Study on the underlying mechanism of choline chloride-lactic acid molar ratio influencing alkali lignin solubility in choline chloride-lactic acid deep eutectic solvents

doi:10.11949/0438-1157.20250383

Abstract

Abstract:

For the increase alkali lignin solubility in choline chloride-lactic acid deep eutectic solvents (ChCl-LA) observed in the experiment when increasing the molar ratio of lactic acid, the intrinsic mechanism of the choline chloride-lactic acid molar ratio affecting the dissolution of alkali lignin in ChCl-LA was studied at atomic and molecular scales. Based on density functional theory, the electrostatic potential distribution of ChCl-LA, interaction and H-bond energy between choline chloride and lactic acid for different molar ratios of lactic acid were examined, and relationships between these factors and the capacity of ChCl-LA to dissolve alkali lignin were discussed. Using molecular dynamics simulations, interactions of lignin with lactic acid solvent and ChCl-LA with different molar ratios of lactic acid were investigated. The number of H-bonds, interaction energy, radial distribution function and spatial distribution function between each component of different ChCl-LA and LA solvent were calculated, and their effects on the process of lignin dissolution were analyzed. It was revealed that the choline chloride-lactic acid molar ratio affects the ability of ChCl-LA to form H-bonds with lignin and to catalyze the lignin depolymerization via the nature of active protons and H-bonds in ChCl-LA, resulting in its influence on the alkali lignin solubility in ChCl-LA. The above results provide theoretical support for regulating the ability of ChCl-LA to dissolve lignin, which is of great significance for the preparation and application of ChCl-LA and the green and efficient dissolution of lignin.

Key words: deep eutectic solvent, lignin, solubility, computational chemistry, molecular simulation

摘要：

本文针对氯化胆碱-乳酸低共熔溶剂（ChCl-LA）的碱木质素溶解度随乳酸摩尔比增大而提升的实验现象，从原子、分子尺度探究ChCl-LA组分配比影响碱木质素溶解度的本质机理。基于密度泛函理论，考察了不同组分配比ChCl-LA的分子表面静电势、组分间的相互作用、氢键键能，分析了这些因素与ChCl-LA溶解木质素能力的内在关系。利用分子动力学模拟，研究了不同组分配比ChCl-LA、纯乳酸与木质素的相互作用，统计分析了各组分与木质素之间的氢键数、相互作用能、径向分布函数、空间分布函数对木质素溶解的影响规律。结果表明，ChCl-LA的组分配比决定了ChCl-LA内的活性质子和氢键性质，进而影响了ChCl-LA与木质素形成氢键、催化木质素解聚的能力，从而改变了ChCl-LA的木质素溶解度。以上结果为调控ChCl-LA溶解木质素的能力提供了理论支撑，对于ChCl-LA的制备和应用以及绿色、高效溶解木质素具有重要意义。

关键词: 低共熔溶剂, 木质素, 溶解性, 计算化学, 分子模拟

CLC Number:

O 641.3

Guoxiang HU, Yikui ZHU, Hua LONG, Xiaowen LIU, Qingang XIONG. Study on the underlying mechanism of choline chloride-lactic acid molar ratio influencing alkali lignin solubility in choline chloride-lactic acid deep eutectic solvents[J]. CIESC Journal, 2025, 76(9): 4449-4461.

胡国祥, 朱忆魁, 龙华, 刘晓雯, 熊勤钢. 组分配比影响氯化胆碱-乳酸低共熔溶剂碱木质素溶解度的底层机理研究[J]. 化工学报, 2025, 76(9): 4449-4461.

