Tuning the Selectivity of Nitrate Reduction via Fine Composition Control of RuPdNP Catalysts.

Herein, aqueous nitrate (NO3 -) reduction is used to explore composition-selectivity relationships of randomly alloyed ruthenium-palladium nanoparticle catalysts to provide insights into the factors affecting selectivity during this and other industrially relevant catalytic reactions. NO3 - reduction proceeds through nitrite (NO2 -) and then nitric oxide (NO), before diverging to form either dinitrogen (N2) or ammonium (NH4 +) as final products, with N2 preferred in potable water treatment but NH4 + preferred for nitrogen recovery. It is shown that the NO3 - and NO starting feedstocks favor NH4 + formation using Ru-rich catalysts, while Pd-rich catalysts favor N2 formation. Conversely, a NO2 - starting feedstock favors NH4 + at ≈50 atomic-% Ru and selectivity decreases with higher Ru content. Mechanistic differences have been probed using density functional theory (DFT). Results show that, for NO3 - and NO feedstocks, the thermodynamics of the competing pathways for N-H and N-N formation lead to preferential NH4 + or N2 production, respectively, while Ru-rich surfaces are susceptible to poisoning by NO2 - feedstock, which displaces H atoms. This leads to a decrease in overall reduction activity and an increase in selectivity toward N2 production. Together, these results demonstrate the importance of tailoring both the reaction pathway thermodynamics and initial reactant binding energies to control overall reaction selectivity.

Green Synthesis of the Triazine Derivatives and their Application for the Benign Electrocatalytic Reaction of Nitrate Reduction to Ammonia.

This work uses green sustainable reactions twice. Firstly, it is microwave synthesis: 2,4,6-tribiphenyl-4-yl-1,3,5-triazine and similar compounds were prepared in a closed microwave reactor in n-octane by the Friedel-Crafts reaction. Second, a hybrid electrocatalyst for the highly demanded electrochemical reaction of nitrate reduction to ammonia (NO3RR) was prepared based on this material. This reaction has great potential to replace the energy-intensive Haber-Bosch process, and in addition, has independent value for the elimination of nitrate contamination of water resources. As shown in the work, microwave synthesis is an eco-friendly method for the synthesis of complex organic compounds; fast, selective and with a high yield of the target product. The electrocatalyst deposited on the graphite electrode consisted of a layer of 2,4,6-tribiphenyl-4-yl-1,3,5-triazine and related compounds coated with cobalt oxide. The hybrid catalyst was firmly retained on the graphite electrode during NO3RR and the material showed impressive stability with almost no decrease in catalytic activity even after the fifth cycle. Both 2,4,6-tribiphenyl-4-yl-1,3,5-triazine and the catalyst based on this substance were characterized by SEM, XPS, XRD, UV-vis spectra, cyclic (and linear) voltammetry, and chronoamperometry. This work can serve as a starting point for the development of stable and durable electrocatalysts for NO3RR using triazine derivatives.

An all-in-one FeOx-rGO sponge fabricated by solid-phase microwave thermal shock for water evaporation and purification.

Developing high-efficiency photothermal seawater desalination devices is of significant importance in addressing the shortage of freshwater. Despite much effort made into photothermal materials, there is an urgent need to design a rapidly synthesized photothermal evaporator for the comprehensive purification of complex seawater. Therefore, we report on all-in-one FeOx-rGO photothermal sponges synthesized via solid-phase microwave thermal shock. The narrow band gap of the semiconductor material Fe3O4 greatly reduces the recombination of electron-hole pairs, enhancing non-radiative relaxation light absorption. The abundant π orbitals in rGO promote electron excitation and thermal vibration between the lattices. Control of the surface hydrophilicity and hydrophobicity promotes salt resistance while simultaneously achieving the purification of various complex polluted waters. The optimized GFM-3 sponge exhibitedan enhanced photothermal conversion rate of 97.3% and a water evaporation rate of 2.04 kg/(m2·hr), showing promising synergistic water purification properties. These findings provide a highly efficient photothermal sponge for practical applicationsof seawater desalination and purification,as well as develop a super-rapid processing methodology for evaporation devices.

Microwave Assisted Fast Synthesis of a Donor-Acceptor COF Towards Photooxidative Amidation Catalysis.

