Computational Advances in Ionic Liquid Applications for Green Chemistry: A Critical Review of Lignin Processing and Machine Learning Approaches.

The valorization and dissolution of lignin using ionic liquids (ILs) is critical for developing sustainable biorefineries and a circular bioeconomy. This review aims to critically assess the current state of computational and machine learning methods for understanding and optimizing IL-based lignin dissolution and valorization processes reported since 2022. The paper examines various computational approaches, from quantum chemistry to machine learning, highlighting their strengths, limitations, and recent advances in predicting and optimizing lignin-IL interactions.

Engineered reduction of S-adenosylmethionine alters lignin in sorghum.

Background: Lignin is an aromatic polymer deposited in secondary cell walls of higher plants to provide strength, rigidity, and hydrophobicity to vascular tissues. Due to its interconnections with cell wall polysaccharides, lignin plays important roles during plant growth and defense, but also has a negative impact on industrial processes aimed at obtaining monosaccharides from plant biomass. Engineering lignin offers a solution to this issue.

Perspective on Lignin Conversion Strategies That Enable Next Generation Biorefineries.

The valorization of lignin, a currently underutilized component of lignocellulosic biomass, has attracted attention to promote a stable and circular bioeconomy. Successful approaches including thermochemical, biological, and catalytic lignin depolymerization have been demonstrated, enabling opportunities for lignino-refineries and lignocellulosic biorefineries. Although significant progress in lignin valorization has been made, this review describes unexplored opportunities in chemical and biological routes for lignin depolymerization and thereby contributes to economically and environmentally sustainable lignin-utilizing biorefineries.

An Engineered Laccase from Accelerates Lignocellulose Degradation.

Laccases from white-rot fungi catalyze lignin depolymerization, a critical first step to upgrading lignin to valuable biodiesel fuels and chemicals. In this study, a wildtype laccase from the basidiomycete (Fom_lac) and a variant engineered to have a carbohydrate-binding module (Fom_CBM) were studied for their ability to catalyze cleavage of β-O-4' ether and C-C bonds in phenolic and non-phenolic lignin dimers using a nanostructure-initiator mass spectrometry-based assay. Fom_lac and Fom_CBM catalyze β-O-4' ether and C-C bond breaking, with higher activity under acidic conditions (pH < 6).

Lignin deconstruction by anaerobic fungi.

Lignocellulose forms plant cell walls, and its three constituent polymers, cellulose, hemicellulose and lignin, represent the largest renewable organic carbon pool in the terrestrial biosphere. Insights into biological lignocellulose deconstruction inform understandings of global carbon sequestration dynamics and provide inspiration for biotechnologies seeking to address the current climate crisis by producing renewable chemicals from plant biomass. Organisms in diverse environments disassemble lignocellulose, and carbohydrate degradation processes are well defined, but biological lignin deconstruction is described only in aerobic systems.

Funneled Depolymerization of Ionic Liquid-Based Biorefinery "Heterogeneous" Lignin into Guaiacols over Reusable Palladium Catalyst.

The efficient utilization of lignin, the direct source of renewable aromatics, into value-added renewable chemicals is an important step towards sustainable biorefinery practices. Nevertheless, owing to the random heterogeneous structure and limited solubility, lignin utilization has been primarily limited to burning for energy. The catalytic depolymerization of lignin has been proposed and demonstrated as a viable route to sustainable biorefinery, however, low yields and poor selectivity of products, high char formation, and limited to no recycling of transition-metal-based catalyst involved in lignin depolymerization demands attention to enable practical-scale lignocellulosic biorefineries.

Advanced one-pot deconstruction and valorization of lignocellulosic biomass into triacetic acid lactone using Rhodosporidium toruloides.

Background: Rhodosporidium toruloides is capable of co-utilization of complex carbon sources and robust growth from lignocellulosic hydrolysates. This oleaginous yeast is therefore an attractive host for heterologous production of valuable bioproducts at high titers from low-cost, deconstructed biomass in an economically and environmentally sustainable manner. Here we demonstrate this by engineering R.

