Acid Catalyst Research Articles

Estimation of catalytic cracking of vacuum gas oil by ZSM-5- and β-zeolite-containing two-layered and novel three-layered hierarchical catalysts using Curie point pyrolyzer

ZSM-5- and β-zeolite-containing two-layered hierarchical catalysts (2 L-Z and 2 L-β) were prepared using a template of malic acid and novel three-layered hierarchical catalysts were also prepared combining mesoporous silica derived from the gel skeletal reinforcement (GSR) method with hexamethyldisiloxane (HMDS) - acetic anhydride (AA) as reinforcing agents. 2 L-Z and 2 L-β catalysts contained mesoporous silica of 50 wt% and microporous zeolite of 50 wt% and were called 2 L-Z-(Z50) and 2 l-β-(Z50) in which the amount of zeolite is shown in parenthesis. 3 L-co-gel and 3 L-mix, two types of three-layered hierarchical catalysts, were prepared by making GSR-silica in the presence of a 2 L catalyst for the former and by combining GSR-silica-gel with 2 L catalyst for the latter. 3 L catalysts contained 50 wt% of the 2 L catalyst and 50 wt% large-mesoporous GSR-silica and revealed three layered properties of microporous zeolite, small mesoporous silica and large mesoporous silica. Signals of zeolite crystals and amorphous phase were observed in XRD measurement for 3 L catalysts. Both smaller size of mesopores and larger size of mesopores were observed in N2 adsorption-desorption measurement. Vacuum gas oil (VGO) was catalytically cracked using 2 L and 3 L hierarchical catalysts with the use of Curie point pyrolyzer (CPP) method. ZSM-5-containing 3 L catalysts exhibited the lower conversions than corresponding 2 L catalyst, kaolin-mixed catalyst and ZSM-5 single while 3 L-co-gel-β-(Z25), which included 25 wt% of β-zeolite, exhibited the highest activity among β-zeolite-containing catalysts. The higher selectivity for p-xylene in xylene mixture was detected in catalytic cracking using 3 L-co-gel-Z-(Z25) and 3 L-mix-Z-(Z25) catalysts. When the relative activity against XRD integral intensity and amounts of acid sites was plotted against average pore diameter derived from N2 adsorption-desorption measurement, the strong correlation was observed, suggesting that the intrinsic activity of active sites of zeolite could be related to the pore size of the whole catalyst.

Hydrophobic Mesoporous Polymeric Acid Catalysts for Glycerol Coetherification with Isobutene and tert-Butanol

Hydrophobic Mesoporous Polymeric Acid Catalysts for Glycerol Coetherification with Isobutene and <i>tert</i>-Butanol

Efficient Flow Synthesis of Glycidyl Ether Using BuSnCl3 as a Mild Lewis Acid

AbstractA ring-opening protocol of epichlorohydrin with 2-ethylhexanol was investigated for the synthesis of the corresponding chlorohydrin ether. BuSnCl3 proved to be an efficient mild Lewis acid catalyst, yielding the product with high selectivity. A scalable flow synthesis was achieved by modifying the flow setup. The flow synthesis of the corresponding glycidyl ether from the chlorohydrin ether was also carried out in an efficient manner by using the basic treatment.

C3-Alkylation of Imidazo[1,2-a]pyridines via Three-Component Aza-Friedel-Crafts Reaction Catalyzed by Y(OTf)3.

As an important class of nitrogen-containing fused heterocyclic compounds, imidazo[1,2-a]pyridines often exhibit significant biological activities, such as analgesic, anticancer, antiosteoporosis, anxiolytic, etc. Using Y(OTf)3 as a Lewis acid catalyst, a simple and efficient method has been developed for the synthesis of C3-alkylated imidazo[1,2-a]pyridines through the three-component aza-Friedel-Crafts reaction of imidazo[1,2-a]pyridines, aldehydes, and amines in the normal air atmosphere without the protection of inert gas and special requirements for anhydrous and anaerobic conditions. A series of imidazo[1,2-a]pyridine derivatives were obtained with moderate to good yields, and their structures were confirmed by 1H NMR, 13C NMR, and HRMS. Furthermore, this conversion has the advantages of simple operation, excellent functional group tolerance, high atomic economy, broad substrate scope, and can achieve gram-level reactions. Notably, this methodology may be conveniently applied to the further design and rapid synthesis of potential biologically active imidazo[1,2-a]pyridines with multifunctional groups.