The synthesis of covalent organic frameworks (COFs) at bulk scale require robust, straightforward, and cost-effective techniques. However, the traditional solvothermal synthetic methods of COFs suffer low scalability as well as requirement of sensitive reaction environment and multiday reaction time (2-10 days) which greatly restricts their practical application. Here, we report microwave assisted rapid and optimized synthesis of a donor-acceptor (D-A) based highly crystalline COF, TzPm-COF in second (10 sec) to minute (10 min) time scale. With increasing the reaction time from seconds to minutes crystallinity, porosity and morphological changes are observed for TzPm-COF. Owing to visible range light absorption, suitable band alignment, and low exciton binding energy (Eb=64.6 meV), TzPm-COF can efficaciously produce superoxide radical anion (O2 .-) after activating molecular oxygen (O2) which eventually drives aerobic photooxidative amidation reaction with high recyclability. This photocatalytic approach works well with a variety of substituted aromatic aldehydes having electron-withdrawing or donating groups and cyclic, acyclic, primary or secondary amines with moderate to high yield. Furthermore, catalytic mechanism was established by monitoring the real-time reaction progress through in situ diffuse reflectance infrared Fourier transform spectroscopic (DRIFTS) study.

Water-Tolerant Superbase Polyoxometalate [H2(Nb6O19)]6- for Homogeneous Catalysis.

Here, doubly protonated Lindqvist-type niobium oxide cluster [H2(Nb6O19)]6-, fabricated by microwave-assisted hydrothermal synthesis, exhibited superbase catalysis for Knoevenagel and crossed aldol condensation reactions accompanied by activating C-H bond with pKa >26 and proton abstraction from a base indicator with pKa=26.5. Surprisingly, [H2(Nb6O19)]6- exhibited water-tolerant superbase properties for Knoevenagel and crossed aldol condensation reactions in the presence of water, although it is well known that the strong basicity of metal oxides and organic superbase is typically lost by the adsorption of water. Density functional theory calculation revealed that the basic surface oxygens that share the corner of NbO6 units in [H2(Nb6O19)]8- maintained the negative charges even after proton adsorption. This proton capacity and the presence of un-protonated basic sites led to the water tolerance of the superbase catalysis.

Architecting the High-Entropy Oxides on 2D MXene Nanosheets by Rapid Microwave-Heating Strategy with Robust Photoelectrochemical Oxygen Evolution Performance.

High-entropy oxides (HEO) have recently concerned interest as the most promising electrocatalytic materials for oxygen evolution reactions (OER). In this work, a new strategy to the synthesis of HEO nanostructures on Ti3 C2 Tx MXene via rapid microwave heating and subsequent calcination at a low temperature is reported. Furthermore, the influence of HEO loading on Ti3 C2 Tx MXene is investigated toward OER performance with and without visible-light illumination in an alkaline medium. The obtained HEO/Ti3 C2 Tx -0.5 hybrid exhibited an outstanding photoelectrochemical OER ability with a low overpotential of 331 mV at 10 mA cm-2 and a small Tafel slope of 71 mV dec-1 , which exceeded that of a commercial IrO2 catalyst (340 mV at 10 mA cm-2 ). In particular, the fabricated water electrolyzer with the HEO/Ti3 C2 Tx -0.5 hybrid as anode required a less potential of 1.62 V at 10 mA cm-2 under visible-light illumination. Owing to the strong synergistic interaction between the HEO and Ti3 C2 Tx MXene, the HEO/Ti3 C2 Tx hybrid has a great electrochemical surface area, many metal active sites, high conductivity, and fast reaction kinetics, resulting in an excellent OER performance. This study offers an efficient strategy for synthesizing HEO-based materials with high OER performance to produce high-value hydrogen fuel.

Biogenic Synthesis of Carboxymethyl Cashew Gum Modified Gold Nanoparticles and its Sensitive and Selective Calorimetric Detection of Hg2+ Ions and Catalytic Reduction of Methyl Red.