Figures/Tables 11

References 40

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ChCl-LA	氢键	类型	BCP	ρ/(a.u.)	(∇²ρ)/(a.u.)	键能/（kcal/mol）
D1	O20—H21⋯Cl	Ch⁺-Cl^-	87	0.023	0.070	-4.39
	O23—H24⋯Cl	Cl^--LA	85	0.046	0.098	-9.52
	C6—H8⋯O26	Ch⁺-LA	42	0.017	0.063	-3.05
	C2—H5⋯ O26	Ch⁺-LA	60	0.014	0.048	-2.38
	C13—H14⋯ O26	Ch⁺-LA	62	0.011	0.038	-1.71
D2	O20—H21⋯Cl	Ch⁺-Cl^-	57	0.020	0.065	-3.72
	O23—H24⋯Cl	Cl^--LA	54	0.036	0.091	-7.29
	O35—H46⋯Cl	Cl^--LA	51	0.033	0.087	-6.62
	C17—H19⋯ O43	Ch⁺-LA	82	0.014	0.045	-2.38
	C2—H3⋯ O43	Ch⁺-LA	91	0.017	0.057	-3.05
	C6—H8⋯ O26	Ch⁺-LA	111	0.013	0.050	-2.16
	C13—H14⋯ O26	Ch⁺-LA	93	0.012	0.042	-1.93
	C2—H5⋯ O26	Ch⁺-LA	97	0.014	0.048	-2.38
D3	O20—H21⋯Cl	Ch⁺-Cl^-	78	0.019	0.063	-3.50
	O47—H58⋯Cl	Cl^--LA	139	0.024	0.071	-4.61
	O35—H46⋯Cl	Cl^--LA	108	0.029	0.081	-5.73
	O23—H24⋯Cl	Cl^--LA	120	0.029	0.083	-5.73
	C17—H19⋯ O43	Ch⁺-LA	79	0.013	0.042	-2.16
	C2—H3⋯ O43	Ch⁺-LA	97	0.017	0.058	-3.05
	C6—H8⋯ O26	Ch⁺-LA	90	0.011	0.042	-1.71
	C2—H5⋯ O26	Ch⁺-LA	106	0.018	0.062	-3.27
	C13—H14⋯ O26	Ch⁺-LA	87	0.010	0.036	-1.49
	C2—H5⋯ O26	Ch⁺-LA	133	0.014	0.052	-2.38
D4	O20—H21⋯Cl	Ch⁺-Cl^-	121	0.018	0.060	-3.27
	O35—H36⋯Cl	Cl^--LA	131	0.023	0.068	-4.39
	O47—H48⋯Cl	Cl^--LA	160	0.026	0.076	-5.06
	O59—H61⋯Cl	Cl^--LA	161	0.028	0.079	-5.50
	O23—H26⋯Cl	Cl^--LA	150	0.014	0.051	-2.38
	C17—H19⋯ O44	Ch⁺-LA	85	0.014	0.047	-2.38
	C2—H3⋯ O44	Ch⁺-LA	101	0.016	0.055	-2.83
	C2—H3⋯ O50	Ch⁺-LA	133	0.011	0.047	-1.71
	C6—H8⋯ O62	Ch⁺-LA	149	0.015	0.054	-2.60
	C2—H5⋯ O62	Ch⁺-LA	156	0.015	0.049	-2.60
	C13—H14⋯ O25	Ch⁺-LA	132	0.013	0.048	-2.16
	C27—H28⋯ O20	Ch⁺-LA	89	0.011	0.042	-1.71
D6	O20—H21⋯Cl	Ch⁺-Cl^-	191	0.017	0.056	-3.05
	O35—H36⋯Cl	Cl^--LA	197	0.025	0.074	-4.83
	O47—H48⋯Cl	Cl^--LA	153	0.021	0.063	-3.94
	O59—H61⋯Cl	Cl^--LA	154	0.022	0.065	-4.17
	O23—H26⋯Cl	Cl^--LA	140	0.013	0.045	-2.15
	C17—H19⋯ O44	Ch⁺-LA	104	0.016	0.055	-2.83
	C2—H3⋯ O44	Ch⁺-LA	178	0.013	0.043	-2.16
	C2—H3⋯ O50	Ch⁺-LA	179	0.014	0.045	-2.38
	C6—H8⋯ O62	Ch⁺-LA	163	0.017	0.058	-3.05