Enantioselective Synthesis of Spiro[cyclopentane-1,3'-oxindole] Scaffolds with Five Consecutive Stereocenters.

A highly diastereo- and enantioselective cascade annulation reaction of Morita-Baylis-Hillman (MBH) maleimides of isatins with ortho-hydroxychalcones was achieved by a chiral N,N'-dioxide/Mg(II) complex Lewis acid catalyst. This strategy provides a concise and efficient route to densely functionalized spiro[cyclopentane-1,3'-oxindole] compounds with five consecutive stereocenters. The reaction itself features mild conditions, good functional group compatibility, and broad substrate scope (62 examples, up to 99% yield, up to >20:1 dr, 97% ee). In addition, an obvious ligand acceleration effect and chiral amplification effect were observed. DFT calculations were performed to elucidate the stereoselectivity observed. The gram-scale synthesis and the inhibitory effect of two products on the viability of A549 cells demonstrate the potential utility of the current method.

Biodiesel production using various methanol sources and catalytic routes: A techno-environmental analysis

The primary objective of this research is to investigate the biodiesel production via the transesterification reaction between triolein and methanol in the presence of a basic and acidic catalysts, namely sodium hydroxide and sulfuric acid, using CHEMCAD simulation software as a process modelling and simulation tool. Methanol, one of the raw-materials used in biodiesel manufacturing, was synthesized using reforming technology applied to: i) coke oven gas and carbon dioxide, and ii) glycerol that represents an important by-product of the biodiesel synthesis. Four different cases were developed and compared, with detailed operating parameters and equipment designs for each of the investigated scenarios. The production capacity was set to 1000.00 kg/h of biodiesel and a purity higher than 98 % was registered in all investigated cases. Based on the material and energy balances derived from modelling and simulation section, an environmental analysis using the Life Cycle Assessment methodology was performed with the aid of the GaBi software. Ten environmental impact categories (i.e., Global Warming Potential, Fossil Depletion Potential, Human Toxicity, Water Depletion, etc.) are generated and relevant discussions about the sub-processes that exhibit the highest influence are given. The environmental evaluation shows that the most environmentally friendly scenario consists of the methanol production using coke oven gas and carbon dioxide, and its subsequent utilization for the biodiesel production following the alkali catalysis. A scenario analysis regarding several electric and thermal energy sources (i.e., natural gas, biogas, biomass, grid mix) was performed. According to this scenario analysis, while evaluating the synthesis of biodiesel through the alkali catalysis pathway, using biomass as a renewable source improves the environmental performances across certain impact categories.

Design of Mn-based nanozymes with multiple enzyme-like activities for identification/quantification of glyphosate and green transformation of organophosphorus

A Mn-based nanozyme, Mn-uNF/Si, with excellent alkali phosphatase-like activity was designed by in-situ growth of ultrathin Mn-MOF on the surface of silicon spheres, and implemented as an effective solid Lewis-Brønsted acid catalyst for broad-spectrum dephosphorylation. H218O-mediated GC-MS studies confirmed the cleavage sites and the involvement of H2O in the new bonds. DRIFT NH3-IR and in-situ ATR-FTIR confirmed the coexistence of Lewis-Brønsted acid sites and the adjustment of adsorption configurations at the interfacial sites. In addition, a green transformation route of “turning waste into treasure” was proposed for the first time (“OPs→PO43−→P food additive”) using edible C. reinhardtii as a transfer station. By alkali etching of Mn-uNF/Si, a nanozyme Mn-uNF with laccase-like activity was obtained. Intriguingly, glyphosate exhibits a laccase-like fingerprint-like response (+,−) of Mn-uNF, and a non-enzyme amplified sensor was thus designed, which shows a good linear relationship with Glyp in a wide range of 0.49–750 μM, with a low LOD of 0.61 μM, as well as high selectivity and anti-interference ability under the co-application of phosphate fertilizers and multiple pesticides. This work provides a controllable methodology for the design of bifunctional nanozymes, which sheds light on the highly efficient green transformation of OPs, and paves the way for the selective recognition and quantification of glyphosate. Mechanistically, we also provided deeper insights into the structure-activity relationship at the atomic scale.