In the present study, we have successfully synthesized and characterized carboxy methyl cashew gum modified gold nanoparticles (CMCG-AuNPs) via a microwave-assisted method and used as a calorimetric probe for selective detection of Hg2+ ions as well as catalytic reduction of methyl red in an aqueous medium. The effect of different parameters including concentration and irradiation time on the formation of CMCG-AuNPs was also investigated. The presence of strong surface plasmon resonance (SPR) peak in the visible region indicated the formation of AuNPs. The characterization techniques were identified the interaction between the CMCG and AuNPs with estimation of size and morphology. The face centred cubic (FCC) crystal structure was identified by using XRD and supporting with SAED pattern. TEM images of CMCG-AuNPs were exhibited as polydispersed with spherical in shape and the average particle size was 12 ± 3 nm. The synthesized CMCG-AuNPs were utilized to sensing Hg2+ ions in an aqueous medium, the presence of Hg2+ ions selectively among other metal ions, the CMCG-AuNPs were aggregated by changing the color from wine red to purple blue accompanied by change in the position of SPR peak and intensity. It was observed as a strong linear relationship based on the change in intensity, the limit of detection was determined to be 0.277 nM. The catalytic activity was also examined for the reduction of methyl red (MR) in the presence of CMCG-AuNPs was completed within 12 min and followed pseudo-first order kinetics with a rate constant of 0.261 min-1. From the obtained results, the synthesized CMCG-AuNPs were useful for detection of heavy metal ions as well as toxic pollutants degradation via a green method, and utilized sensing, environmental, and biomedical application in future.

Jamun Seed-Derived Nitrogen-Doped Carbon Dots: A Novel Microwave-Assisted Synthesis for Ultra-Bright Fluorescence and Mn7+ Detection.

For the synthesis of heteroatom-doped carbon nanostructures, biomass is considered as a promising option. Utilizing the microwave-assisted method, we have demonstrated an easy and straightforward one-pot synthesis of nitrogen-doped luminous carbon dots (NCDs) from jamun seed powder and guanidine hydrochloride. Structural and morphological analyses were performed using various analytical techniques. Under ultraviolet light of 315 nm, NCDs emit a bright blue fluorescence, possess a high quantum yield of 26.90%, exhibit strong water dispersion, and demonstrated excellent stability. The average particle size of the NCDs was found to be 7.5±1.2 nm, with a spherical shape. NCDs exhibit high selectivity and sensitivity in fluorescence quenching when exposed to Mn7+ ions. Over a concentration range of 2-30 µM, the fluorescence response (F0/F) shows a linear relationship with Mn7+ concentration, with a detection limit of 0.81 µM. The probe exhibited negligible interference and proved to be effective in accurately quantifying Mn7+ in spiked real-water samples.

Microwave produced 8-methyl-1,2,4,8-tetraazaspiro[4.5]dec-2-en-3-amine derivatives: their in vitro and in silico analysis.

Compound 1 is formed by a microwave-assisted multicomponent reaction of 1-methylpiperidin-4-one, 2-amino-4-methoxy-6-methyl-1,3,5-triazine, and thiosemicarbazide, followed by the synthesis of Schiff base 2a-l with a variety of aldehydes. A comparison was made between the conventional and microwave methods, and the microwave approach was shown to be considerably superior to the classical method since it takes less time and produces higher yields. Several spectral investigations, including 1H NMR, 13C NMR, Mass, and IR spectroscopy, are used to characterize the complete series. In vitro antibacterial testing suggests that compounds 2c, 2f, and 2g are promising antibacterial agents, although compounds 2d, 2e, and 2l are effective antimycobacterial agents when compared to the conventional medicine Rifampicin. The docking score from docking studies is considerable, which validates the results of the biological examination. Molecular docking was performed on Escherichia coli DNA gyrase. According to the in silico ADME analysis, each drug molecule is ideal for use in terms of drug solubility, hydrogen bonding, and cell permeability.

In silico screening, synthesis, and antimalarial evaluation of PABA substituted 1,3,5-triazine derivatives as Pf-DHFR inhibitors.

