Dissociation Energy Research Articles

Low-Migration Compounds with Amine Functionality as Coinitiators of Radical Polymerization.

The utilization of two-component systems comprising camphorquinone (CQ) and aromatic amines has become prevalent in the photopolymerization. However, there are still concerns about the safety of this CQ/amine system, mainly because of the toxicity associated with the leaching of aromatic amines. In light of these concerns, this study aims to develop novel coinitiator combinations featuring CQ and amines which cannot be leached out of materials, enabling free radical polymerization of representative dentalmethacrylate resins under blue light irradiation. This approach involves the initial design and analysis of hydrogen donors with low C─H bond dissociation energy through molecular modeling. Subsequently, copolymerizable methacrylate functional groups are incorporated via chemical modification, allowing it to act as both coinitiator and copolymerization monomer to achieve low migrationand leachability properties. This work presents, for the first time, the synthesis of the innovative coinitiator and compares its performance with the benchmark CQ/ethyl-4-dimethylaminobenzoate (EDB)-based photoinitiation system (PIS). The results demonstrate the effectiveness of the newly proposed PIS. Finally, an in-depth investigation is conducted into the reaction mechanism associated with this PIS through molecular orbital calculations and electron spin resonance studies.

Tert‐Butyl as a Functional Group: Non‐Directed Catalytic Hydroxylation of Sterically Congested Primary C−H Bonds

AbstractThe tert‐butyl group is a common aliphatic motif extensively employed to implement steric congestion and conformational rigidity in organic and organometallic molecules. Because of the combination of a high bond dissociation energy (~100 kcal mol−1) and limited accessibility, in the absence of directing groups, neither radical nor organometallic approaches are effective for the chemical modification of tert‐butyl C−H bonds. Herein we overcome these limits by employing a highly electrophilic manganese catalyst, [Mn(CF3bpeb)(OTf)2], that operates in the strong hydrogen bond donor solvent nonafluoro‐tert‐butyl alcohol (NFTBA) and catalytically activates hydrogen peroxide to generate a powerful manganese‐oxo species that effectively oxidizes tert‐butyl C−H bonds. Leveraging on the interplay of steric, electronic, medium and torsional effects, site‐selective and product chemoselective hydroxylation of the tert‐butyl group is accomplished with broad reaction scope, delivering primary alcohols as largely dominant products in preparative yields. Late‐stage hydroxylation at tert‐butyl sites is demonstrated on 6 densely functionalized molecules of pharmaceutical interest. This work uncovers a novel disconnection approach, harnessing tert‐butyl as a potential functional group in strategic synthetic planning for complex molecular architectures.

Tert-Butyl as a Functional Group: Non-Directed Catalytic Hydroxylation of Sterically Congested Primary C-H Bonds.

The tert-butyl group is a common aliphatic motif extensively employed to implement steric congestion and conformational rigidity in organic and organometallic molecules. Because of the combination of a high bond dissociation energy (~ 100 kcal mol-1) and limited accessibility, in the absence of directing groups, neither radical nor organometallic approaches are effective for the chemical modification of tert-butyl C-H bonds. Herein we overcome these limits by employing a highly electrophilic manganese catalyst, [Mn(CF3bpeb)(OTf)2], that operates in the strong hydrogen bond donor solvent nonafluoro-tert-butyl alcohol (NFTBA) and catalytically activates hydrogen peroxide to generate a powerful manganese-oxo species that effectively oxidizes tert-butyl C-H bonds. Leveraging on the interplay of steric, electronic, medium and torsional effects, site-selective and product chemoselective hydroxylation of the tert-butyl group is accomplished with broad reaction scope, delivering primary alcohols as largely dominant products in preparative yields. Late-stage hydroxylation at tert-butyl sites is demonstrated on 6 densely functionalized molecules of pharmaceutical interest. This work uncovers a novel disconnection approach, harnessing tert-butyl as a potential functional group in strategic synthetic planning for complex molecular architectures.

High-Rate and Selective C2H6-to-C2H4 Photodehydrogenation Enabled by Partially Oxidized Pdδ+ Species Anchored on ZnO Nanosheets under Mild Conditions.