	C2—H5⋯ O62	Ch⁺-LA	206	0.015	0.047	-2.60
	C13—H14⋯ O25	Ch⁺-LA	141	0.009	0.032	-1.26
	C27—H28⋯ O20	Ch⁺-LA	145	0.016	0.055	-2.83
	C6—H8⋯ O65	Ch⁺-LA	198	0.012	0.042	-1.93
	O45—H46⋯ O91	LA-LA	221	0.017	0.058	-3.05
	C85—H86⋯ O80	LA-LA	215	0.009	0.032	-1.26
	C73—H74⋯ O45	LA-LA	165	0.012	0.042	-1.93
D8	O20—H21⋯Cl	Ch⁺-Cl^-	265	0.016	0.05	-2.82
	O35—H36⋯Cl	Cl^--LA	228	0.018	0.060	-3.27
	O47—H48⋯Cl	Cl^--LA	253	0.020	0.06	-3.72
	O59—H61⋯Cl	Cl^--LA	202	0.023	0.067	-4.39
	O23—H26⋯Cl	Cl^--LA	242	0.021	0.063	-3.94
	C17—H19⋯ O44	Ch⁺-LA	247	0.013	0.043	-2.16
	C2—H3⋯ O44	Ch⁺-LA	232	0.015	0.047	-2.60
	C2—H3⋯ O50	Ch⁺-LA	179	0.014	0.045	-2.38
	C6—H8⋯ O62	Ch⁺-LA	251	0.010	0.036	-1.49
	C2—H5⋯ O62	Ch⁺-LA	159	0.016	0.055	-2.83
	C13—H14⋯ O25	Ch⁺-LA	226	0.015	0.047	-2.60
	C27—H28⋯ O20	Ch⁺-LA	167	0.013	0.043	-2.16
	C10—H11⋯ O44	Ch⁺-LA	189	0.014	0.045	-2.38
	C10—H15⋯ O44	Ch⁺-LA	162	0.009	0.032	-1.26
	C87—H89⋯ O79	LA-LA	138	0.019	0.063	-3.50
	C73—H74⋯ O45	LA-LA	129	0.012	0.042	-1.93
	O83—H94⋯ O45	LA-LA	187	0.018	0.062	-3.27
	O45—H46⋯ O91	LA-LA	315	0.009	0.032	-1.26
	C85—H86⋯ O80	LA-LA	180	0.010	0.036	-1.49
D10	O20—H21⋯Cl	Ch⁺-Cl^-	193	0.015	0.054	-2.60
	O35—H36⋯Cl	Cl^--LA	172	0.019	0.063	-3.50
	O47—H48⋯Cl	Cl^--LA	204	0.017	0.056	-3.05
	O59—H61⋯Cl	Cl^--LA	183	0.021	0.063	-3.94
	O23—H26⋯Cl	Cl^--LA	197	0.022	0.065	-4.17
	C17—H19⋯ O44	Ch⁺-LA	280	0.010	0.036	-1.49
	C2—H3⋯ O44	Ch⁺-LA	219	0.014	0.045	-2.38
	C2—H3⋯ O50	Ch⁺-LA	264	0.016	0.055	-2.83
	C6—H8⋯ O62	Ch⁺-LA	260	0.013	0.045	-2.15
	C2—H5⋯ O62	Ch⁺-LA	228	0.013	0.048	-2.16
	C13—H14⋯ O25	Ch⁺-LA	222	0.014	0.045	-2.38
	C27—H28⋯ O20	Ch⁺-LA	282	0.014	0.045	-2.38
	C10—H11⋯ O44	Ch⁺-LA	291	0.015	0.047	-2.60
	C10—H15⋯ O44	Ch⁺-LA	248	0.013	0.048	-2.16
	C87—H89⋯ O79	LA-LA	233	0.010	0.036	-1.49
	C73—H74⋯ O45	LA-LA	158	0.014	0.045	-2.38
	O83—H94⋯ O45	LA-LA	197	0.016	0.055	-2.83
	O45—H46⋯ O91	LA-LA	353	0.013	0.048	-2.16
	C85—H86⋯ O80	LA-LA	376	0.009	0.032	-1.26
	O71—H82⋯ O104	LA-LA	365	0.014	0.045	-2.38
	O116—H117⋯ O35	LA-LA	279	0.009	0.032	-1.26

