Machine-Learning-Assisted Design of Deep Eutectic Solvents Based on Uncovered Hydrogen Bond Patterns

Non-ionic deep eutectic solvents(DESs)are non-ionic designer solvents with various applications in catalysis,extraction,carbon capture,and pharmaceuticals.However,discovering new DES candidates is challenging due to a lack of efficient tools that accurately predict DES formation.The search for DES relies heavily on intuition or trial-and-error processes,leading to low success rates or missed opportunities.Recognizing that hydrogen bonds(HBs)play a central role in DES formation,we aim to identify HB features that distinguish DES from non-DES systems and use them to develop machine learning(ML)models to discover new DES systems.We first analyze the HB properties of 38 known DES and 111 known non-DES systems using their molecular dynamics(MD)simulation trajectories.The analysis reveals that DES systems have two unique features compared to non-DES systems:The DESs have①more imbalance between the numbers of the two intra-component HBs and②more and stronger inter-component HBs.Based on these results,we develop 30 ML models using ten algorithms and three types of HB-based descriptors.The model performance is first benchmarked using the average and minimal receiver operating characteristic(ROC)-area under the curve(AUC)values.We also analyze the importance of individual features in the models,and the results are consistent with the simulation-based statistical analysis.Finally,we validate the models using the experimental data of 34 systems.The extra trees forest model outperforms the other models in the validation,with an ROC-AUC of 0.88.Our work illustrates the importance of HBs in DES formation and shows the potential of ML in discovering new DESs.

Optimizing extractants selection for efficient separation of phenols and nitrogen-containing heteroaromatics using hydrogen bond interaction strategies

Focusing on the use of imidazolium ionic liquids and quaternary ammonium salts-based deep eutectic solvents for the separation of phenols and nitrogen-containing heteroaromatics,the role of heteroaromatics as specific sites for hydrogen bond-based separation has been investigated.These environmentally friendly solvents are known for their ability to form hydrogen bonds with heteroatoms,a key aspect in separation processes.We quantified the hydrogen bond interaction energy to reach the threshold energy for efficient O-and N-heteroaromatics separation.This article provides an in-depth study of the structural nuances of different hydrogen bonding sites and their affinity properties while conducting a comparative evaluation of the separation efficiency of ionic liquids and deep eutectic solvents from a thermodynamic perspective.Results showed that phenols with dual hydrogen bonding recognition sites were easier to separate than nitrogen-containing heteroaromatics.Imidazolium ionic liquids were more suitable for the extraction of nonbasic nitrogen-containing heteroaromatics,and quaternary ammonium salts-based deep eutectic solvents are more effective for phenols and basic nitrogen-containing heteroaromatics,which was confirmed by Fourier transform infrared spectroscopy and empirical tests.Therefore,this study provides a theoretical basis for the strategy design and selection of extractants for the efficient separation of O-and N-containing aromatic compounds.

Solvent effects on hydrogen bonding between primary alcohols and esters

The interaction by hydrogen bond formation of some primary alcohols （ l-heptanol, l-octanol and l-decanol） with esters （methyl methacrylate, ethyl methacrylate and butyl methacrylate） was investigated in non-polar solvents viz., n-heptane, CC14 and benzene by means of FTIR spectroscopy. Formation constants and free energy changes of complex formation were determined. The dependence of the equilibrium constants and free energy changes of complex formation on the alkyl chain length of both the alcohols and esters are discussed. The solvent interaction between the solute and solvent. effect on the hydrogen bond formation is discussed in terms of specific

Effects of Hydrogen-bonding Interaction and Polarity on Emission Spectrum of Naphthalene-Triethylamine in Mixed Solvent

The effects of the protic and aprotic polar solvents on the emission spectrum of the naphthalene-triethyl-amine system in THF were studied under conditions of steady-state illumination. The fluorescence spectrum of the naphthalene-triethylamine system consists of two emission bands, the fluorescence band of naphthalene(band A, 329 nm) and the emission band of the exciplex(band B, 468 nm). The intensities of both the emission bands decrease with increasing the solvent polarity. The intensity of band B also decreases due to the hydrogen-bonding interaction between triethylamine and protic solvent, while that of band A increases. It is thus suggested that the quenching of naphthalene fluorescence by triethylamine in THF occurs through the charge transfer and electron transfer reactions. The spectral changes upon the increase of solvent polarity can be explained by the dependences of the equilibrium constant between exciplex and ion-pair and the rate constant for the electron transfer reaction from triethylamine to the excited naphthalene on the relative permittivity of solvent. It is shown that the formation of intermolecular hydrogen-bonding between triethylamine and protic solvent suppresses the quenching reaction by the decrease in free amine. Acetonitrile has only a polar effect and trichloroacetic acid only a hydrogen-bonding(or protonation) effect, while alcohols have both the effects. The effects of alcohols could be separated into the effects of solvent polarity and intermolecular hydrogen-bonding interaction quantitatively.

