Hydrolysis of triacylglyceridesin the presence of tin(IV) catalysts

Silva, Eid C. da; Mendes, Paula; Brito, Yariadner C.; Meneghetti, Mário R.; Meneghetti, Simoni Margareti Plentz

doi:10.1016/j.catcom.2016.01.032

Cited by 17 publications

(5 citation statements)

References 19 publications

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“…9,10 For example, organotin nanoclusters can function as catalytic supports 1,11 or as catalysts for transesterification and esterification reactions. 2,3 Organotin materials have been shown to exhibit both antiviral and anticancer activity mainly because of their ability to interact with DNA. 6−8 Organotin nanoclusters can be synthesized with precise atomic-scale control, where manipulation of size, shape, or structure allows for a range of chemical compositions and properties.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Organotin compounds have a wide range of potential applications, including use as catalysts, − biocides, polymer stabilizers, , anticancer agents, − and precursors for nanoscale materials. , For example, organotin nanoclusters can function as catalytic supports , or as catalysts for transesterification and esterification reactions. , Organotin materials have been shown to exhibit both antiviral and anticancer activity mainly because of their ability to interact with DNA. − Organotin nanoclusters can be synthesized with precise atomic-scale control, where manipulation of size, shape, or structure allows for a range of chemical compositions and properties. , This precise control provides for promising applications, which include their use as inorganic photoresists for extreme ultraviolet (EUV) photolithography. − …”

Section: Introductionmentioning

confidence: 99%

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Ambient-Pressure X-ray Photoelectron Spectroscopy Characterization of Radiation-Induced Chemistries of Organotin Clusters

Diulus

Frederick

et al. 2018

ACS Appl. Mater. Interfaces

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Advances in extreme ultraviolet (EUV) photolithography require the development of next-generation resists that allow high-volume nanomanufacturing with a single nanometer patterning resolution. Organotin-based photoresists have demonstrated nanopatterning with high resolution, high sensitivity, and low-line edge roughness. However, very little is known regarding the detailed reaction mechanisms that lead to radiation-induced solubility transitions. In this study, we investigate the interaction of soft Xray radiation with organotin clusters to better understand radiation-induced chemistries associated with EUV lithography. Butyltin Keggin clusters (β-NaSn 13 ) were used as a model organotin photoresist, and characterization was performed using ambient-pressure X-ray photoelectron spectroscopy. The changes in relative atomic concentrations and associated chemical states in β-NaSn 13 resists were evaluated after exposure to radiation for a range of ambient conditions and photon energies. A significant reduction in the C 1s signal versus exposure time was observed, which corresponds to the radiation-induced homolytic cleavage of the butyltin bond in the β-NaSn 13 clusters. To improve the resist sensitivity, we evaluated the effect of oxygen partial pressure during radiation exposures. We found that both photon energy and oxygen partial pressure had a strong influence on the butyl group desorption rate. These studies advance the understanding of radiation-induced processes in β-NaSn 13 photoresists and provide mechanistic insights for EUV photolithography.

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Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Ambient-Pressure X-ray Photoelectron Spectroscopy Characterization of Radiation-Induced Chemistries of Organotin Clusters

Diulus

Frederick

et al. 2018

ACS Appl. Mater. Interfaces

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“…In the literature, there have been several studies documenting the use of organometallic tin(IV) compounds as esterification and transesterification catalysts. − Silva et al reported the ordering of reactivity for several catalysts as di- n -butyl-oxo-stannane (Bu 2 SnO) > di- n -butyltin dilaurate (Bu 2 SnLau 2 ) > n -butyl stannoic acid (BuSnO(OH)) > Bu 2 SnCl 2 > BuSnCl 3 for the glycerolysis of triacylglycerides to produce monoacylglycerols and diacylglycerols. Meneghetti et al suggested the Lewis acid and exchange/insertion mechanism to catalyze the transesterification reaction by various tin-based catalysts (i.e., R 2 Sn(OAc) 2 , R 2 SnO, R 2 SnCl 2 , R 2 SnS, etc.)…”

Section: Resultsmentioning

confidence: 99%

Transesterification in Vitrimer Polymers Using Bifunctional Catalysts: Modeled with Solution-Phase Experimental Rates and Theoretical Analysis of Efficiency and Mechanisms

