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Molecules (Basel, Switzerland) Jun 2024In this study, the optimal microwave-assisted sol-gel synthesis parameters for achieving TiO nanoparticles with the highest specific surface area and photocatalytic...
In this study, the optimal microwave-assisted sol-gel synthesis parameters for achieving TiO nanoparticles with the highest specific surface area and photocatalytic activity were determined. Titanium isopropoxide was used as a precursor to prepare the sol (colloidal solution) of TiO. Isopropanol was used as a solvent; acetylacetone was used as a complexation moderator; and nitric acid was used as a catalyst. Four samples of titanium dioxide were synthesized from the prepared colloidal solution in a microwave reactor at a temperature of 150 °C for 30 min and at a temperature of 200 °C for 10, 20, and 30 min. The phase composition of the TiO samples was determined by X-ray diffraction analysis (XRD) and Fourier-transform infrared spectroscopy (FTIR). Nitrogen adsorption/desorption isotherms were used to determine the specific surface area and pore size distributions using the Brunauer-Emmett-Teller (BET) method. The band-gap energy values of the TiO samples were determined by diffuse reflectance spectroscopy (DRS). The distribution of Ti and O in the TiO samples was determined by SEM-EDS analysis. The effects of adsorption and photocatalytic activity of the prepared TiO samples were evaluated by the degradation of ciprofloxacin (CIP) as an emerging organic pollutant (EOP) under UV-A light (365 nm). The results of the photocatalytic activity of the synthesized TiO nanoparticles were compared to the benchmark Degussa P25 TiO. Kinetic parameters of adsorption and photocatalysis were determined and analyzed. It was found that crystalline TiO nanoparticles with the highest specific surface area, the lowest energy band gap, and the highest photocatalytic degradation were the samples synthesized at 200 °C for 10 min. The results indicate that CIP degradation by all TiO samples prepared at 200 °C show a synergistic effect of adsorption and photocatalytic degradation in the removal process.
PubMed: 38930999
DOI: 10.3390/molecules29122935 -
Molecules (Basel, Switzerland) Jun 2024In-depth insights into the oligomers of carbon dots (CDs) prepared from small-molecule precursors are important in the study of the carbonization mechanism of CDs and...
In-depth insights into the oligomers of carbon dots (CDs) prepared from small-molecule precursors are important in the study of the carbonization mechanism of CDs and for our knowledge of their complex structure. Herein, citric acid (CA) and ethylenediamine (EDA) were used as small-molecule precursors to prepare CDs in an aqueous solution. The structure of oligomers acquired from CA and EDA in different molar ratios and their formation process were first studied using density functional theory, including the dispersion correction (DFT-D3) method. The results showed that the energy barrier of dimer cyclization was higher than that of its linear polymerization, but the free energy of the cyclized product was much lower than that of its reactant, and IPCA (5-oxo-1,-2,3,5-tetrahydroimidazo [1,2-a]pyridine-7-carboxylic acid) could therefore be obtained under certain conditions. The oligomers obtained from different molar ratios of EDA and CA were molecular clusters formed by short polyamide chains through intermolecular forces; with the exception of when the molar ratio of EDA to CA was 0.5, excessive CA did not undergo an amidation reaction but rather attained molecular clusters directly through intermolecular forces. These oligomers exhibited significant differences in their surface functional groups, which would affect the carbonization process and the surface structure of CDs.
PubMed: 38930988
DOI: 10.3390/molecules29122920 -
The Grafting of Hydroxyaromatic Organics within Layered Perovskites via a Microwave-Assisted Method.Molecules (Basel, Switzerland) Jun 2024A new series of inorganic-organic hybrid perovskite materials were prepared by microwave-assisted grafting reactions. Simple carboxylic acids, acetic acid, and propionic...
