Carboxylate Hydrogen Bonds Research Articles

Dramatical enhancement of circular dichroism in chiral hybrid perovskites via carboxylic hydrogen bond engineering

Dramatical enhancement of circular dichroism in chiral hybrid perovskites via carboxylic hydrogen bond engineering

Toughening Self-Healing Elastomers with Chain Mobility.

Enhancing fracture toughness and self-healing within soft elastomers is crucial to prolonging the operational lifetimes of soft devices. Herein, it is revealed that tuning the polymer chain mobilities of carboxylated-functionalized polyurethane through incorporating plasticizers or thermal treatment can enhance these properties. Self-healing is promoted as polymer chains gain greater mobility toward the broken interface to reassociate their bonds. Raising the temperature from 80 to 120°C, the recovered work of fracture is increased from 2.86 to 123.7MJ m-3. Improved fracture toughness is realized through two effects. First, strong carboxyl hydrogen bonds dissipate large energies when broken. Second, chain mobilities enable the redistribution of localized stress concentrations to allow crack blunting, enlarging the size of dissipation zones. At optimal conditions of plasticizers (3 wt.%) or temperature (40°C) to promote chain mobilities, fracture toughness improves from 16.3 to 19.9 and 25.6kJ m-2, respectively. Insights of fracture properties at healed soft interfaces are revealed through double cantilever beam tests. These measurements indicate that fracture mechanics play a critical role in delaying complete failure at partial self-healing. By imparting optimal polymer chain mobilities within tough and self-healing elastomers, effective prevention against damage and better recovery are realized.

Activation of peroxymonosulfate by a novel stratiform Co-MOF as catalyst for degradation of dyes in water

Cobalt-based metal-organic frameworks (MOFs) have been used as catalysts to remove macromolecular organic pollutants from wastewater. In this work, a novel type of cobalt-based MOF, CUST-593, was synthesized from cobalt nitrate hexahydrate (Co(NO3)2·6H2O), 2,2-bipyridine (BIPY), and 4,4ˊ,4ˊˊ-nitrilotrisbenzoic acid (NTB) using solvothermal method. The catalytic properties of CUST-593 for degrading dyes in water were then investigated. CUST-593, with the chemical formula {Co(NTB)(BIPY)(H2O)·0.5H2O·0.1DMA}, exhibited excellent catalytic activity in degrading dyes such as methyl orange (MO) and rhodamine B (RhB) in aqueous solutions. CUST-593 has a multi-layered structure, connected by carboxylate hydrogen bonds, which is beneficial to improving its water stability. Synthetic test results showed that CUST-593 effectively attacked dyes by primarily generating sulfate radicals (SO4•−) and a portion of hydroxyl radicals (•OH). Under the testing conditions, MO removal efficiency reached approximately 95 %. Moreover, CUST-593 exhibited remarkable cycling catalytic properties, broad pH range applicability, and long-term effectiveness. A mechanism for the degradation of dyes by CUST-593 was proposed. The experimental findings in this study collectively support the conclusion that CUST-593 serves as a green and environmentally friendly catalyst for the degradation of dyes in polluted water.

Performance evaluation of phosphonium based deep eutectic solvents coated cerium oxide nanoparticles for CO2 capture

The critical challenge being faced by our current modern society on a global scale is to reduce the surging effects of climate change and global warming, being caused by anthropogenic emissions of CO2 in the environment. Present study reports the surface driven adsorption potential of deep eutectic solvents (DESs) surface functionalized cerium oxide nanoparticles (CeNPs) for low pressure CO2 separation. The phosphonium based DESs were prepared using tetra butyl phosphoniumbromide as hydrogen bond acceptor (HBA) and 6 acids as hydrogen bond donors (HBDs). The as-developed DESs were characterized and employed for the surface functionalization of CeNPs with their subsequent utilization in adsorption-based CO2 adsorption. The synthesis of as-prepared DESs was confirmed through FTIR measurements and absence of precipitates, revealed through visual observations. It was found that DES6 surface functionalized CeNPs demonstrated 27% higher adsorption performance for CO2 capturing. On the contrary, DES3 coated CeNPs exhibited the least adsorption progress for CO2 separation. The higher adsorption performance associated with DES6 coated CeNPs was due to enhanced surface affinity with CO2 molecules that must have facilitated the mass transport characteristics and resulted an enhancement in CO2 adsorption performance. Carboxylic groups could have generated an electric field inside the pores to attract more polarizable adsorbates including CO2, are responsible for the relatively high values of CO2 adsorption. The quadruple movement of the CO2 molecules with the electron-deficient and pluralizable nature led to the enhancement of the interactive forces between the CO2 molecules and the CeNPs decorated with the carboxylic group hydrogen bond donor rich DES. The current findings may disclose the new research horizons and theoretical guidance for reduction in the environmental effects associated with uncontrolled CO2 emission via employing DES surface coated potential CeNPs.