Bhusal

Kang

et al. 2021

J. Phys. Chem. B

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Recently, thermoset vitrimer polymers have shown significant promise for structural applications because of their ability to be reshaped and remolded due to their covalent adaptive network (CAN). In these vitrimers, the transesterification reaction is responsible for the CAN, where the efficiency of the reaction is controlled either by organic or by organometallic catalysts. Understanding the mechanism of the transesterification reaction in the bulk phase using direct experimental techniques is extremely difficult due to the highly cross-linked complex structure of thermosetting vitrimers. Therefore, we use solution-phase experiments to investigate the catalytic efficiency and to guide density functional theory (DFT) simulations of the transesterification reaction mechanism with catalysts triazabicyclodecene (TBD), zinc acetate (Zn(OAc) 2 ), 1-methylimidazole (1-MI), and dibutyltin oxide (DBTO). The estimated catalytic efficiency from the detailed DFT reaction path calculations follows the order TBD ≳ DBTO ≳ Zn(OAc) 2 > 1-MI, which agrees with the experimental results. In addition to reaction path modeling, the mechanism and the relative rates of the transesterification reaction are analyzed with the assistance of Fukui indices as a measure of electrophilicity and nucleophilicity of atomic sites and with partial charges. It was found that the sum of the nucleophilicity index of the base and the electrophilicity index of the acid of the bifunctional catalysts correlates with the S N 2 transition state and tetrahedral intermediate energies, which are related to the barrier of the rate-limiting step. This correlation provides a hypothesis for computational prescreening of potentially better catalysts that have an index in a range of values. These results provide a basis for understanding an important part of the mechanism of transesterification in vitrimer systems and may assist with designing new catalysts.

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“…The usual industrial process for the hydrolysis to take place, the Colgate-Emery process, entails high temperature (at least 250°C) and pressure (4.82 MPa) ( Barnebey and Brown, 1948), implying in a high energy cost in addition to undesirable reactions and by-products formation (Rooney and Weatherley, 2001). Oil hydrolysis can also be performed by employing chemical catalysts (Da Silva et al, 2016;Devaraj et al, 2018;Ong et al, 2016), enzymatic catalysts (lipases) (Cavalcanti-Oliveira et al, 2010;Corradini et al, 2019;de Sousa et al, 2010;El-Hefnawy and Sakran, 2014;Goñi et al, 2018;Santos et al, 2013), using subcritical water (Almeida et al, 2017;dos Santos et al, 2019;Ilham and Saka, 2010;Xiao et al, 2017) or other less conventional methods as microwave irradiation (Nguyen et al, 2020) and the use of ionic liquids (Han et al, 2019).…”

Section: Introductionmentioning

confidence: 99%

Rapid Enzymatic Hydrolysis of Crambe Oil Catalyzed by Castor Seeds Lipases

Tavares

Sackser

Borba

et al. 2020

Preprint

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A rapid and eco-friendly method, using ultrasound power, was successfully employed to hydrolyze Crambe oil using lipase enzymes directly from castor seeds, in oil-free and in natura forms. A yield of 86% conversion of triglycerides into free fatty acids (FFA) was achieved in 5 minutes using in natura seeds and 73% of conversion when performing the reaction with oil-free seeds. The operational conditions of ultrasound power, mass ratio of buffer solution and oil, catalyst, and total substrate were evaluated using a central composite rotatable design (CCRD). The hydrolysis yield was optimized by Response Surface Methodology. The optimum conditions were approximately 70% of ultrasound power (350 W), 1.79 buffer solution/oil mass ratio, and 0.25 catalyst/substrate mass ratio for in natura seeds. For the oil-free seeds, the optimal conditions found were 68% (340 W) of ultrasound power, 1.67 buffer solution/oil mass ratio, and 0.06 catalyst/substrate mass ratio. Mathematical modeling was applied to the experimental kinetic data, and it was possible to predict FFA concentration values from independent experiments.

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Hydrolysis of triacylglyceridesin the presence of tin(IV) catalysts

Cited by 17 publications

References 19 publications

Ambient-Pressure X-ray Photoelectron Spectroscopy Characterization of Radiation-Induced Chemistries of Organotin Clusters

Ambient-Pressure X-ray Photoelectron Spectroscopy Characterization of Radiation-Induced Chemistries of Organotin Clusters

Transesterification in Vitrimer Polymers Using Bifunctional Catalysts: Modeled with Solution-Phase Experimental Rates and Theoretical Analysis of Efficiency and Mechanisms

Rapid Enzymatic Hydrolysis of Crambe Oil Catalyzed by Castor Seeds Lipases

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