A new series of inorganic-organic hybrid perovskite materials were prepared by microwave-assisted grafting reactions. Simple carboxylic acids, acetic acid, and propionic acid, as well as hydroxyaromatic carboxylic acids, 3,5-dihydroxy benzoic acid (DBA), 5-hydroxyisophthalic acid (HPA), 4-hydroxybenzoic acid (HBA), and 4-hydroxy-4-biphenyl carboxylic acid (HBCA), were reacted with the Dion-Jacobson double-layered perovskite, HLaNbO and its alcoxy derivatives. Grafting was found to not occur with simple carboxylic acids, while those molecules with hydroxyls were all attached to the perovskite interlayers. Reactivity of the hydroxyaromatic carboxylic acids varied with the different layered perovskite hosts where reactions with HLaNbO did not occur, and those with n-propoxy-LaNbO were limited; the greatest extent of reactivity was seen with n-decoxy-LaNbO. This is attributed to the larger interlayer spacing available for the insertion of the various hydroxyaromatic carboxylic acid compounds. The loading exhibited by the grafting species was less than that seen with well-known long-chain alkoxy grafting groups. It is expected that the width of the molecules contributes to this where, due to the benzyl groups, the interlayer volume of the grafted moieties occupies a larger horizontal fraction, therefore minimizing the loading to the below half. X-ray powder diffraction and transmission electron microscopy studies found that grafting of the n-decoxy-LaNbO intermediates with the series of hydroxyaromatics resulted in a reduction in crystallinity along with a disruption of the layer structure. Raman data on the series show little variation in local structure except for HBCA, where there appears to be a lengthening of the Nb-O apical linkage and a possible reduction in the distortion of inner-layer NbO octahedra. The optical properties of the hydroxyaromatic carboxylic acid grafted perovskites were also investigated using diffuse-reflectance UV-Vis spectroscopy. The band gaps of DBA, HPA, and HBA were found to be similar to the parent (E ≈ 3.4 eV), while the HBCA was significantly less by ca. 0.6 eV. This difference is attributed to electron withdrawal from the perovskite block to the HBCA ligand, leading to a lower band gap for the HBCA compound. The methods described herein allow for the formation of a new series of inorganic-organic hybrid materials where the products are of interest as precursors to more complex architectures as well as models for band gap modification of metal oxide photocatalysts.
PubMed: 38930953
DOI: 10.3390/molecules29122888 -
Molecules (Basel, Switzerland) Jun 2024The selective hydrogenation of the biomass platform molecule furfural (FAL) to produce furfuryl alcohol (FA) is of great significance to alleviate the energy crisis....
The selective hydrogenation of the biomass platform molecule furfural (FAL) to produce furfuryl alcohol (FA) is of great significance to alleviate the energy crisis. Cu-based catalysts are the most commonly used catalysts, and their catalytic performance can be optimized by changing the preparation method. This paper emphasized the effect of calcination atmosphere on the performance of a Cu/AlO catalyst for the selective hydrogenation of FAL. The precursor of the Cu/AlO catalyst prepared by the ammonia evaporation method was treated with different calcination atmospheres (N and air). On the basis of the combined results from the characterizations using in situ XRD, TEM, NO titration, H-TPR and XPS, the Cu/AlO catalyst calcined in the N atmosphere was more favorable for the dispersion and reduction of Cu species and the reduction process could produce more Cu and Cu species, which facilitated the selective hydrogenation of FAL to FA. The experimental results showed that the N calcination atmosphere improved the FAL conversion and FA selectivity, and the FAL conversion was further increased after reduction. Cu/AlO-N-R exhibited the outstanding performance, with a high yield of 99.9% of FA after 2 h at 120 °C and an H pressure of 1 MPa. This work provides a simple, efficient and economic method to improve the C=O hydrogenation performance of Cu-based catalysts.
PubMed: 38930819
DOI: 10.3390/molecules29122753 -
Micromachines Jun 2024This study investigated the influence of microstructure on the performance of Ag inkjet-printed, resistive temperature detectors (RTDs) fabricated using particle-free...