ChCl-LA	氢键	类型	BCP	ρ/(a.u.)	(∇²ρ)/(a.u.)	键能/（kcal/mol）
D1	O20—H21⋯Cl	Ch⁺-Cl^-	87	0.023	0.070	-4.39
	O23—H24⋯Cl	Cl^--LA	85	0.046	0.098	-9.52
	C6—H8⋯O26	Ch⁺-LA	42	0.017	0.063	-3.05
	C2—H5⋯ O26	Ch⁺-LA	60	0.014	0.048	-2.38
	C13—H14⋯ O26	Ch⁺-LA	62	0.011	0.038	-1.71
D2	O20—H21⋯Cl	Ch⁺-Cl^-	57	0.020	0.065	-3.72
	O23—H24⋯Cl	Cl^--LA	54	0.036	0.091	-7.29
	O35—H46⋯Cl	Cl^--LA	51	0.033	0.087	-6.62
	C17—H19⋯ O43	Ch⁺-LA	82	0.014	0.045	-2.38
	C2—H3⋯ O43	Ch⁺-LA	91	0.017	0.057	-3.05
	C6—H8⋯ O26	Ch⁺-LA	111	0.013	0.050	-2.16
	C13—H14⋯ O26	Ch⁺-LA	93	0.012	0.042	-1.93
	C2—H5⋯ O26	Ch⁺-LA	97	0.014	0.048	-2.38
D3	O20—H21⋯Cl	Ch⁺-Cl^-	78	0.019	0.063	-3.50
	O47—H58⋯Cl	Cl^--LA	139	0.024	0.071	-4.61
	O35—H46⋯Cl	Cl^--LA	108	0.029	0.081	-5.73
	O23—H24⋯Cl	Cl^--LA	120	0.029	0.083	-5.73
	C17—H19⋯ O43	Ch⁺-LA	79	0.013	0.042	-2.16
	C2—H3⋯ O43	Ch⁺-LA	97	0.017	0.058	-3.05
	C6—H8⋯ O26	Ch⁺-LA	90	0.011	0.042	-1.71
	C2—H5⋯ O26	Ch⁺-LA	106	0.018	0.062	-3.27
	C13—H14⋯ O26	Ch⁺-LA	87	0.010	0.036	-1.49
	C2—H5⋯ O26	Ch⁺-LA	133	0.014	0.052	-2.38
D4	O20—H21⋯Cl	Ch⁺-Cl^-	121	0.018	0.060	-3.27
	O35—H36⋯Cl	Cl^--LA	131	0.023	0.068	-4.39
	O47—H48⋯Cl	Cl^--LA	160	0.026	0.076	-5.06
	O59—H61⋯Cl	Cl^--LA	161	0.028	0.079	-5.50
	O23—H26⋯Cl	Cl^--LA	150	0.014	0.051	-2.38
	C17—H19⋯ O44	Ch⁺-LA	85	0.014	0.047	-2.38
	C2—H3⋯ O44	Ch⁺-LA	101	0.016	0.055	-2.83
	C2—H3⋯ O50	Ch⁺-LA	133	0.011	0.047	-1.71
	C6—H8⋯ O62	Ch⁺-LA	149	0.015	0.054	-2.60
	C2—H5⋯ O62	Ch⁺-LA	156	0.015	0.049	-2.60
	C13—H14⋯ O25	Ch⁺-LA	132	0.013	0.048	-2.16
	C27—H28⋯ O20	Ch⁺-LA	89	0.011	0.042	-1.71
D6	O20—H21⋯Cl	Ch⁺-Cl^-	191	0.017	0.056	-3.05
	O35—H36⋯Cl	Cl^--LA	197	0.025	0.074	-4.83
	O47—H48⋯Cl	Cl^--LA	153	0.021	0.063	-3.94
	O59—H61⋯Cl	Cl^--LA	154	0.022	0.065	-4.17
	O23—H26⋯Cl	Cl^--LA	140	0.013	0.045	-2.15
	C17—H19⋯ O44	Ch⁺-LA	104	0.016	0.055	-2.83
	C2—H3⋯ O44	Ch⁺-LA	178	0.013	0.043	-2.16
	C2—H3⋯ O50	Ch⁺-LA	179	0.014	0.045	-2.38
	C6—H8⋯ O62	Ch⁺-LA	163	0.017	0.058	-3.05
	C2—H5⋯ O62	Ch⁺-LA	206	0.015	0.047	-2.60
