodologies are arising, aiming to improve process yields and/or the properties of the resulting products. In this work, skins removed from salt brine Atlantic cod (Gadus morhua) were used to extract collagen, using water acidified with CO2, obtaining an extraction yield of 13.8% (w/w). Acidified water extracted collagen (AWC) presented a total content of proline-like amino acids of 151/1000 residues, with a degree of hydroxylation of 38%, and its SDS-PAGE profile is compatible with type I collagen. Moreover, FTIR, CD and XRD results suggest the presence of preserved triple helix, having a denaturation temperature of 32.3 °C as determined by micro-DSC. AWC exhibited a typical shear thinning behavior, interesting regarding their further processing, namely in jelly-like formulations. Additionally, the presence of AWC in MRC-5 human fibroblasts culture did not affect cell viability, demonstrating the non-cytotoxic behavior. Overall, the results support the efficiency of the proposed approach for collagen extraction and further enable the design of methodologies to address AWC use in biomedical or cosmetic context.

L-Lysine-modified Fe3O4 nanoparticles for magnetic cell labeling

The efficiency of magnetic labeling with L-Lys-modified Fe3O4 magnetic nanoparticles (MNPs) and the stability of magnetization of rat adipose-derived mesenchymal stem cells, lineage-negative (Lin(–)) hematopoietic progenitor cells from mouse bone marrow and human leukemia K562 cells were studied. For this purpose, covalent modification of MNPs with 3-aminopropylsilane and N-di-Fmoc-L-lysine followed by removal of N-protecting groups was carried out. Since the degree of hydroxylation of the surface of the starting nanoparticles plays a crucial role in the silanization reaction and the possibility of obtaining stable colloidal solutions. In present work we for the first time performed a comparative qualitative and quantitative evaluation of the number of adsorbed water molecules and hydroxyl groups on the surface of chemically and physically obtained Fe3O4 MNPs using comprehensive FTIR spectroscopy and thermogravimetric analysis. The results obtained can be further used for magnetic labeling of cells in experiments in vitro and in vivo.