Photocatalytic C2H6-to-C2H4 conversion is very promising, yet it remains a long-lasting challenge due to the high C-H bond dissociation energy of 420 kJ mol-1. Herein, partially oxidized Pdδ+ species anchored on ZnO nanosheets are designed to weaken the C-H bond by the electron interaction between Pdδ+ species and H atoms, with efforts to achieve high-rate and selective C2H6-to-C2H4 conversion. X-ray photoelectron spectra, Bader charge calculations, and electronic localization function demonstrate the presence of partially oxidized Pdδ+ sites, while quasi-in situ X-ray photoelectron spectra disclose the Pdδ+ sites initially adopt and then donate the photoexcited electrons for C2H6 dehydrogenation. In situ electron paramagnetic resonance spectra, in situ Fourier transform infrared spectra, and trapping agent experiments verify C2H6 initially converts to CH3CH2OH via ·OH radicals, then dehydroxylates to CH3CH2· and finally to C2H4, accompanied by H2 production. Density-functional theory calculations elucidate that loading Pd site can lengthen the C-H bond of C2H6 from 1.10 to 1.12 Å, which favors the C-H bond breakage, affirmed by a lowered energy barrier of 0.04 eV. As a result, the optimized 5.87% Pd-ZnO nanosheets achieve a high C2H4 yield of 16.32 mmol g-1 with a 94.83% selectivity as well as a H2 yield of 14.49 mmol g-1 from C2H6 dehydrogenation in 4 h, outperforming all the previously reported photocatalysts under similar conditions.

Derivation of Morse potential

The Morse potential is widely used in chemistry, physics, and material science to describe interatomic interactions. We show that the Morse potential can be derived from a simple screened charge model accounting for the shielding of the nuclear charge by electron density. In this model, the parameter governing the width of the potential is related to the average shielding strength and the exponents of the atomic orbitals used in electronic structure calculations. The parameter representing the bond dissociation energy of a diatomic molecule is derived by combining the quantum mechanical covalent and classical electrostatic interactions. Moreover, the revealed connection between the parameters of the Morse potential and Pauling’s bond order and electronegativity provides insight into the relation between the classical and quantum mechanical descriptions of chemical bonds. This derivation of the Morse potential from the atomic quantities is expected to contribute to the development of the new basis sets incorporating Slater-type orbitals for electronic structure calculations and the transferable reactive force fields for molecular dynamics simulations. Furthermore, this interpretation of the Morse potential helps to understand the relationships between widely used chemical concepts, including effective atomic charge, bond dissociation energy, electronegativity, and bond order.

Exploring factors affecting the dissociation energies of C–O and C–C bonds in lignin oligomers

The bond dissociation energy (BDE) of lignin is a key factor for lignin depolymerization, assisting in revealing the depolymerization mechanism. However, the impact of substituent as well as solvent, which usually stay together, on BDE of lignin remains unclear. Here, density functional theory (DFT) calculation is employed to compute the BDE of C–O and C–C bonds in lignin oligomers with six substituents in four solvents. The relationship models between multiple factors and BDE are established using random forest algorithm, achieving a predictive accuracy of 0.97. The results show that oxidating hydroxyl to ketone benefits the cleavage of β-O-4 and β-1 bonds. Hydroxyl and methoxy effectively contribute to breaking the Cβ-1 and Cα–Cβ bonds in the β-1 dimer. Polar solvents combined with hydroxyl promote C–O bond dissociation, while alkyl-containing solvents favor C–C bond dissociation. These findings provide valuable insights into lignin depolymerization, pre-depolymerization structural modifications, and the prediction of depolymerization pathways.

Nonlinear optical properties of KnCl (n = 2–7) superalkali clusters

The lowest energy structures along with the low lying isomer, stabilities, electronic properties, optical properties and nonlinear optical responses of KnCl (n = 2–7) clusters were studied within the density functional theory. The second order energy difference, dissociation energy and GH-L (HOMO–LUMO gap) point out that KnCl (n = 3, 5, 7) clusters are more stable. The calculated adiabatic ionization energies (AIE) for the KnCl (n = 2–6) clusters are in agreement with the measured ionization energies. The optical properties, namely optical electronegativity and refractive index, depends on the GH-L energy values. The K atom capped planar rhombus geometry of the K4Cl causes the noticeable vibrational frequency shift compared to the rest of IR spectra of the clusters. The first static hyperpolarizability (β o) values are in the range of 2.33 × 103 –2.87 × 104 au and the second static hyperpolarizability varies between 5.74 × 106 au and 38.9 × 106 au for the cluster. The nonlinear optical response is due to the superalkali nature of KnCl (n = 2–7) clusters. From computed β vec values, the hyperpolarizability has projection on the dipole moment vector for the superalkalis except the K2Cl and K5Cl. The absorption spectra point out that KnCl (n = 6–7) clusters can be suitable as a NLO material since they have transparency in the deep UV region (λ< 300 nm).