Flexing of a Metal–Organic Framework upon Hydrocarbon Adsorption: Atomic Level Insights from Neutron Scattering

Metal–organic frameworks (MOFs) offer considerable opportunities for gas uptake, storage, and separation due to their porosity, chemical tunability, and flexibility. Flexible MOFs undergo reversible structural transformations triggered by external stimuli such as adsorption of specific guest molecules. The MUF-16 family of materials has exceptional gas adsorption properties including selective uptake of carbon dioxide over other gases. We observed one member of this family, MUF-16(Mn), to be flexible upon the adsorption of hydrocarbon gases. We used a combination of in situ synchrotron X-ray and neutron diffraction to identify the framework–gas interactions that underlie the structural flexibility. Inelastic neutron scattering, along with calculations, also enables an understanding of the dynamics of the flexibility. In essence, C3 hydrocarbons effectively bridge across hydrogen-bonded carboxyl dimers in the framework, triggering pore expansion and inhibiting certain types of motion in the framework.

Mechanically robust and fast room-temperature self-healing waterborne polyurethane constructed by coordination bond and hydrogen bond with antibacterial and photoluminescence functions

It is still a great challenge to synthesize waterborne polyurethane (WPU) with excellent mechanical performance and fast room-temperature self-healing ability because of the mutually exclusive nature of these properties. Herein, a room-temperature self-healing waterborne polyurethane based on Zn2+-carboxyl coordination bond and hydrogen bond was prepared by adding zinc ion buffer solution to WPU emulsion. Due to the synergistic effect of dynamic coordination bonds and hydrogen bonds, the optimized sample (WPU-Zn-3) exhibited excellent mechanical properties (a tensile strength of 7.26 MPa, a elongation at break of 855 % and an exceptional toughness of 26.76 MJ/m3) and fast room-temperature self-healing capacity under ethanol induction (a high healing efficiency of 88 % within 4 h), showing a good balance between fast room temperature healing ability and excellent mechanical properties. Interestingly, this method also works for nickel ions but not for iron and aluminum ions. Furthermore, compared with zinc chloride and zinc nitrate, the waterborne polyurethane containing zinc acetate showed the best comprehensive performance. Due to the presence of zinc ions, the sterilization rates of WPU-Zn-3 film samples against Escherichia coli and Staphylococcus were 97.1 % and 97.8 %, respectively. Specially, we introduced graphene quantum dots into the waterborne polyurethanes to construct photoluminescence films and demonstrated their potential applications prospect in the fields of information encryption and anti-counterfeiting. This work broadens the avenue for fabricating room-temperature self-healing and multifunctional waterborne polyurethanes.

Water Sorption Controls Extreme Single-Crystal-to-Single-Crystal Molecular Reorganization in Hydrogen Bonded Organic Frameworks.

As hydrogen bonded frameworks are held together by relatively weak interactions, they often form several different frameworks under slightly different synthesis conditions and respond dynamically to stimuli such as heat and vacuum. However, these dynamic restructuring processes are often poorly understood. In this work, three isoreticular hydrogen bonded organic frameworks assembled through charge-assisted amidinium⋅⋅⋅carboxylate hydrogen bonds (1C/C , 1Si/C and 1Si/Si ) are studied. Three distinct phases for 1C/C and four for 1Si/C and 1Si/Si are fully structurally characterized. The transitions between these phases involve extreme yet recoverable molecular-level framework reorganization. It is demonstrated that these transformations are related to water content and can be controlled by humidity, and that the non-porous anhydrous phase of 1C/C shows reversible water sorption through single crystal to crystal restructuring. This mechanistic insight opens the way for the future use of the inherent dynamism present in hydrogen bonded frameworks.