OBJECTIVES: Drug resistance in malaria parasites necessitates the development of new antimalarial drugs with unique mechanisms of action. In the present research work, the PABA conjugated 1,3,5-triazine derivatives were designed as an antimalarial agent. METHODS: In this present work, a library of two hundred-seven compounds was prepared in twelve different series such as [4A (1-23), 4B(1-22), 4C(1-21), 4D(1-20), 4E(1-19), 4F(1-18), 4G(1-17), 4H(1-16), 4I(1-15), 4J(1-13), 4K(1-12) and 4L(1-11) ] respectively using different primary and secondary aliphatic and aromatic amines. Ten compounds were ultimately selected through in silico screening. They were synthesized by conventional and microwave-assisted methods followed by in vitro antimalarial evaluations performed in chloroquine-sensitive (3D7) and resistant (DD2) strains of P. falciparum. RESULTS: The docking results showed that compound 4C(11) had good binding interaction with Phe116, Met55 (-464.70 kcal/mol) and Phe116, Ser111 (-432.60 kcal/mol) against wild (1J3I) and quadruple mutant (1J3K) type of Pf-DHFR. Furthermore, in vitro, antimalarial activity results indicated that compound 4C(11) showed potent antimalarial activity against chloroquine-sensitive (3D7) and chloroquine-resistant (Dd2) strain of P. falciparum along with IC50 (14.90 µg mL-1) and (8.30 µg mL-1). CONCLUSION: These PABA-substituted 1,3,5-triazine compounds could be exploited to develop a new class of Pf-DHFR inhibitors as a lead candidate.

Fuel-dependent, shape-selective, distinct blue and green photoluminescence from α-Bi2 O3 and ß-Bi2 O3 synthesised using microwave combustion.

In the current study, α-Bi2 O3 and ß-Bi2 O3 were synthesised using a one-step, novel, solid-solid combustion technique. The reaction rate was increased with the use of microwaves (molecular heating) compared to direct or indirect heating. A strong relationship was observed between the fuel, polymorphic structure, shape and optical properties of the synthesised Bi2 O3 . Photoluminescence studies reveal that two major visible emissions are observed for all samples. The two emissions are distinct with a broad peak in blue and a narrow peak in green. The intensity of the green characteristic emission depends strongly on the heating method used for synthesis and is more intense for microwave-synthesised samples.

Citrus/urea nitrogen-doped carbon quantum dots as nanosensors for vanillin determination in infant formula and food products via factorial experimental design fluorimetry and smartphone.

Vanillin is a flavouring agent that is prohibited for use in infant food products with ages lower than 6 months. Excessive vanillin usage could lead to eating disorders, nausea, headache, and vomiting. Therefore, it is essential to control the contents of vanillin in food samples, especially in infant formula. Here, we developed a highly sensitive nanosensor for vanillin based on using green synthesized highly fluorescent (QY = 29.5%) N-doped carbon quantum dots (N-CQDs) as a turn-off fluorescent nanoprobe. The N-doped CQDs synthesis was adopted using citrus bulb squeeze extract and the commonly used fertilizer, urea, as substrates. After mixing with vanillin, the fluorescence of the N-CQDs was largely quenched in a vanillin concentration-dependent manner. The sensing conditions were optimized by quality-by-design using a two-level full factorial design (22 FFD). The N-doped CQDs could detect vanillin in the range 0.1-12.0 µg/ml with a limit of detection of 0.013 µg/ml. Next, a smartphone imaging-based assay combined with a UV chamber was adopted and applied for vanillin determination. This simple detection technique showed sensitivity similar to that of the conventional fluorimetric method. Both conventional and smartphone-based methods were successfully applied for the determination of vanillin in infant milk formula and biscuits and could detect real vanillin concentrations in the analyzed samples with high % recoveries (94.5% to 105.5%). At last, the biocompatibility of the newly synthesized N-CQDs was tested, and it was found to be an excellent candidate for cancer cell imaging.

Development of Polymer-Encapsulated, Amine-Functionalized Zinc Ferrite Nanoparticles as MRI Contrast Agents.

The need for stable and well-defined magnetic nanoparticles is constantly increasing in biomedical applications; however, their preparation remains challenging. We used two different solvothermal methods (12 h reflux and a 4 min microwave, MW) to synthesize amine-functionalized zinc ferrite (ZnFe2O4-NH2) superparamagnetic nanoparticles. The morphological features of the two ferrite samples were the same, but the average particle size was slightly larger in the case of MW activation: 47 ± 14 nm (Refl.) vs. 63 ± 20 nm (MW). Phase identification measurements confirmed the exclusive presence of zinc ferrite with virtually the same magnetic properties. The Refl. samples had a zeta potential of -23.8 ± 4.4 mV, in contrast to the +7.6 ± 6.8 mV measured for the MW sample. To overcome stability problems in the colloidal phase, the ferrite nanoparticles were embedded in polyvinylpyrrolidone and could be easily redispersed in water. Two PVP-coated zinc ferrite samples were administered (1 mg/mL ZnFe2O4) in X BalbC mice and were compared as contrast agents in magnetic resonance imaging (MRI). After determining the r1/r2 ratio, the samples were compared to other commercially available contrast agents. Consistent with other SPION nanoparticles, our sample exhibits a concentrated presence in the hepatic region of the animals, with comparable biodistribution and pharmacokinetics suspected. Moreover, a small dose of 1.3 mg/body weight kg was found to be sufficient for effective imaging. It should also be noted that no toxic side effects were observed, making ZnFe2O4-NH2 advantageous for pharmaceutical formulations.