Estimation of the Dissociation Energies of Donor–Acceptor Complexes of Group 13–15 Element Compounds within the Framework of the Statistical EC Model

Estimation of the Dissociation Energies of Donor–Acceptor Complexes of Group 13–15 Element Compounds within the Framework of the Statistical EC Model

Ultrahigh Heat/Fire-Resistant, Mechanically Robust, and Closed-Loop Chemical Recyclable Polycarbonate Enabled by Facile Bond Dissociation Energy Modulation.

Plastics serve as an essential foundation in contemporary society. Nevertheless, meeting the rigorous performance demands in advanced applications and addressing their end-of-life disposal are two critical challenges that persist. Here, an innovative and facile method is introduced for the design and scalable production of polycarbonate, a key engineering plastic, simultaneously achieving high performance and closed-loop chemical recyclability. The bisphenol framework of polycarbonate is strategically adjusted from the low-bond-dissociation-energy bisphenol A to high-bond-dissociation-energy 4,4'-dihydroxydiphenyl, in combination with the incorporation of polysiloxane segments. As expected, the enhanced bond dissociation energy endows the polycarbonate with an extremely high glow-wire flammability index surpassing 1025°C, a 0.8mm UL-94V-0 rating, a high LOI value of 39.2%, and more than 50% reduction of heat and smoke release. Furthermore, the π-π stacking interactions within biphenyl structures resulted in a significant enhancement of mechanical strength by as more as 37.7%, and also played a positive role in achieving a lower dielectric constant. Significantly, the copolymer exhibited outstanding closed-loop chemical recyclability, allowing for facile depolymerization into bisphenol monomers and the repolymerized copolymer retains its high heat and fire resistance. This work provides a novel insight in the design of high-performance and closed-loop chemical recyclable polymeric materials.

Cost-efficient sunlight-driven thermoelectric electrolysis over Mo-doped Ni5P4 nanosheets for highly efficient alkaline water/seawater splitting

Thermoelectric water spitting to hydrogen systems has great potential in the production of environment-friendly fuel using renewable solar energy in the future. In this work, we prepared porous nanosheet Mo doping Ni5P4 catalysts on nickel foam with efficient hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) performance in alkaline media. Density Functional Theory (DFT) calculations and experimental studies have shown that Mo doping deadeneds the interaction between H and O atomic orbitals of transition state water molecules, effectively weakening the activation energy of H2O dissociation. Therefore, Mo doping is favorable for enhancing HER activity with overpotential at 10 mA cm–2 of 93 mV and Tafel slope of 40.1 mV dec–1 in 1 M KOH. Besides, it exhibits high alkaline OER activity with an ultra-low overpotential of 200 mV at 10 mA cm–2. Moreover, this catalyst only needs 1.537 V in a dual-electrode configuration of the electrolytic cell, which is much lower than the commercial Pt/C-RuO2 couple (1.614 V). In addition, we have developed and constructed a solar thermoelectric generator (TEG) that is capable of floating on water. This TEG has a continuous power output and an exceptionally long lifespan, providing a stable power supply to the synthesized catalyst electrolyzer. It can produce a maximum power output of over 90 mW, meeting the requirement of converting solar radiation heat into usable electricity. As a result, the system achieves productivity of 0.11 mL min–1 H2. This solar thermal energy conversion technology shows the possibility of large-scale industrial production of H2 and provides a new idea for exploring heat source utilization.

Theoretical and experimental study of a new antioxidant xanthone: Solvent and intramolecular hydrogen bond effects

Free radicals are harmful reactive species that cause various problems in the human body. Antioxidant compounds, such as xanthones found in natural products, can help prevent these effects. This study focuses on the antioxidant behavior of ravenelin (RVL) and ravenelin B (RVLB), a newly discovered xanthone in the Exserohilum rostratum fungus. Both experimental and in silico tests were conducted, comparing them to ascorbic acid, a standard antioxidant. The results showed that RVL has a lower bond dissociation energy (312 kJ/mol) than ascorbic acid (313 kJ/mol), indicating comparable antioxidant performance. This difference is mild but agrees with the experiment that indicates RVL efficiency is equivalent to ascorbic acid at low concentrations. RVLB, however, demands higher dissociation energy (323 kJ/mol) and consequently it has a lower antioxidative efficiency. Thus, antioxidant capacity is found as RVL>ascorbic acid>RVLB. From experimental assays, the RVL performance was confirmed through experimental tests at different solute concentrations. The study also examines the effects of solvents and intramolecular hydrogen bonds. Ravenelin molecules present three hydroxyl groups involved in intramolecular OH⋯O interactions. However, analysis based on the infrared spectra, as well as Bader's theory and non-covalent interactions done in water solvent showed that the two strongest H-bonds (≈−37 kJ/mol) better stabilize the molecular structure, but are not favorable to antioxidant reactions, indicating that hydrogen scavenging occurs at the less hydrogen-bonded hydroxyl group. The solvent also plays an active role first in facilitating hydrogen abstraction besides changing the hydrogen scavenging mechanism according to the environmental polarizability. Additionally, the antioxidant mechanism of ravenelin molecules changes from nonpolar to polar solvents, allowing for hydrogen abstraction.