Effect of hydrogen bonds on the thermal transport in a precisely branched polyethylene with ordered and amorphous structures

Hydrogen bonds are considered to be bridges in forming networks for heat transfer in polymers. Nevertheless, a large number of polymer systems with hydrogen bonds have very low thermal conductivity (TC). The role of hydrogen bonds in regulating TC of polymers is still beyond fully understood. Herein, we systematically investigate the effect of hydrogen bonds on the intrinsic TC of polymers with ordered and amorphous structures by using molecular dynamics simulations. The ordered polymer (termed as ar-P21AA) has lamella structure with stacked layers alternatively composed of aligned polymer chains and hydrogen-bonded functional groups, which provides an ideal model for studying hydrogen-bond-mediated heat transfer. We find that significant ITR exists at the interface composed of hydrogen-bonded carboxyl groups; nevertheless, ITR of that hydrogen-bonded interface is about 2 times smaller than that of a typical VdWs interface. The Role of hydrogen bonds in enhancing the interfacial thermal transport is analyzed. As for the amorphous ar-P21AA, increasing the hydrogen-bonding strength does not change much TC due to the invariance of stiffness and packing density of the structure, in terms of the minimum thermal conductivity model. A consequent effect on the chain morphology when introducing hydrogen bonds may be a factor to be considered for improving the thermal conductivity. The work provides insight into the design of thermally conductive polymers by introducing hydrogen-bonding interaction.

The structural pathway from its solvated molecular state to the solution crystallisation of the α- and β-polymorphic forms of para amino benzoic acid.

Para amino benzoic acid (PABA) has two well-characterised α- and β-polymorphic forms and, whilst both crystallise in the monoclinic space group P21/n, they have quite different crystal chemistry and crystallisability behaviour. Previous work has shown that the molecular conformation deformation energy in the crystalline state is higher for the β-form than for the α-form and that the lattice energy for the former converges more slowly than for the latter overall. This suggests that not only is there a higher barrier to crystallisation for the β-form but also that low solution supersaturations might be needed for it to preferentially nucleate. Additionally, solute cluster propensity and solute solvation energetic analysis highlight the importance of an aqueous solvation environment in inhibiting the α-form's strong OH⋯O carboxylic acid hydrogen bond (H-bond) dimer. Despite this, the detailed molecular-scale pathway from solvated molecules to 3D crystallographic structure still remains unclear, most notably regarding how the nucleation process is activated and how, as a result, this mediates the preferential formation of either of the two polymorphic forms. Molecular dynamics (MD) simulations coupled with FTIR studies and intermolecular synthon analysis address this issue through characterisation of the propensity of the incipient bulk synthons that are important in the crystallisation of the two polymorphic forms within the solution state. MD molecular trajectory analysis within crystallisation solutions reveals a greater propensity for OH⋯O synthons (both single H-bonds and homodimers) typical of the α-form and NH⋯O synthons found in both the α- and β-forms when compared to aqueous solution but much lower propensities for the β-form's "fingerprinting" OH⋯N and π-π stacking synthons. In contrast, data from the aqueous solution environment reveals a much greater propensity for the β-form's π-π interaction synthons. IR dilution studies in acetonitrile in the carbonyl region reveal the presence of two CO vibrational stretching bands, whose relative intensities vary as a function of solution dilution. These were assigned to the solvated PABA monomer and a COOH dimer of PABA. Similar data in ethanol shows a main CO stretching band with a shoulder peak suggesting a similar monomer vs. dimer speciation may exist in this solvent. The IR data is consistent with the organic solvent MD data, albeit the corresponding analysis for the aqueous solution was precluded due to the latter's strong OH vibrational mode which restricted validation in aqueous solutions.

Rac-1,8-Bis(2-carbamoyleth-yl)-5,5,7,12,12,14-hexa-methyl-1,4,8,11-tetra-aza-cyclo-tetra-deca-ne]copper(II) di-acetate tetra-hydrate: crystal structure and Hirshfeld surface analysis.

