Manussada Ratanasak

Metal–organic framework (MOF) catalysts are promising platforms for hydrogen energy systems, enabling CO ₂ conversion to formic acid (HCOOH), a liquid organic hydrogen carrier (LOHC) for hydrogen storage and release. Density functional theory (DFT) calculations (M06‐2X/6‐31G(d)/LANL2DZ) are performed to investigate CO ₂ hydrogenation on PCN‐250(Fe) clusters featuring frustrated Lewis pair (FLP) sites formed by linker removal. The full hydrogenation pathway, including H ₂ adsorption, activation, and HCOOH formation, is explored, with HCOOH formation identified as the rate‐determining step. Activation barriers from large and small cluster models are consistent (10.0 and 9.4 kcal mol ⁻¹ ). Secondary metal substitution at the Fe ₂ MO node is screened using first‐ and second‐row transition metals (Mn–Zn and Tc–Cd). Results show electronic effects dominate first‐row metals, whereas steric effects govern second‐row systems. Kinetic volcano analysis identifies Cu(II) and Ru(III) as optimal catalysts for efficient CO ₂ hydrogenation, supporting rational design of MOF‐based hydrogen storage and conversion systems for sustainable energy applications.

Metal-organic framework (MOF) catalysts are highly adjustable platforms for converting CO2 into valuable chemicals, especially formic acid (HCOOH), which is a promising liquid organic hydrogen carrier (LOHC) for safe and efficient energy storage. In this work, density functional theory (DFT) calculations at the M06-2X/6-31G(d)/LANL2DZ level were used to study CO2 hydrogenation to HCOOH over PCN-250(Fe) clusters with Frustrated Lewis pair (FLP) sites created by linker removal. The entire reaction pathway, including H2 absorption, H2 dissociation, and HCOOH formation, was mapped out, with HCOOH formation identified as the rate-determining step. To improve catalytic performance, auxiliary secondary metal substitution (M) at the Fe2MO node was systematically investigated using first-row (Mn, Co, Ni, Cu, Zn) and second-row (Tc, Ru, Rh, Pd, Ag, Cd) transition metals. Mechanistic analysis shows electronic effects primarily govern activation barriers for first-row metals, while steric effects are more impactful for second-row metals within the MOF structure. Finally, kinetic volcano plots based on the Gibbs free energy of key intermediates highlight Cu(II), Ru(III), and Tc(II) as the most promising secondary metals for efficient CO2 utilization. These insights offer a rational, bottom-up approach for designing defect-engineered Fe-based MOFs for sustainable fuel production.

2-Mercaptophenylboronic acid (2-MPBA) facilitates the efficient hydrolysis of peptide thioesters under mild conditions via tandem thiol–thioester exchange and borate-assisted water activation.

DFT study reveals TsNCO enhances PU selectivity over PPC. Tosyl and QA cation cooperatively stabilize key intermediates, lowering activation barriers and suppressing cyclic by-product pathways.

Ligand design for H₂ oxidation/production activity of Ni complex via tuning dihedral angle. Tetrahedral constraint leads to H₂ oxidation while square-planar constraint switches to H₂ production.

DFT calculations explored the ethylene polymerization mechanism of 11 M-α-diimine catalysts, revealing the crucial role of steric interactions in modulating activity and guiding catalyst design.

This study presents a novel and practical strategy for synthesizing cannabinoids using a fluorinated alcohol solvent for the first time. Hexafluoroisopropanol (HFIP) was found to efficiently promote intermolecular Friedel–Crafts alkylation between allylic alcohols and electron‐rich aromatics. This approach enabled the successful synthesis of cannabidiol (CBD) derivatives bearing various alkyl substituents, as well as the corresponding unnatural regioisomer (abnCBD), achieving moderate to high yields under mild conditions without the need for additional catalysts or other reagents. Insights in the mechanistic details were obtained through DFT calculations. Furthermore, a streamlined three‐step synthesis of 5‐alkyl resorcinol derivatives, essential starting materials for CBD synthesis, from the readily available chalcones was developed. Preliminary cytotoxicity assays using MTT revealed that some synthetic CBD derivatives exhibited promising anticancer activities.

Global concerns regarding the depletion and strategic importance of phosphorus resources have increased demand for the recovery and recycling. However, waste-derived phosphorus compounds, primarily as chemically inert phosphoric acid or its salts, present a challenge to their direct conversion into high-value chemicals. We aimed to develop an innovative technology that bypasses the use of white phosphorus and enables direct esterification of phosphoric acid to produce widely applicable phosphate triesters. Tetraalkyl orthosilicates emerged as highly effective reagents for the direct triple esterification of 85% phosphoric acid, as well as the esterification of organophosphinic and phosphonic acids. Furthermore, we achieved direct esterification of recovered phosphoric acid with tetraalkyl orthosilicate, thus pioneering a recycling pathway from sewage waste to valuable phosphorus chemicals. Experimental and theoretical investigations revealed a novel mechanism, wherein tetraalkyl orthosilicates facilitate multimolecular aggregation to achieve alkyl transfer from tetraalkylorthosilicate to phosphoric acid via multiple proton shuttling.

Given the industrial importance of (meth)acrylate esters, various groups have devoted considerable effort to investigating their chemoselective transesterification. In 2021, we developed magnesium(II) and sodium(I) complexes derived from 2,6-di-tert-butyl-p-cresol (BHT-H) as chemoselective catalysts for the transesterification of methyl acrylate (MA) and methyl methacrylate (MMA), respectively. Based on our results, we report the discovery of magnesium(II) and sodium(I) salts derived from 6,6’-(propane-2,2’-diyl)bis(2,4-di-tert-butylphenol) (PBTP-H₂), i.e. Mg(PBTP) and Na₂(PBTP), which are 41 and 81 times more effective catalysts than Mg(BHT)₂ and Na(BHT) for the transesterification of MA and MMA, respectively. These new catalysts are highly effective across an extensive range of alcohols, including primary and secondary alcohols, diols, and triols. Overall, this efficient transesterification technology can be expected to find practical applications in industrial process chemistry.