A^1HNMR STUDY ON THE FORMATION AND BREAKING OF INTRAMOLECULAR HYDROGEN BONDS OF BILIRUBIN IN CDCl_3-DMSO-d_6 BINARY SOLVENT

The formation and breaking of intramolecular hydrogen bonds of bilirubin in CDCl_3-DMSO-d_6 binary solvent have been investigated by means of NMR spectroscopy.The chemical shifts of protons at dipyrrinone lactam C=O and N-H,Pyrrole N-H,C-5,C-15 and methylene groups of 8,12-propionic acid side-chains changed markedly as a function of composition of the binary solvent.The hydrogen bond formation is dependent on the conformation of propionic acid side-chains.

EFFECT OF HYDROGEN BONDING ON DIRECTION OF PHOTOISOMERIZATION OF RETINOIDS:THE ORIGIN OF THE SOLVENT POLARITY EFFECT.

Studies of direction of photoisomerization of retinal,retinonitrile,a- retinonitrile and a trienenitrile analog in different solvents with varying wave- lengths of excitation and reaction temperature led to the conclusion that the well known solvent dependent photochemistry of retinoids is due to selective excitation of the hydrogen bonded species.

低共熔溶剂抑制煤自燃的机理

化学阻化是防治煤自燃的重要手段之一,提出了一种基于低共熔溶剂(DES)的类离子液体阻化方法。首先,采用加热法制备并筛选了7种室温低共熔溶剂,分析了不同DES处理后煤样的官能团及热力学特性变化规律,在此基础上采用密度泛函理论分析了DES中氢键强度对煤理化性质的改性差异,推导了低共熔溶剂的阻化机制及其最佳氢键强度。研究结果表明:DES处理后煤中氢键网络被破坏重排,脂肪烃与芳香烃相对丰度增加了10%~37%,脂肪族支链结构参数降低了9.38%~20.65%,含氧官能团(C=O和C—O)相对丰度下降了22.88%~56.94%,游离的小分子化合物和矿物质被溶出。DES处理后煤的蒸发脱附阶段质量损失和吸氧增重阶段的吸氧量减小,低温氧化阶段和热分解阶段放热量降低,减小幅度分别为8.94%~77.51%和5.40%~26.20%。氢键受体(HBD)作用点位电负性越强,与氢键供体(HBA)形成的DES团簇氢键强度越大。DES中氢键强度与煤中氢键网络破坏程度呈正相关关系,与吸氧增重阶段的吸氧量和低温氧化放热量及矿物质脱除率呈局部相关性。DES通过溶解煤中活性成分削弱煤的低温氧化强度。并通过促进氢键重排,将低热稳定性氢键转换为热稳定性更高的环状氢键四聚体和OH—N氢键,以此提高煤的断键吸热量。但过高的氢键强度将会抑制活性侧链的脱除和溶解,因此抑制煤自燃的低共熔溶剂的最佳氢键强度应控制在69.45~160.00 kJ/mol。

苦参碱-脂肪酸低共熔溶剂的制备及物性

构建了一系列基于苦参碱和脂肪酸的低共熔溶剂(Deep Eutectic Solvent,DES),探讨了脂肪酸烷基链长、氢键供体(HBD)与氢键受体(HBA)的物质的量之比对DES的理化性质的影响。结果表明:DES的密度、表面张力、电导率、极性随脂肪酸烷基链长度的增加而降低,黏度随脂肪酸链长的增大而增加;密度、表面张力和黏度随苦参碱与脂肪酸物质的量之比的减小而降低,电导率则随苦参碱与脂肪酸物质的量之比的减小而增加,上述不同的变化趋势源于苦参碱和脂肪酸分子之间相互作用的变化。