The title CuII macrocyclic complex salt tetra-hydrate, [Cu(C22H46N6O2)](C2H3O2)2·4H2O, sees the metal atom located on a centre of inversion and coordinated within a 4+2 (N4O2) tetra-gonally distorted coordination geometry; the N atoms are derived from the macrocycle and the O atoms from weakly associated [3.2048 (15) Å] acetate anions. Further stability to the three-ion aggregate is provided by intra-molecular amine-N-H⋯O(carboxyl-ate) hydrogen bonds. Hydrogen bonding is also prominent in the mol-ecular packing with amide-N-H⋯O(amide) inter-actions, leading to eight-membered {⋯HNCO}2 synthons, amide-N-H⋯O(water), water-O-H⋯O(carboxyl-ate) and water-O-H⋯O(water) hydrogen bonds featuring within the three-dimensional architecture. The calculated Hirshfeld surfaces for the individual components of the asymmetric unit differentiate the water mol-ecules owing to their distinctive supra-molecular association. For each of the anion and cation, H⋯H contacts predominate (50.7 and 65.2%, respectively) followed by H⋯O/O⋯H contacts (44.5 and 29.9%, respectively).

Bis(pyrazol-1-yl)methane-4,4′-dicarboxylic Acid

The molecular structure of bis(pyrazol-1-yl)methane-4,4′-dicarboxylic acid (H2bpmdc) was determined by single crystal X-Ray diffraction analysis. The compound crystallizes in a monoclinic crystal system; the unit cell contains four formula units. The molecules of H2bpmdc are linked into zig-zag chains by intermolecular carboxyl–carboxyl hydrogen bonds. Other types of supramolecular interactions, namely, CH···N and CH···O short contacts, CH–π interactions and carbonyl–carbonyl interactions were detected in the crystal structure.

Crystal structure of strontium hydrogen citrate monohydrate, Sr(HC6H5O7)(H2O)

The crystal structure of strontium hydrogen citrate monohydrate has been solved using laboratory X-ray powder diffraction data, refined using both laboratory and synchrotron data, and optimized using density functional techniques. Strontium hydrogen citrate monohydrate crystallizes in space groupC2/c(#15) witha= 25.15601(17),b= 10.90724(6),c= 6.37341(4) Å,β= 91.9846(6)°,V= 1747.704(12) Å3, andZ= 8. The Sr coordination and the hydrogen bonding result in a layered structure. The SrO8coordination polyhedra share edges to form corrugated layers parallel to thebc-plane. Hydrogen bonds between the carboxylic acid groups and water molecules link the layers. Intermolecular hydroxyl–carboxyl hydrogen bonds also link the layers in a ring pattern with a graph set symbolR2,2(12). After storage for 2 years, partial re-crystallization occurred, to an as-yet unknown compound with a triclinic unit cell.

An Investigation of Five Component [3+2] Self-Assembled Cage Formation Using Amidinium···Carboxylate Hydrogen Bonds

The assembly of hydrogen bonded cages using amidinium···carboxylate hydrogen bonding interactions was investigated. A new tris-amidinium hydrogen bond donor tecton based on a tetraphenylmethane scaffold was prepared and its self-assembly with the terephthalate anion studied, and a new tricarboxylate hydrogen bond acceptor tecton was synthesised and its assembly with the 1,3-benzenebis(amidinium) hydrogen bond donor explored. In both cases, molecular modelling indicated that the formation of the cages was geometrically feasible and 1H NMR spectroscopic evidence was consistent with interactions between the components in competitive d6-DMSO solvent mixtures. DOSY NMR spectroscopy of both systems indicated that both components diffuse at the same rate as each other, and diffusion coefficients were consistent with cage formation, and with the formation of assemblies significantly larger than the individual components. An X-ray crystal structure showed that one of the assemblies did not have the desired cage structure in the solid state.

Amidinium⋯carboxylate frameworks: predictable, robust, water-stable hydrogen bonded materials.

In the last few years, the amidinium⋯carboxylate interaction has emerged as a powerful tool for the relatively predictable construction of families of three dimensional hydrogen bonded organic frameworks. These frameworks can be prepared in water and are surprisingly stable, including to heating in polar organic solvents and water. This feature article describes the design and synthesis of these materials, discusses their structures and stability, and highlights their recent applications for enzyme encapsulation and as precursors for the synthesis of molecularly thin hydrogen bonded 2D nanosheets.