Catalytic Asymmetric Access to Structurally Diverse N-Alkoxy Amines via a Kinetic Resolution Strategy.

Chiral N-alkoxy amines are increasingly vital substrates in bioscience. However, asymmetric synthetic strategies for these compounds remain scarce. Catalytic kinetic resolution represents an attractive approach to prepare structurally diverse enantiopure N-alkoxy amines, which has remained elusive due to the notably reduced nucleophilicity of the nitrogen atom together with the low bond dissociation energies of labile NO-C and N-O bonds. We here report a general kinetic resolution of N-alkoxy amines through chemo- and enantioselective oxygenation. The mild and green titanium-catalyzed approach features broad substrate scope (55 examples), noteworthy functional group compatibility, high catalyst turnover number (up to 5200), excellent selectivity factor (s > 150), and scalability.

Multiple Bonding in AeN- (Ae=Ca, Sr, Ba).

Quantum chemical calculations using ab initio methods at the MRCI+Q(8,9)/def2-QZVPPD and CCSD(T)/def2-QZVPPD levels as well as using density functional theory are reported for the diatomic molecules AeN- (Ae=Ca, Sr, Ba). The anions CaN- and SrN- have electronic triplet (3Π) ground states with nearly identical bond dissociation energies De ~57 kcal/mol calculated at the MRCI+Q(8,9)/def2-QZVPPD level. In contrast, the heavier homologue BaN- has a singlet (1Σ+) ground state, which is only 1.1 kcal/mol below the triplet (3Σ-) state. The computed bond dissociation energy of (1Σ+) BaN- is 68.4 kcal/mol. The calculations at the CCSD(T)-full/def2-QZVPPD and BP86-D3(BJ)/def2-QZVPPD levels are in reasonable agreement with the MRCI+Q(8,9)/def2-QZVPPD data, except for the singlet (1Σ+) state, which has a large multireference character. The calculated atomic partial charges given by the CM5, Voronoi and Hirshfeld methods suggest small to medium-sized Ae←N- charge donation for most electronic states. In contrast, the NBO method predicts for all species medium to large Ae→N- electronic charge donation, which is due to the neglect of the (n)p AOs of Ae atoms as genuine valence orbitals. Neither the bond orders nor the bond lengths correlate with the bond dissociation energies. The EDA-NOCV calculations show that the heavier alkaline earth atoms Ca, Sr, Ba use their (n)s and (n-1)d orbitals for covalent bonding.

Modulating Ionic Linkages in the Heterocyclic Sulfated Polysaccharide Carrageenan for Enhanced Selectivity Against Amelanotic Melanoma Cells

AbstractThe present research is the use of Heterocyclic sulfated polysaccharides, exemplified by carrageenan, with the high selective anti‐cancer against melanoma cancer. This study focuses on optimizing the ionic linkage of carrageenan to enhance its selectivity and activity against skin cancer cells with the help of cell line assays and in‐silico studies. The cytotoxicity and selectivity of the optimized derivatives were assessed in‐vitro against skin cancer cells and normal skin cells. The barium‐linked carrageenan demonstrated significantly increased selectivity against skin cancer cells with a selectivity index of 45, however, the reference drug was found with a selectivity index of 23. The selectivity of the compound 3 (Ba ion linked) was analysed through the ion dissociation energy and found that the more energy is require to dissoxiate in the ion, which signifiacnlty absorbs inside the cell because of non‐ionic form. The selectivity sequence of K+&lt;Ca2+&lt;Ba2+ as a targeted anti‐cancer agent. The present research unfold the importance of ion linkage of chromophore, to get the more active and selective compounds, which will be a path to get the ion activity relationship of various drugs without interfering the chromophore. The findings suggest a promising avenue for the development of targeted therapies with the change of ions, emphasizing the potential of heterocyclic sulfated polysaccharides in the field of cancer treatment with enhanced tuning of selectivity. The further scope is the gel formation of the Ba2+ carrageenan which will be the first API (Active Pharmaceuitical Ingredients) based formulation for skin cancer.