This study investigated the influence of microstructure on the performance of Ag inkjet-printed, resistive temperature detectors (RTDs) fabricated using particle-free inks based on a silver nitrate (AgNO) precursor and ethylene glycol as the ink solvent. Specifically, the temperature coefficient of resistance (TCR) and sensitivity for sensors printed using inks that use monoethylene glycol (mono-EG), diethylene glycol (di-EG), and triethylene glycol (tri-EG) and subjected to a low-pressure argon (Ar) plasma after printing were investigated. Scanning electron microscopy (SEM) confirmed previous findings that microstructure is strongly influenced by the ink solvent, with mono-EG inks producing dense structures, while di- and tri-EG inks produce porous structures, with tri-EG inks yielding the most porous structures. RTD testing revealed that sensors printed using mono-EG ink exhibited the highest TCR (1.7 × 10/°C), followed by di-EG ink (8.2 × 10/°C) and tri-EG ink (7.2 × 10/°C). These findings indicate that porosity exhibits a strong negative influence on TCR. Sensitivity was not strongly influenced by microstructure but rather by the resistance of RTD. The highest sensitivity (0.84 Ω/°C) was observed for an RTD printed using mono-EG ink but not under plasma exposure conditions that yield the highest TCR.
PubMed: 38930719
DOI: 10.3390/mi15060749 -
Microorganisms May 2024Stevioside is a secondary metabolite of diterpenoid glycoside production in plants. It has been used as a natural sweetener in various foods because of its high...
Stevioside is a secondary metabolite of diterpenoid glycoside production in plants. It has been used as a natural sweetener in various foods because of its high sweetness and low-calorie content. In this study, we constructed a strain for the complete synthesis of stevioside using a metabolic engineering strategy. Firstly, the synthesis pathway of steviol was modularly constructed in BY4742, and the precursor pathway was strengthened. The yield of steviol was used as an indicator to investigate the expression effect of different sources of diterpene synthases under different combinations, and the strains with further improved steviol yield were screened. Secondly, glycosyltransferases were heterologously expressed in this strain to produce stevioside, the sequence of glycosyltransferase expression was optimized, and the uridine diphosphate-glucose (UDP-Glc) supply was enhanced. Finally, the results showed that the strain SST-302III-ST2 produced 164.89 mg/L of stevioside in a shake flask experiment, and the yield of stevioside reached 1104.49 mg/L in an experiment employing a 10 L bioreactor with batch feeding, which was the highest yield reported. We constructed strains with a high production of stevioside, thus laying the foundation for the production of other classes of steviol glycosides and holding good prospects for application and promotion.
PubMed: 38930507
DOI: 10.3390/microorganisms12061125 -
Materials (Basel, Switzerland) Jun 2024This paper investigates the high temperature resistance performance and mechanism of potassium-activated blended precursor geopolymer with silica fume. The failure...
This paper investigates the high temperature resistance performance and mechanism of potassium-activated blended precursor geopolymer with silica fume. The failure morphology, volume, and mass loss, compressive strength deterioration, hydration production, and pore structure are measured and analyzed. The results show that introducing slag into fly ash-based geopolymer could greatly improve the 28 d compressive strength but reduce the thermal stability. In contrast, the partial substitution of fly ash by metakaolin contributes to excellent high temperature resistance with slightly enhanced 28 d compressive strength. After being exposed at 800 °C, the residual compressive strength of F7M3 remains at 37 MPa, almost 114% of the initial ambient-temperature strength. An appropriately enlarged silica fume content in geopolymer results in increased compressive strength and enhanced thermal stability. However, an excessive silica fume content is detrimental to the generation of alkali-aluminosilicate gels and ceramic-like phases and thus exacerbates the high temperature damage.
PubMed: 38930345
DOI: 10.3390/ma17122975 -
Materials (Basel, Switzerland) Jun 2024Antibiotic resistance is a global health crisis caused by the overuse and misuse of antibiotics. Accordingly, bacteria have developed mechanisms to resist antibiotics....