A Comparative Study of Proton Conduction Between a 2D Zinc(II) MOF and Its Corresponding Organic Ligand

Until now, comparative studies on proton conductivity between organic ligands and related metal-organic frameworks (MOFs) have been very limited. Herein, a stable 2D Zn(II) MOF, [Zn(L)Cl]n (1), has been successfully synthesized by using a zwitterionic-type organic ligand, 2-(1-(carboxymethyl)-1H-benzo[d]imidazol-3-ium-3-yl)acetate (HL). It is found that there are a large amount of free carboxyl groups and hydrogen bonds in the solid-state structure of HL, and a large number of chlorine ions are aligned in the channels of 1, which is favorable to the efficient proton transfer. Correspondingly, the proton conductivity values of 1 and HL are almost of the same order of magnitude under the same conditions. Moreover, the optimal σ value of 1 (4.72 × 10-3 S/cm at 100 °C and 98% relative humidity) is almost four times higher than that (1.36 × 10-3 S/cm) of the HL ligand. On the basis of the crystal data, SEM images, and calculated Ea values, we discuss the differences on proton conductivities and conduction mechanisms of 1 and HL. This report provides an inspiration for the preparation of highly conductive materials with free carboxyl groups and chloride ions.

Synthesis, structure, computational and molecular docking studies of asymmetrically di-substituted ureas containing carboxyl and phosphoryl hydrogen bond acceptor functional groups

Abstract Two asymmetrically substituted ureas N,N -(2-carboxylphenyl)phenyl urea (L1) and diethyl 4-(3-phenylureido)benzylphosphonate (L2) were synthesized and characterized by spectroscopic and X-ray crystallographic analysis. The two compounds crystallized in the centrosymmetric monoclinic crystal system and P21/n space group. The carboxyl substituted urea L1 crystallized with one molecule in the asymmetric unit. A hydrogen-bonded dimer is formed between the carboxyl group of the urea and a second molecule of the compound. The urea functional group is involved in both intramolecular and intermolecular hydrogen bonding with the carboxyl and carbonyl oxygens, respectively. The interplay of intermolecular and intramolecular hydrogen bonding in the compound results in a 2-D hydrogen-bonded structure. The phosphoryl-substituted urea L2, on the other hand, crystallized with two molecules in the asymmetric unit, resulting in a hydrogen-bonded tetramer in the crystal lattice. Non-covalent interactions (NCI) analysis of the two compounds revealed the presence of competitive interactions between the urea functional group and the carboxyl and phosphoryl substituents in L1 and L2, respectively. Molecular docking calculations predicted favorable binding interactions between the ureas and the two anticancer protein targets EGFR kinase (2J5F) and anaplastic lymphoma kinase (5J7H).

Crystal structure, Hirshfeld surface analysis and inter-action energy and DFT studies of methyl 4-[3,6-bis-(pyridin-2-yl)pyridazin-4-yl]benzoate.

The title com-pound, C22H16N4O2, contains two pyridine rings and one meth-oxy-carbonyl-phenyl group attached to a pyridazine ring which deviates very slightly from planarity. In the crystal, ribbons consisting of inversion-related chains of mol-ecules extending along the a-axis direction are formed by C-HMthy⋯OCarbx (Mthy = methyl and Carbx = carboxyl-ate) hydrogen bonds. The ribbons are connected into layers parallel to the bc plane by C-HBnz⋯π(ring) (Bnz = benzene) inter-actions. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (39.7%), H⋯C/C⋯H (27.5%), H⋯N/N⋯H (15.5%) and O⋯H/H⋯O (11.1%) inter-actions. Hydrogen-bonding and van der Waals inter-actions are the dominant inter-actions in the crystal packing. Computational chemistry indicates that in the crystal, C-HMthy⋯OCarbx hydrogen-bond energies are 62.0 and 34.3 kJ mol-1, respectively. Density functional theory (DFT) optimized structures at the B3LYP/6-311G(d,p) level are com-pared with the experimentally determined mol-ecular structure in the solid state. The HOMO-LUMO behaviour was elucidated to determine the energy gap.

Bis(mefloquinium) butane-dioate ethanol monosolvate: crystal structure and Hirshfeld surface analysis.