“溶剂剪刀”克服惰性氢键促进常压氧气下高效催化氧化芳香烃

氢键是调节各类催化反应体系中分子行为的重要作用力,能够有效活化分子、改变作用位置及控制反应途径,具有重要的科学意义和应用潜力.然而,氢键的利用过程存在着惰性效应难题,严重阻碍反应的顺利进行.如何有针对性地打破惰性的氢键作用力,探索氢键的构建与破坏机制,成为提高反应转化效率和选择性的重要途径,有利于实现高原子经济性并减少碳足迹.芳香烃氧化制羧酸是工业上重要的催化氧化过程,但存在高能耗、副产物多以及二氧化碳排放等问题.本文以甲苯液相氧气氧化制苯甲酸为模型反应,提出了旨在克服惰性氢键的"溶剂剪刀"策略.通过利用氢键受体溶剂(如醋酸、醋酸乙酯、氯乙酸乙酯或氯乙酸甲酯)作为破坏试剂,与强氢键供体溶剂六氟异丙醇(HFIP)形成氢键,从而将关键中间体苯甲醛从惰性的氢键结合状态中释放出来,将甲苯在温和条件下高效氧化为苯甲酸.使用NHPI/金属醋酸盐/HFIP-HOAc作为催化体系,在温和的反应条件(45°C,0.1 MPa O_(2))下反应4 h,甲苯转化率达到96.8%,苯甲酸选择性达98.7%.该方法不仅成功实现了甲苯到苯甲酸的高效转化,还可进一步拓展至邻(间,对)甲基甲苯等甲基芳烃,在25‒45°C和常压氧气条件下高效氧化制备芳香羧酸.利用变浓度核磁共振实验,定量测定了氢键供体HFIP与不同“剪刀溶剂”形成氢键的标准吉布斯自由能变化(ΔG^(0)).结果显示,‒ΔG^(0)顺序为醋酸>醋酸乙酯>氯乙酸乙酯>氯乙酸甲酯,其中醋酸的ΔG^(0)达到‒4.319 kJ/mol,具有最强的氢键裁剪能力.实验显示,‒ΔG^(0)与周转次数(TON)值(促进苯甲醛氧化的能力)的顺序一致,表明氢键裁剪能力越强的“溶剂-剪刀”越有利于促进苯甲醛的氧化.综上,本文利用“溶剂-剪刀”重建了甲基芳烃氧化反应中的氢键平衡体系,切断了使苯甲醛惰性化的氢键,促进游离苯甲醛的释放,使甲基芳香烃能在温和条件下高效氧化为芳香酸.本研究为有机合成普遍存在的氢键惰性化效应提供了解决思路,有利于促进“氢键调控”在有机合成的应用.

胆碱基DES在EOR及CCUS中的应用与展望

深共晶溶剂(Deep Eutectic Solvent,DES)具有低饱和蒸气压、不易燃、不易爆、无毒、易降解、电化学和热稳定性好等优点。DES具有很好的表面活性,DES中的氢键网络与阴、阳离子表面活性剂具有很好的协同驱油作用。关于DES与常用表面活性剂的协同作用研究尚处于起步阶段,二者复配体系提高采收率(Enhanced Oil Recovery,EOR)机理尚不明确。在全面分析归纳总结胆碱基DES物理化学性质的基础上,探究了DES及其与阴或阳离子表面活性剂复配体系EOR机理,揭示了DES吸收二氧化碳机理,提出了DES在稠油油藏、低渗透油藏EOR以及碳捕集、利用与封存(Carbon Capture,Utilization and Storage,CCUS)中的应用建议。研究结果对DES在EOR和CCUS的应用推广具有重要的指导意义。

低共熔溶剂改性聚丁内酰胺的结晶性能

以氯化胆碱为氢键受体,尿素、草酸和甘油为氢键供体制备了氯化胆碱-尿素、氯化胆碱-草酸和氯化胆碱-甘油三种低共熔溶剂(DES),并用DES改性聚丁内酰胺(PBL)使其熔点降低。通过差示扫描量热、热重分析、红外光谱和X射线衍射研究了DES对PBL的热稳定性、熔点和结晶的影响,并分析了内在作用机理。利用拉伸测试法及熔融指数测定验证了DES对PBL力学性能及加工性能的影响。研究结果表明,氯化胆碱-尿素通过形成新的氢键抑制PBL(200)晶面生长,使结晶度降低了16.2%,从而使熔点降低至253℃。氯化胆碱-草酸通过草酸羧基与PBL的游离羰基形成氢键,氯化胆碱-甘油则以增塑作用为主,两者对PBL氢键的破坏作用有限,改性效果略差,结晶度分别降低了4.4%和1.9%,熔点分别降低了8℃和6℃。

基于酰基氨基脲和脲键协同作用的自愈合聚脲材料的制备及性能

[目的]制备具有优异力学性能和室温自愈合能力的材料具有极大的挑战性。[方法]以间苯二甲酰肼(IPDH)和硫脲为扩链剂,通过在聚合物硬段中引入酰基氨基脲和脲键基团来制备室温自愈合聚脲材料,分析了不同氢键密度下聚合物的化学结构、热学性能、力学性能和自愈合性能。[结果]以IPDH与硫脲的物质的量比3∶2所制备的材料显示了较好的综合力学性能:拉伸强度19.33 MPa,断裂伸长率929.6%,韧性52.69 MJ/m^(3)。聚合物中存在的多种氢键作用赋予了材料优异的自愈合能力。断裂试样经25℃修补5 h后断裂面基本消失,36 h后拉伸强度和断裂伸长率均恢复了至少80%。[结论]该材料可以在温和的条件下愈合,在智能保护材料方面有潜在的应用前景。