Renewable Schiff-Base Ionic Liquids for Lignocellulosic Biomass Pretreatment.

Growing interest in sustainable sources of chemicals and energy from renewable and reliable sources has stimulated the design and synthesis of renewable Schiff-base (iminium) ionic liquids (ILs) to replace fossil-derived ILs. In this study, we report on the synthesis of three unique iminium-acetate ILs from lignin-derived aldehyde for a sustainable “future” lignocellulosic biorefinery. The synthesized ILs contained only imines or imines along with amines in their structure; the ILs with only imines group exhibited better pretreatment efficacy, achieving >89% sugar release.

Clozapine Induced Hypertension and its Association with Autonomic Dysfunction.

Clozapine is a second generation antipsychotic agent which is drug of choice for treatment resistant schizophrenia. Tachycardia and postural hypotension are most frequently observed cardiovascular adverse effects, but reports on new-onset persistently elevated blood pressure are sparse. Mechanisms underlying clozapine induced hypertension also remain unclear.

Solubility Studies of Cyclosporine Using Ionic Liquids.

Six ionic liquids (ILs) were selected based on their chemical and physical properties to study the solubility of cyclosporine A. Of these, cyclosporine exhibited higher room temperature solubility in 1-ethyl-3-methylimidazolium acetate ([Cmim][OAc]) than in acetone, an effective molecular solvent used to solubilize and purify cyclosporine. The solubility of cyclosporine in the ILs dramatically increased at higher temperatures, a critical factor that cannot be varied in a wide range with low boiling molecular solvents.

Azolate Anions in Ionic Liquids: Promising and Under-Utilized Components of the Ionic Liquid Toolbox.

Owing to their ease of synthesis, diffuse positive charge, and chemical stability, 1-alkyl-3-methylimidazolium cations (i.e., [C mim] ) are one of the most routinely utilized and historically important components in ionic liquid (IL) chemistry.

Ionic liquids in cross-coupling reactions: "liquid" solutions to a "solid" precipitation problem.

To alleviate the problem of solid salt precipitation when using inorganic bases in cross-coupling reactions, basic anions were combined with the trihexyl(tetradecyl)phosphonium ([P]) cation to ensure an ionic liquid byproduct. If the starting base is also an ionic liquid, as is the case for [P][OH]·4MeOH, it can be used as both base and solvent.

Selective Oxidation of 1,6-Hexanediol to 6-Hydroxycaproic Acid over Reusable Hydrotalcite-Supported Au-Pd Bimetallic Catalysts.

Selective oxidation of 1,6-hexanediol into 6-hydroxycaproic acid was achieved over hydrotalcite-supported Au-Pd bimetallic nanoparticles as heterogeneous catalyst using aqueous H2 O2 . N,N-dimethyldodecylamine N-oxide (DDAO) was used as an efficient capping agent. Spectroscopic analyses by UV/Vis, TEM, XPS, and X-ray absorption spectroscopy suggested that interactions between gold and palladium atoms are responsible for the high activity of the reusable Au40 Pd60 -DDAO/HT catalyst.

Direct synthesis of 1,6-hexanediol from HMF over a heterogeneous Pd/ZrP catalyst using formic acid as hydrogen source.

A new approach is developed for hydrogenolytic ring opening of biobased 5-hydroxymethylfurfural (HMF), dehydration product of hexoses, towards 1,6-hexanediol (HDO) under atmospheric pressure. The highest yield of HDO, 43%, is achieved over reusable Pd/zirconium phosphate (ZrP) catalyst at 413 K in the presence of formic acid as hydrogen source. In comparison with various Brønsted and/or Lewis acidic supports, the specific Brønsted acidity on ZrP support effectively accelerated the cleavage of C-O bond in a furan ring.