Microwave-Assisted Synthesis of Zeolite A from Metakaolinite for CO2 Adsorption.

The global demand for energy and industrial growth has generated an exponential use of fossil fuels in recent years. It is well known that carbon dioxide (CO2) is mainly produced, but not only from fuels, which has a negative impact on the environment, such as the increasing emission of greenhouse gases. Thus, thinking about reducing this problem, this study analyzes microwave irradiation as an alternative to conventional heating to optimize zeolite A synthesis conditions for CO2 capture. Synthesis reaction parameters such as different temperatures (60-150 °C) and different time durations (1-6 h) were evaluated. The CO2 adsorption capacity was evaluated by CO2 adsorption-desorption isotherms at 25 °C and atmospheric pressure. The results showed that the synthesis of zeolite A by microwave irradiation was successfully obtained from natural kaolinite (via metakaolinization), reducing both temperature and time. Adsorption isotherms show that the most promising adsorbent for CO2 capture is a zeolite synthesized at 100 °C for 4 h, which reached an adsorption capacity of 2.2 mmol/g.

Simplified Synthesis of the Amine-Functionalized Magnesium Ferrite Magnetic Nanoparticles and Their Application in DNA Purification Method.

For pathogens identification, the PCR test is a widely used method, which requires the isolation of nucleic acids from different samples. This extraction can be based on the principle of magnetic separation. In our work, amine-functionalized magnesium ferrite nanoparticles were synthesized for this application by the coprecipitation of ethanolamine in ethylene glycol from Mg(II) and Fe(II) precursors. The conventional synthesis method involves a reaction time of 12 h (MgFe2O4-H&R MNP); however, in our modified method, the reaction time could be significantly reduced to only 4 min by microwave-assisted synthesis (MgFe2O4-MW MNP). A comparison was made between the amine-functionalized MgFe2O4 samples prepared by two methods in terms of the DNA-binding capacity. The experimental results showed that the two types of amine-functionalized magnesium ferrite magnetic nanoparticles (MNPs) were equally effective in terms of their DNA extraction yield. Moreover, by using a few minutes-long microwave synthesis, we obtained the same quality magnesium ferrite particles as those made through the long and energy-intensive 12-h production method. This advancement has the potential to improve and expedite pathogen identification processes, helping to better prevent the spread of epidemics.

Scalable approach to fabricate paper-based biomass reduced graphene sensor for the detection of exhaled diabetic breath.

Herein, we demonstrate a microwave-assisted chemical reduction technique to exfoliate a few layers of graphene from the natural waste material, 'coconut shell'. The microwave irradiation coconut shell is subjected to structural, morphological and functional groups characterization methods including SEM, Raman, FTIR and XPS spectroscopic analyses. The formation of biomass reduced graphene (BRG) has been confirmed through Raman and FTIR spectroscopic analyzes with the presence of D, G and 2D and other functional spectral bands, respectively. The surface topography of the BRG exhibits two-dimensional mat structures with wrinkle topography, imaged by electron microscopic techniques. The metallic behaviour of the BRG is evaluated by band structure calculation using density functional theory. The synthesized nanostructure has been evaluated for exhaled diabetic breath sensing application by fabricating sensor device on the paper-based substrate by roll-to-roll coating technique. The BRG sensor exhibited enhanced sensing response at a very lower concentration of diabetic biomarker with long term stability and rapid response/recovery time of 1.11 s/41.25 s, respectively. Based on our findings, the microwave-assisted BRG is a potential candidate for fabricating highly scalable, inherently safe, economically viable and excellent sensing performance to detect exhaled diabetic breath at room temperature.