L-proline H2SO4 catalyzed synthesis of novel coumarin-based spiroindolino-3,4-dihydropyrimidin-2(1H)-ones: in vitro cytotoxic assay and molecular docking study.

Development of environmentally benign catalyst systems, especially those derived from readily available nature's pool, in multicomponent synthesis, consolidates multiple facets of green chemistry. Here, an L-proline derived green acid catalyst in the form of L-proline⋅H2SO4 was developed and employed for multicomponent synthesis of coumarin-based spiroindolino-3,4-dihydropyrimidin-2(1H)-ones from the reaction of 4-hydroxycoumarin, isatin and urea/thiourea. Preliminary cytotoxicity studies showed that a couple of compounds (M5 and M6) have good cytotoxicity (40-50%) against in Dalton's Lymphoma (DL) cells while demonstrating minimal cytotoxicity (10-12%) for normal non-cancerous cell lines. Molecular docking simulations for the least and most cytotoxic compounds, M3 and M6 respectively, against nineteen tumor target proteins were carried out, and seven of them were identified to test against all the sixteen compounds. Based on the estimated docking score and inhibition constants (Ki), the interaction of the compounds with the tumor target protein, beta-hexosaminidase B (PDB ID: 1NOW) matched closely with in vitro cytotoxicity data.

Stereoselective Organocatalyzed Glycosylation of Glycosyl Trichloroacetimidate Donors: Thiouracil as Brønsted Acid Catalyst

AbstractHerein, we report thiouracil‐catalyzed α‐selective O‐glycosylations employing easily accessible glycosyl trichloroacetimidate donors without using any co‐catalyst or additive. A variety of alcohol nucleophiles including saccharides, and amino acids with different protecting groups containing glycosyl trichloroacetimidate donors were successfully α‐glycosylated using an operationally simple protocol. Moreover, mechanistic investigations suggest that thiouracil functions as Brønsted acid/base catalyst in this glycosylation process.

Structural Engineering of l-Aspartic Amphiphilic Polyesters for Enzyme-Responsive Drug Delivery and Bioimaging in Cancer Cells.

Design and development of amphiphilic polyesters based on bioresources are very important to cater to the ever-growing need for biodegradable polymers in biomedical applications. Here, we report structural engineering of enzyme-responsive amphiphilic polyesters based on l-amino acid bioresources and study their drug delivery aspects in the cancer cell line. For this purpose, an l-aspartic acid-based polyester platform is chosen, and two noncovalent forces such as hydrogen bonding and side-chain hydrophobic interactions are introduced to study their effect on the aqueous self-assembly of nanoparticles. The synthetic strategy involves the development of l-aspartic acid-based dimethyl ester monomers with acetal and stearate side chains and subjecting them to solvent-free melt polycondensation reactions to produce side-chain-functionalized polyesters in the entire composition range. Postpolymerization acid catalyst deprotection of acetal yielded hydroxyl-functionalized polyesters. Amphiphilicity of the polymer is carefully fine-tuned by varying the composition of the stearate and hydroxyl units in the polymer chains to produce self-assembly in water. Various drugs such as camptothecin (CPT), curcumin (CUR), and doxorubicin (DOX) and biomarkers like 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (HPTS), rose bengal (RB), and Nile red (NR) are successfully encapsulated in the polymer nanoparticles. Cytotoxicity of biodegradable polymer nanoparticles is tested in normal and breast cancer cell lines. The polymer nanoparticles are found to be highly biocompatible and delivered the anticancer drugs in the intracellular compartments of the cells.

Exploring the Impact of Elements on the Reactivity of a Straightforward Procedure for Generating Vinyl-Carbazole Derivatives via a Frustrated Lewis Pair Mechanism.