New lead barium borate glass system for radiation shielding applications: impacts of copper (II) oxide on physical, mechanical, and gamma-ray attenuation properties

Abstract The current work seeks to develop a novel CuO-doped lead calcium barium borate glass using the melt quenching method at 1100 °C. There was a 3.91–4.49 g/cm3 change in the fabricated glasses’ density, with a respective 0–15 mol.% increase in the CuO concentration. Additionally, substituting CuO for B2O3 reduced the fabricated glasses mechanical properties due to the decreased dissociation energy between 63.99 and 60.50 kcal/cm3, and the packing factor decreased between 15.22 and 13.23 cm3/mol. Through increasing the fabricated glasses’ CuO concentration, there was a decrease in the bulk, longitudinal, shear, and mechanical Young moduli. Moreover, Monte Carlo simulation (energy interval: 0.033–2.506 MeV) was employed to evaluate the fabricated glasses’ ability to shield gamma rays. A 0–15 mol.% increase in the CuO concentration raised the linear attenuation coefficient (LAC) between 14.081 and 16.797 cm−1 (0.059 MeV), 0.325–0.371 cm−1 (0.662 MeV), and 0.154–0.176 cm−1 (2.506 MeV). The LAC enhancement reduced the required half value thickness of the fabricated glasses by 16.2 %, 12.53 %, and 12.85 % at the of 0.059, 0.662, and 2.506 MeV gamma ray energies.

Facile routes to enhance doping efficiency using nanocomposite structures for high-mobility and stable PEALD-ITGO TFTs

In–Sn–Ga–O (ITGO) thin-film transistors (TFTs) fabricated by atomic layer deposition (ALD) are promising candidates for widespread semiconductor applications because of their high mobility and stability. To further improve the device characteristics, the doping efficiency of each cation must be increased. Here, we propose a facile method to enhance the device characteristics using plasma-enhanced ALD-nanocomposite (NC) structures. The deposition of SnO2 materials within the In2O3 layer of the ITGO film with the NC-ITO structure accelerates the reduction of In2O3 (In0: 35.3 % →46.1 %), thereby stabilizing SnO2 (Sn4+: 71.0 % →89.1 %). In addition, this process significantly decreases the fraction of oxygen-related defects (Odefect: 24.0 % →17.6 %) because Sn–O has a substantially higher bond dissociation energy than In–O. Consequently, the ITGO TFT with the NC-ITO active layer exhibits considerable improvements in the electrical parameters, such as an increase in the field-effect mobility from 41.9 to 54.5 cm2/V s and an enhancement in the subthreshold swing from 69.8 to 64.8 mV/decade. In addition, the device shows excellent results for negative bias illumination stress and positive bias temperature stress, with the differences in the threshold voltage shift being −0.22 and + 0.06 V, respectively.

Effects of Laser Treatment of Terbium-Doped Indium Oxide Thin Films and Transistors.

In this study, a KrF excimer laser with a high-absorption coefficient in metal oxide films and a wavelength of 248 nm was selected for the post-processing of a film and metal oxide thin film transistor (MOTFT). Due to the poor negative bias illumination stress (NBIS) stability of indium gallium zinc oxide thin film transistor (IGZO-TFT) devices, terbium-doped Tb:In2O3 material was selected as the target of this study. The XPS test revealed the presence of both Tb3+ and Tb4+ ions in the Tb:In2O3 film. It was hypothesized that the peak of the laser thermal effect was reduced and the action time was prolonged by the f-f jump of Tb3+ ions and the C-T jump of Tb4+ ions during the laser treatment. Studies related to the treatment of Tb:In2O3 films with different laser energy densities have been carried out. It is shown that as the laser energy density increases, the film density increases, the thickness decreases, the carrier concentration increases, and the optical band gap widens. Terbium has a low electronegativity (1.1 eV) and a high Tb-O dissociation energy (707 kJ/mol), which brings about a large lattice distortion. The Tb:In2O3 films did not show significant crystallization even under laser energy density treatment of up to 250 mJ/cm2. Compared with pure In2O3-TFT, the doping of Tb ions effectively reduces the off-state current (1.16 × 10-11 A vs. 1.66 × 10-12 A), improves the switching current ratio (1.63 × 106 vs. 1.34 × 107) and improves the NBIS stability (ΔVON = -10.4 V vs. 6.4 V) and positive bias illumination stress (PBIS) stability (ΔVON = 8 V vs. 1.6 V).