Chromium (VI) detection by microbial carbon dots: Microwave synthesis and mechanistic study.

Functionalized carbon dots (CDs) derived from Citrobacter freundii bacterial cells were used for selective detection of Cr(VI). A microwave-heating-based green synthesis approach is adopted to produce functionalized CDs from C. freundii bacterial cells (CF-CDs). The reaction was carried out in a 500 W microwave digester at 200°C for 20 min. The supernatant was filtered with a 0.2 µm filter and highly monodisperse CDs were obtained. Inherent functionalization of CF-CDs with nitrogen and oxygen-containing functional groups made them extremely selective toward Cr(VI) with a lower limit of detection of ~1.7 ppm. More importantly, CF-CDs could distinguish between Cr(VI) and Cr(III), which is highly desirable for practical applications. The fabricated sensor had a dual linear response range between 0 and 50 µM and 50-250 µM. The synthesized CDs were inherently functionalized which made them highly selective for Cr(VI) detection. CF-CDs also possess high stability over long storage period. This study reports the facile synthesis and characterization of a highly selective sensor for Cr(VI). As opposed to similar CDs sensors reported for Cr(VI), based on inner-filter effect, CF-CDs exhibit a strong, specific interaction toward Cr(VI), indicated by the large binding constant.

A Convenient Way to Quinoxaline Derivatives through the Reaction of 2-(3-Oxoindolin-2-yl)-2-phenylacetonitriles with Benzene-1,2-diamines.

Microwave-assisted reaction between 2-(3-oxoindolin-2-yl)-2-phenylacetonitriles andbenzene-1,2-diamines leads to the high-yielding formation of the corresponding quinoxalines as sole, easily isolaable products. The featured transformation involves unusual extrusion of phenylacetonitrile molecule and could be performed in a short sequence starting from commonly available indoles and nitroolefins.

Design, Synthesis and Biological Evaluation of Novel 1,3,5-Triazines: Effect of Aromatic Ring Decoration on Affinity to 5-HT7 Receptor.

Considering the key functions of the 5-HT7 receptor, especially in psychiatry, and the fact that effective and selective 5-HT7 receptor ligands are yet to be available, in this work, we designed and synthesized novel 1,3,5-triazine derivatives particularly based on the evaluation of the effect of substituents at aromatic rings on biological activity. The tested compounds showed high affinity to the 5-HT7 receptor, particularly ligands N2-(2-(5-fluoro-1H-indol-3-yl)ethyl)-N4-phenethyl-1,3,5-triazine-2,4,6-triamine 2 (Ki = 8 nM) and N2-(2-(1H-indol-3-yl)ethyl)-N4-(2-((4-fluorophenyl)amino)ethyl)-1,3,5-triazine-2,4,6-triamine 12 (Ki = 18 nM) which showed moderate metabolic stability, and affinity to the CYP3A4 isoenzyme. As for the hepatotoxicity evaluation, the tested compounds showed moderate cytotoxicity only at concentrations above 50 µM. Compound 12 exhibited less cardiotoxic effect than 2 on Danio rerio in vivo model.

Polytopal Rearrangement Governing Stereochemistry of Bicyclic Oxime Ether Synthesis.

In the present study, four O-substituted oximes of quinuclidin-3-one were synthesized using appropriate O-substituted hydroxylamine hydrochlorides. In order to perform these reactions in a solvent, a mixture of (E) and (Z) products was yielded. Using mechanochemical and microwave synthesis, we then obtained pure (E) oximes. In almost all cases, the conversion to oxime ethers was completed. Reactions were monitored by ATR spectroscopy and the ratios of (E) and (Z) oxime ethers were deduced from 1H NMR data. Several reactions were very rapid (1 min) with 100% conversion and stereospecificity. To investigate the reaction mechanisms, full conformational analyses of the reaction intermediates were performed and the lowest energy conformers were determined. These conformers differed in spatial arrangement around the nitrogen atom of the amino group and were in the correct orientation for reactions to occur. Calculated standard Gibbs energies of the formation were in agreement with the experimentally obtained ratios of (E) and (Z) isomers. This work shows alternatives to the classical synthesis of O-substituted oxime ether precursors and highlights the fast reaction rate and stereoselectivity of microwave synthesis as well as the "green" aspects of mechanochemistry.