The effect of chemical element on the reactivity for carbazolation reaction of phenylacetylene utilizing G13(C6F5)3 (Lewis acid) and G15-carbazole (Lewis base) was theoretically investigated using density functional theory (M06-2X-D3/def2-TZVP), where G13 represents Group 13 elements and G15 represents Group 15 elements. Through activation strain model (ASM) analysis, it is apparent that the reactivity of the entire carbazolation reaction is chiefly governed by the structural strain energy of the alkyne fragment. In other words, if G13(C6F5)3 or G15-carbazole features an atomic radius that is either too small (e.g., B atom) or too large (e.g., Tl or Bi atom), it results in inadequate orbital overlap between the reactants due to the impact of steric effects. This, in turn, results in an elevation of the activation energy for such reactions, thereby impeding the alkyne from undergoing the carbazole catalytic reaction. In light of the above analyses, our theoretical findings suggest that, except for Tl(C6F5)3, the other four Lewis acid catalysts (B(C6F5)3, Al(C6F5)3, Ga((C6F5)3, and In((C6F5)3) demonstrate effectiveness in catalyzing the carbazolation reaction of alkyne alongside with N-carbazole. Additionally, it is anticipated that, among the five categories of G15-carbazole molecules studied, only N-carbazole can participate in the carbazolation reaction with alkyne catalyzed by B(C6F5)3, considering both kinetic and thermodynamic factors at room temperature. Our theoretical investigations, as outlined in this study, indicate that the carbazolation reaction of the alkyne, catalyzed by G13(C6F5)3 and G15-carbazole, follows Hammond's postulate. To put it more plainly, when the transition state of the chemical reaction occurs earlier, it results in a decrease in activation energy.

Hydrogen Bonding Promotes 1-Butanol-3-Carbocation to 4-Methyl-1,3-Dioxane in Prins Condensation of Formaldehyde with Propene on Solid Acid Catalysts

Hydrogen Bonding Promotes 1-Butanol-3-Carbocation to 4-Methyl-1,3-Dioxane in Prins Condensation of Formaldehyde with Propene on Solid Acid Catalysts

Efficient synthesis of some [1,3]-oxazine derivatives in the presence of solid acid nano catalyst based on ferrierite and study on their activity against breast cancer through molecular docking calculation

In this research, the magnetic solid acid nanocatalyst based on ferrierite has been prepared and used as catalyst for the green synthesis of some [1,3]-oxazine derivatives in water at room temperature. The synthesized compounds were obtained in high to excellent yields after short reaction times and the structure of synthesized products were investigated by spectroscopic methods such as: FT-IR, 1H NMR and 13C NMR. The prepared magnetic solid acid catalyst was characterized using XRD, FT-IR, FE-SEM, EDX, elemental mapping, TGA and VSM analysis methods. Magnetic catalyst has easy separation ability, which leads to better and easier recycling. The preparation and synthesis of [1,3]-oxazine derivatives were carried out at room temperature in the presence of M-FER/TEPA/SO3H. Easy workup, green solvent (water) and also short reaction times with high to excellent yield of products, are some of advantageous of presented method. Docking calculations on the structure of the synthesized compounds proved their medicinal properties against breast cancer cells.

Recyclable Covalent Adaptable Polystyrene Networks Using Boronates and TetraAzaADamantanes.

With an ever-increasing annual production of polymers and the accumulation of polymer waste leading to progressively adverse environmental consequences, it has become important that all polymers can be efficiently recycled at the end of their life cycle. Especially thermosets are intrinsically difficult to recycle because of their permanent covalent cross-links. A possible solution is to switch from using thermosets to covalent adaptable networks, sparking the rapid development of novel dynamic covalent chemistries and derived polymer materials. Next to development of these innovative polymer materials, there is also an evident advantage of merging the virtues of covalent adaptable networks with the proven material properties of widely used commodity plastics, by introducing dynamic covalent bonds in these original thermoplastic materials to obtain recyclable thermosets. Here we report the synthesis and characterization of a polystyrene polymer, functionalized with TetraAzaADamantanes and cross-linked with dynamic covalent boronic esters. The material properties were characterized for different degrees of cross-linking. The materials showed good solvent resistance with a high remaining insoluble fraction. In line with the typical behavior of traditional covalent adaptable networks, the prepared polystyrene-based boronate-TetraAzaADamantane materials were able to undergo stress relaxation. The material relaxation was also shown to be tunable by mixing with an acid catalyst. Lastly, the materials could be recycled at least 2 times.