Antibiotic resistance is a global health crisis caused by the overuse and misuse of antibiotics. Accordingly, bacteria have developed mechanisms to resist antibiotics. This crisis endangers public health systems and medical procedures, underscoring the urgent need for novel antimicrobial agents. This study focuses on the green synthesis of ZnO nanoparticles (NPs) using aqueous extracts from subps. leaves and stems, employing different zinc sulfate concentrations (0.5, 1, and 2 M). NP characterization included transmission electron microscopy (TEM), scanning electron microscopy (SEM), and X-ray diffraction (XRD), along with Fourier transform infrared spectroscopy (FTIR) analysis. This study aimed to assess the efficacy of ZnO NPs, prepared at varying concentrations of zinc sulfate, for their capacity to inhibit both Gram-positive and Gram-negative bacteria, as well as their antioxidant potential using the 2,2-diphenyl-1-picrylhydrazyl (DPPH) method. SEM and TEM results showed predominantly spherical NPs. The smallest size (18.5 ± 1.3 nm for leaves and 18.1 ± 1.3 nm for stems) occurred with the 0.5 M precursor concentration. These NPs also exhibited remarkable antibacterial activity against both Gram-positive and Gram-negative bacteria at 10 µg/mL, as well as the highest antioxidant activity, with an IC (the concentration of NPs that scavenge 50% of the initial DPPH radicals) of 62 ± 0.8 (µg/mL) for the leaves and 35 ± 0.6 (µg/mL) for the stems. NPs and precursor concentrations were modeled to assess their impact on bacteria using a 2D polynomial equation. Response surface plots identified optimal concentration conditions for antibacterial effectiveness against each species, promising in combating antibiotic resistance.
PubMed: 38930221
DOI: 10.3390/ma17122853 -
Life (Basel, Switzerland) Jun 2024Amino acids are one of the most important building blocks of life. During the biochemical process of translation, cells sequentially connect amino acids via amide bonds...
From Zero to Hero: The Cyanide-Free Formation of Amino Acids and Amides from Acetylene, Ammonia and Carbon Monoxide in Aqueous Environments in a Simulated Hadean Scenario.
Amino acids are one of the most important building blocks of life. During the biochemical process of translation, cells sequentially connect amino acids via amide bonds to synthesize proteins, using the genetic information in messenger RNA (mRNA) as a template. From a prebiotic perspective (i.e., without enzymatic catalysis), joining amino acids to peptides via amide bonds is difficult due to the highly endergonic nature of the condensation reaction. We show here that amides can be formed in reactions catalyzed by the transition metal sulfides from acetylene, carbon monoxide and ammonia under aqueous conditions. Some α- and β-amino acids were also formed under the same conditions, demonstrating an alternative cyanide-free path for the formation of amino acids in prebiotic environments. Experiments performed with stable isotope labeled precursors, like NHCl and C-acetylene, enabled the accurate mass spectroscopic identification of the products formed from the starting materials and their composition. Reactions catalyzed using the transition metal sulfides seem to offer a promising alternative pathway for the formation of amides and amino acids in prebiotic environments, bypassing the challenges posed by the highly endergonic condensation reaction. These findings shed light on the potential mechanisms by which the building blocks of life could have originated on early Earth.
PubMed: 38929702
DOI: 10.3390/life14060719 -
Life (Basel, Switzerland) May 2024Endometriosis is a frequent, estrogen-dependent, chronic disease, characterized by the presence of endometrial glands and stroma outside of the uterine cavity. Although... (Review)
Review
Endometriosis is a frequent, estrogen-dependent, chronic disease, characterized by the presence of endometrial glands and stroma outside of the uterine cavity. Although it is not considered a precursor of cancer, endometriosis is associated with ovarian cancer. In this review, we summarized the evidence that clear-cell and endometrioid ovarian carcinomas (endometriosis-associated ovarian carcinoma-EAOC) may arise in endometriosis. The most frequent genomic alterations in these carcinomas are mutations in the AT-rich interaction domain containing protein 1A (ARID1A) gene, a subunit of the SWI/SNF chromatin remodeling complex, and alterations in phosphatidylinositol 3-kinase (PI3K) which frequently coexist. Recent studies have also suggested the simultaneous role of the tumor-suppressor gene in the early malignant transformation of endometriosis and the contribution of deficient MMR (mismatch repair) protein status in the pathogenesis of EAOC. In addition to activating and inactivating mutations in cancer driver genes, the complex pathogenesis of EAOC involves multiple other mechanisms such as the modulation of cancer driver genes via the transcriptional and post-translational (miRNA) modulation of cancer driver genes and the interplay with the inflammatory tissue microenvironment. This knowledge is being translated into the clinical management of endometriosis and EAOC. This includes the identification of the new biomarkers predictive of the risk of endometriosis and cancer, and it will shape the precision oncology treatment of EAOC.
PubMed: 38929687
DOI: 10.3390/life14060704