Direct Functionalization of para‐Quinones: A Historical Review and New Perspectives

The direct functionalization of quinones has always fascinated research communities due to their biological and redox activities and subsequent application. Quinone motifs play a vital role as precursors for many bioactive compounds and materials; hence, many ingenious methodologies have been elaborated for exploring these units. A significant part of the synthetic strategies towards the functionalized quinones has been achieved by installing substituents on hydroquinones, phenols, or quinone itself by different oxidative coupling reactions via radical pathways with or without the utilization of metal catalysts. The functionalization of simple quinones via direct C‐H bond remains challenging due to their inherited electronic nature and high bond dissociation energy. This review article summarizes the recent advancement made for functionalized quinones through direct functionalization of simple quinones. Our primary focus will be on the synthetic approaches and mechanistic pathways of these reactions that have appeared in the last two decades, along with a short historical importance of the quinone family.

Bio‐based and effective: Cardanol‐piperidine derivatives for enhanced polypropylene resistance against thermo‐ and photo‐oxidative aging

AbstractBio‐based antioxidants have garnered attention for their sustainability and environmental benefits. In this study, we designed and synthesized three cardanol‐piperidine derivatives (HSs) by utilizing hydrogenated cardanol (HC) and piperidine derivatives to improve the aging inhibition of polypropylene (PP). These bio‐based antioxidants were intended as eco‐friendly alternatives to conventional synthetic antioxidants. The impact of these HSs on the thermal stability, thermo‐oxidative stability, and light stability of PP was thoroughly evaluated. The results unveiled that after 5 h of interaction with 2,2‐diphenyl‐1‐picrylhydrazyl free radical, HSs exhibited a remarkable over 5‐fold increase in free radical scavenging efficiency as compared to HC. Moreover, the addition of HSs significantly increased the oxidation induction time and the initial oxidation temperature compared to pristine PP. After photo‐oxidative aging and thermo‐oxidative aging, the HS‐dosed PP demonstrated remarkable retention of elongation at break, reaching more than 72% and 69%. From the comparison with physical mixtures and the density functional theory calculations, an intramolecular synergism mechanism is proposed. The intramolecular synergism between hydrogenated cardanol and piperidine derivatives may be the main reason for the inhibition of PP aging.Highlights A method for constructing simultaneous efficient light, thermal, and oxygen stable polypropylene. The mechanism for achieving simultaneous stabilization of light, heat, and oxygen is the intramolecular synergy of phenol piperidine. The essence of intramolecular synergy of cardanol and piperidine derivatives is its' reduced hydrogen bond dissociation energy and energy gap.

Promotion of lignin depolymerization and cellulose utilization via the coupling effects of DDQ pre-oxidation and HCOOH extraction

The full utilization of biomass plays an important role in the environment and energy. In this study, the coupling pretreatment of DDQ pre-oxidation and HCOOH extraction was employed to realize the separation and modification of three components of sugarcane bagasse for full utilization. Especially, the modified lignin was depolymerized to obtain aromatic monomers, and cellulose-rich residue was used to prepare lignocellulose straws. Furthermore, the coupling effects between DDQ pre-oxidation and HCOOH extraction on chemical and physical properties of modified lignin and lignocellulose straws were studied. In addition, the mechanism of lignin depolymerization and lignocellulose straw synthesis were explored as well as the mass balance of the biorefinery process. The results showed that the total yield of aromatic monomers increased by nearly 2 times and the conversion of lignin was 95.1 % after DDQ pre-oxidation. The mechanism showed that DDQ selectively oxidized Cα-OH bond of lignin to Cα = O bond, which not only avoided the formation of carbocation, but also reduced the bond dissociation energy of β-O-4 bond. Moreover, the tensile strength of hydrophobic lignocellulose straw increased by nearly 2 times and its flexural strength was 10.36 MPa. Modified lignin and modified cellulose were connected via hydrogen bonds, which enhanced the intermolecular crosslinking of molecules, thus improving the mechanical properties of lignocellulose straws. Besides, the maximum xylose relative content and concentration of xylose were 61.16 % and 17.57 g/L, respectively. This study provides a method for high-value and green utilization of sugarcane bagasse.