	C13—H14⋯ O25	Ch⁺-LA	141	0.009	0.032	-1.26
	C27—H28⋯ O20	Ch⁺-LA	145	0.016	0.055	-2.83
	C6—H8⋯ O65	Ch⁺-LA	198	0.012	0.042	-1.93
	O45—H46⋯ O91	LA-LA	221	0.017	0.058	-3.05
	C85—H86⋯ O80	LA-LA	215	0.009	0.032	-1.26
	C73—H74⋯ O45	LA-LA	165	0.012	0.042	-1.93
D8	O20—H21⋯Cl	Ch⁺-Cl^-	265	0.016	0.05	-2.82
	O35—H36⋯Cl	Cl^--LA	228	0.018	0.060	-3.27
	O47—H48⋯Cl	Cl^--LA	253	0.020	0.06	-3.72
	O59—H61⋯Cl	Cl^--LA	202	0.023	0.067	-4.39
	O23—H26⋯Cl	Cl^--LA	242	0.021	0.063	-3.94
	C17—H19⋯ O44	Ch⁺-LA	247	0.013	0.043	-2.16
	C2—H3⋯ O44	Ch⁺-LA	232	0.015	0.047	-2.60
	C2—H3⋯ O50	Ch⁺-LA	179	0.014	0.045	-2.38
	C6—H8⋯ O62	Ch⁺-LA	251	0.010	0.036	-1.49
	C2—H5⋯ O62	Ch⁺-LA	159	0.016	0.055	-2.83
	C13—H14⋯ O25	Ch⁺-LA	226	0.015	0.047	-2.60
	C27—H28⋯ O20	Ch⁺-LA	167	0.013	0.043	-2.16
	C10—H11⋯ O44	Ch⁺-LA	189	0.014	0.045	-2.38
	C10—H15⋯ O44	Ch⁺-LA	162	0.009	0.032	-1.26
	C87—H89⋯ O79	LA-LA	138	0.019	0.063	-3.50
	C73—H74⋯ O45	LA-LA	129	0.012	0.042	-1.93
	O83—H94⋯ O45	LA-LA	187	0.018	0.062	-3.27
	O45—H46⋯ O91	LA-LA	315	0.009	0.032	-1.26
	C85—H86⋯ O80	LA-LA	180	0.010	0.036	-1.49
D10	O20—H21⋯Cl	Ch⁺-Cl^-	193	0.015	0.054	-2.60
	O35—H36⋯Cl	Cl^--LA	172	0.019	0.063	-3.50
	O47—H48⋯Cl	Cl^--LA	204	0.017	0.056	-3.05
	O59—H61⋯Cl	Cl^--LA	183	0.021	0.063	-3.94
	O23—H26⋯Cl	Cl^--LA	197	0.022	0.065	-4.17
	C17—H19⋯ O44	Ch⁺-LA	280	0.010	0.036	-1.49
	C2—H3⋯ O44	Ch⁺-LA	219	0.014	0.045	-2.38
	C2—H3⋯ O50	Ch⁺-LA	264	0.016	0.055	-2.83
	C6—H8⋯ O62	Ch⁺-LA	260	0.013	0.045	-2.15
	C2—H5⋯ O62	Ch⁺-LA	228	0.013	0.048	-2.16
	C13—H14⋯ O25	Ch⁺-LA	222	0.014	0.045	-2.38
	C27—H28⋯ O20	Ch⁺-LA	282	0.014	0.045	-2.38
	C10—H11⋯ O44	Ch⁺-LA	291	0.015	0.047	-2.60
	C10—H15⋯ O44	Ch⁺-LA	248	0.013	0.048	-2.16
	C87—H89⋯ O79	LA-LA	233	0.010	0.036	-1.49
	C73—H74⋯ O45	LA-LA	158	0.014	0.045	-2.38
	O83—H94⋯ O45	LA-LA	197	0.016	0.055	-2.83
	O45—H46⋯ O91	LA-LA	353	0.013	0.048	-2.16
	C85—H86⋯ O80	LA-LA	376	0.009	0.032	-1.26
	O71—H82⋯ O104	LA-LA	365	0.014	0.045	-2.38
	O116—H117⋯ O35	LA-LA	279	0.009	0.032	-1.26