The asymmetric unit of the centrosymmetric title salt solvate, 2C17H17F6N2O+· C4H4O4 2-·CH3CH2OH, (systematic name: 2-{[2,8-bis-(tri-fluoro-meth-yl)quinolin-4-yl](hy-droxy)meth-yl}piperidin-1-ium butane-dioate ethanol monosolvate) comprises two independent cations, with almost superimposable conformations and each approximating the shape of the letter L, a butane-dioate dianion with an all-trans conformation and an ethanol solvent mol-ecule. In the crystal, supra-molecular chains along the a-axis direction are sustained by charge-assisted hy-droxy-O-H⋯O(carboxyl-ate) and ammonium-N-H⋯O(carboxyl-ate) hydrogen bonds. These are connected into a layer via C-F⋯π(pyrid-yl) contacts and π-π stacking inter-actions between quinolinyl-C6 and -NC5 rings of the independent cations of the asymmetric unit [inter-centroid separations = 3.6784 (17) and 3.6866 (17) Å]. Layers stack along the c-axis direction with no directional inter-actions between them. The analysis of the calculated Hirshfeld surface reveals the significance of the fluorine atoms in surface contacts. Thus, by far the greatest contribution to the surface contacts, i.e. 41.2%, are of the type F⋯H/H⋯F and many of these occur in the inter-layer region. However, these contacts occur at separations beyond the sum of the van der Waals radii for these atoms. It is noted that H⋯H contacts contribute 29.8% to the overall surface, with smaller contributions from O⋯H/H⋯O (14.0%) and F⋯F (5.7%) contacts.

Synthesis, structural and mass spectrometric investigations of pyridinium bis(thiosalicylato)mercurate(II)

This work investigates the synthesis and structural properties of a hydrogen-bonded salt of the [Hg(SC6H4-2-CO2)2]2− ion. The known bis(thiosalicylato)mercury(II) complex [Hg(SC6H4-2-CO2H)2], dissolves in pyridine (py), from which the crystalline pyridinium salt (pyH)2[Hg(SC6H4-2-CO2)2] can be isolated. Single crystal X-ray crystallography reveals two distinct three-molecule aggregates, namely {Hg[SC6H4-2-C(=O)OH]2(NC5H5)2} and {Hg[SC6H4-2-C(=O)O]2(HNC5H5)2}, which differ in the location of the acidic hydrogen atoms, i.e. either compound-bound for the former species or located on the pyridinium cations in the latter. The thiolate ligands are S,O-chelating and the resultant O2S2 four-coordinate geometries are each based on a distorted disphenoidal geometry. The three-molecule aggregates are sustained by hydroxylOH⋯N(pyridine) hydrogen bonds in the case of {Hg[SC6H4-2-C(=O)OH]2(NC5H5)2} whereas the second aggregate features charge-assisted pyridiniumNH⋯O(carboxylate) hydrogen bonds. (pyH)2[Hg(SC6H4-2-CO2)2] was also characterised by negative-ion ESI mass spectrometry, where it showed appreciable stability towards capillary exit voltage-induced fragmentation. In contrast, the S-bonded monodentate thiosalicylate complexes RHg(SC6H4-2-CO2)− (R = Et, Ph or ferrocenyl) undergo facile decarboxylation at relatively low voltages, with the phenyl and ferrocenyl complexes subsequently forming RHgS− as an additional fragment ion at high voltages. Aggregate ions formed with the sodium counter-cations of the type [(RHgSC6H4-2-CO2)nNan−1]− show appreciable stability towards fragmentation.

Effect of functional groups in acid constituent of deep eutectic solvent for extraction of reactive lignin

In this study, acidic deep eutectic solvents (DES) synthesized from various organic carboxylic acid hydrogen bond donors were applied to lignocellulosic oil palm empty fruit bunch (EFB) pretreatment. The influence of functional group types on acid and their molar ratios with hydrogen bond acceptor on lignin extraction were evaluated. The result showed presence of hydroxyl group and short alkyl chain enhanced biomass fractionation and lignin extraction. Choline chloride:lactic acid (CC-LA) with the ratio of 1:15 and choline chloride:formic acid (CC-FA) with 1:2 ratio extracted more than 60 wt% of lignin. CC-LA DES-extracted lignin (DEEL) exhibited comparable reactivity with technical and commercial lignin based on its phenolic hydroxyl content (3.33–3.72 mmol/glignin). Also, the DES-pretreated EFB comprised of enriched glucan content after biopolymer fractionation. Both DES-pretreated EFB and DEEL can be potential feedstock for subsequent conversion processes. This study presented DES as an effective and facile pretreatment method for reactive lignin extraction.