Synthesis and E-metric Studies of an Economically Viable Heterogeneous Acid Catalyst for Production and Upscaling of Solketal

Synthesis and E-metric Studies of an Economically Viable Heterogeneous Acid Catalyst for Production and Upscaling of Solketal

Reaction Pathway Analysis of PET Deconstruction via Methanolysis and Tertiary Amine Catalysts.

Polyethylene terephthalate (PET) is a type of polymer frequently used in plastic packaging that significantly adds the amount of plastic waste found in landfills. One of the ways to recover valuable raw materials from postconsumer plastic is by depolymerizing PET into its monomeric constituents, which are dimethyl terephthalate (DMT) and ethylene glycol. PET depolymerization is often done in methanolysis with the help of acidic or base catalysts. Tertiary amine is one of the most attractive base catalysts for PET depolymerization in methanolysis since it does not lead to the generation of potentially environmentally harmful waste, unlike metal-based catalysts. However, the mechanism by which tertiary amines catalyze PET depolymerization in methanolysis remains unexplored. Developing a detailed mechanistic understanding of this process is important for improving plastic upcycling since it opens the possibility of employing various cheaper and more environmentally friendly reaction conditions. Using density functional theory and transition state analysis, we show that in the presence of tertiary amine catalysts, methanolysis of PET consists of multiple discrete-step reactions rather than a single concerted step. Furthermore, by comparing our calculations to recent experimental results, we were able to rationalize the DMT yield from the depolymerization process by relating it to charge polarization within tertiary amine catalysts, thus opening a pathway to identify atomic descriptors for future catalyst design.

Iron-sulphur protein catalysed [4+2] cycloadditions in natural product biosynthesis

To the best of our knowledge, enzymes that catalyse intramolecular Diels-Alder ([4+2] cycloaddition) reactions are frequently reported in natural product biosynthesis; however, no native enzymes utilising Lewis acid catalysis have been reported. Verticilactam is a representative member of polycyclic macrolactams, presumably produced by spontaneous cycloaddition. We report that the intramolecular [4+2] cycloadditions can be significantly accelerated by ferredoxins (Fds), a class of small iron-sulphur (Fe-S) proteins. Through iron atom substitution by Lewis acidic gallium (Ga) iron and computational calculations, we confirm that the ubiquitous Fe-S cluster efficiently functions as Lewis acid to accelerate the tandem [4+2] cycloaddition and Michael addition reactions by lowering free energy barriers. Our work highlights Nature’s ingenious strategy to generate complex molecule structures using the ubiquitous Fe-S protein. Furthermore, our study sheds light on the future design of Fd as a versatile Lewis acid catalyst for [4+2] cycloaddition reactions.

Design, synthesis and biological Evaluation of novel chromones having 3,4-dihydropyrimidin-2(1H)-one core at C-8 in combination with triazoles: New α-glucosidase inhibitors and anti-bacterial agents

The Biginelli reaction synthesizes dihydropyrimidones through a multi-component reaction. A β-ketoester, aldehyde, and urea or thiourea react in the presence of an acid catalyst to form these dihydropyrimidones. 3,4-Dihydropyrimidin-2(1H)-One/Chromone/Triazole hybrids (9a-9l) were synthesized by multiple steps including one pot Biginelli multicomponent reaction depicted in the scheme. An efficient method for the Biginelli reaction of Chromone aldehyde, acetoacetate esters, and urea employed in the presence of ferric chloride is described. In the end, we have successfully synthesized twelve derivatives of 3,4-Dihydropyrimidin-2(1H)-One/Chromone/Triazole hybrids and subjected them to testing for Antibacterial activity and α-glucosidase inhibition activity. Among these derivatives, compound 9g (IC50 = 142.92 nmol) and 9e (144.49 nmol) exhibited significant inhibitory activity in comparison to the positive control acarbose (IC50 = 350.91 nmol). Compound 9g demonstrated the most significant suppression against Escherichia coli and Bacillus cereus, with zone diameters of 8.8 ± 1.35 mm and 9.1 ± 0.23 mm, respectively. Compound 9b displayed a clear area where bacterial growth was inhibited, measuring 7.5 ± 1.25 mm against Klebsiella pneumonia. Compound 9k exhibited a zone of inhibition measuring 8 ± 1.2 mm in radius against Staphylococcus epidermidis. The docking results for the synthesized compounds indicate that compound 9b exhibited the most favorable docking score of −10 kcal/mol, whereas compound 9a had the second-best docking score of −8.7 kcal/mol. Molecular docking was utilized to examine the interactions between the title compounds and α-glucosidase, in order to provide valuable insights. The data obtained revealed significant interactions that contribute to the inhibitory effects of the drugs against α-glucosidase. These compounds exhibit significant potential as attractive initial candidates for the development of new α-glucosidase inhibitors.

Evaluation of homogeneous and heterogeneous catalytic strategies for furfural production from sugar-derived biomass in a solvent-free green pressurized reaction media (subcritical water-CO2)

A green organic, solvent-free, subcritical water-CO2 (subW-CO2) system was proposed for the production of furfural from the main hemicellulose's sugar, xylose. Despite subW itself showed potential for furfural generation due to its catalytic properties under subcritical conditions; when CO2 was added into the system as pressurization agent, higher yields were reached due to its effect as a Brønsted acid when dissolved in water. Furthermore, its combination with different Lewis acidic catalysts showed a synergistic effect, further improving furfural yield. In a batch configuration, five homogeneous and four heterogeneous catalysts were tested at 180 °C and 5.5 MPa and compared for the first time in a subW-CO2 reaction medium. Different furfural production paths were determined for the two catalysts types, with higher xylose isomerization rates to xylulose when homogeneous trivalent metal catalysts were used. CrCl3 and Nafion NR50 resin were selected as best catalysts from each of the groups due to higher furfural production rates (51.9 ± 0.9 % yield/h) and higher furfural selectivity (60.9 %), respectively. Furthermore, Nafion NR50 catalytic activity remained unchanged after 10 runs at 180 °C. The green subW-CO2 system furfural yields were comparable to water-organic solvent biphasic ones, proving to be a promising green alternative.

Intensification of valorization of cooked rice water through energy-efficient synthesis of drop-in biofuel (butyl levulinate): engine performance, emission profile, and environmental impact assessments.

For the first time, an energy-efficient and eco-friendly technology for the conversion of abundantly available kitchen waste, specifically waste cooked rice water (WCRW) to drop-in- biofuels, namely, butyl levulinate (BL), has been explored. The synthesis of BL was accomplished employing butyl alcohol (BA) and WCRW in an energy-efficient UV (5W each UVA and UVB)-near-infrared (100W) irradiation assisted spinning (120rpm) batch reactor (UVNIRSR) in the presence of TiO2-Amberlyst 15 (TA15) photo-acidic catalyst system (PACS). The optimal 95.81% yield of BL (YBL) could be achieved at 10 wt% catalyst concentration, 60°C reaction temperature, 80min time, and 1:10 WCRW: BA concentration as per Taguchi statistical design. Moreover, additional combination of different PACS such as TiO2-Amberlyst 16, TiO2-Amberlyst 36, and TiO2-Amberlite IRC120 H rendered 86.72% YBL, 90.04% YBL, and 93.47% YBL, respectively, proving superior efficacy compared to individual activity of the acidic catalysts and photocatalysts. The heterogeneous reaction kinetics study for TA15 PACS suggested Langmuir-Hinshelwood model to be the best fitted model. A significant 63.33% energy could be saved by UVNIRSR as compared to conventional heated reactor at the optimized experimental condition using PACS TA15. An overall alleviation in environmental pollution with 59.259% reduction in GWP, 15.254% decline in terrestrial ecotoxicity, 18.238% diminution in marine ecotoxicity, 17.25% decrease in ozone formation affecting human health, 5.865% reduction in human non-carcinogenic toxicity, 18.65% diminution in ozone formation affecting terrestrial ecosystem, 55.17% significant decrease in terrestrial acidification, and 25.619% mitigation in fresh water ecotoxicity could be observed. Furthermore, BL-biodiesel-diesel blends (3% BL, 7% biodiesel, and 90% diesel) exhibited significant reduction (25.45% and 36%, respectively, for CO and HC) in harmful engine exhaust emissions demonstrating environmental sustainability of the overall process.