脂肪酸低共熔溶剂对姜黄素的溶解作用

制备了辛酸(C8)分别与癸酸(C10)、月桂酸(C12)及肉豆蔻酸(C14)形成的C8-C10、C8-C12、C8-C143种脂肪酸低共熔溶剂(DES)。C8-C10、C8-C12、C8-C14对姜黄素的溶解度分别为1.11、1.24、1.44 mmol/L,比姜黄素在水中的溶解度分别提高了约29、32、38倍。通过Gaussian模拟计算,得到姜黄素与C8、C10、C12、C14形成的分子缔合物的吉布斯自由能分别为−48.49、−64.27、−91.26、−120.59 kJ/mol。姜黄素与烷基链最长的C14形成“三明治”型分子缔合物,具有最强的氢键和疏水缔合作用,使姜黄素在C8-C14脂肪酸DES中表现出最高的溶解度和最强的紫外吸收及荧光发射强度。姜黄素在C8-C10、C8-C12、C8-C143种脂肪酸DES中均具有显著提高的稳定性和1,1-二苯基-2-三硝基苯肼(DPPH)自由基清除能力。

低共熔溶剂的性质与应用研究进展

随着绿色化学的兴起,绿色低污染、无污染溶剂备受关注。低共熔溶剂被认为是一种类离子液体的新型绿色溶剂,具有低饱和蒸汽压、低熔点、无毒环保、可降解及价格低等优势。综述了低共熔溶剂的组成和种类、制备方法、理化性质(如熔点、粘度、表面张力等),以及在萃取分离、生物化工、电化学等领域的应用,并总结了目前低共熔溶剂应用存在的问题,对未来研究方向进行展望。

Preparation of Co/S co-doped carbon catalysts for excellent methylene blue degradation

S and Co co-doped carbon catalysts were prepared via pyrolysis of MOF-71 and thiourea mixtures at 800℃at a mass ratio of MOF-71 to thiourea of 1:0.1 to effectively activate peroxymonosulfate(PMS)for methylene blue(MB)degradation.The effects of two different mixing routes were identified on the MB degradation performance.Particularly,the catalyst obtained by the alcohol solvent evaporation(MOF-AEP)mixing route could degrade 95.60%MB(50 mg/L)within 4 min(degradation rate:K=0.78 min^(-1)),which was faster than that derived from the direct grinding method(MOF-DGP,80.97%,K=0.39 min^(-1)).X-ray photoelectron spectroscopy revealed that the Co-S content of MOF-AEP(43.39at%)was less than that of MOF-DGP(54.73at%),and the proportion of C-S-C in MOF-AEP(13.56at%)was higher than that of MOF-DGP(10.67at%).Density functional theory calculations revealed that the adsorption energy of Co for PMS was -2.94 eV when sulfur was doped as C-S-C on the carbon skeleton,which was higher than that when sulfur was doped next to cobalt in the form of Co-S bond(-2.86 eV).Thus,the C-S-C sites might provide more contributions to activate PMS compared with Co-S.Furthermore,the degradation parameters,including pH and MOF-AEP dosage,were investigated.Finally,radical quenching experiments and electron paramagnetic resonance(EPR)measurements revealed that ^(1)O_(2)might be the primary catalytic species,whereas·O~(2-)might be the secondary one in degrading MB.

线性氨基醇分子内氢键相互作用的溶剂效应

采用受激拉曼光谱技术测量4种线性氨基醇NH_(2)(CH_(2))_nOH(n=2,3,4,5)的气相拉曼光谱,同时采用自发拉曼光谱技术测量其液相拉曼光谱.结果表明:气相状态下,除n=5外,n=2,3,4的线性氨基醇分子中观察到显著的O—H…N分子内氢键相互作用;在纯液相和水溶液(摩尔分数为0.5)状态下,由于分子间氢键相互作用的竞争,4种线性氨基醇的分子内氢键相互作用均消失;在非极性CCl4溶液(摩尔分数为0.001)中,除n=2中可观察到微弱的分子内氢键外,其余线性氨基醇中均未观察到分子内氢键相互作用.因此,不管极性还是非极性溶剂均显著影响线性氨基醇的分子内氢键相互作用.

FeCl_(3)基三元低共熔溶剂分离毛竹木质素效率研究

提高低共熔溶剂(DES)分离木质素效率是实现木质纤维资源高值化利用的前提。本研究基于酸性、中性及碱性二元DES分离毛竹木质素的方法,设计三元DES以提高木质素分离效率,优化三元DES分离木质素的工艺条件,采用Kamlet-Taft溶剂化显色参数,定量分析DES的氢键性能,并对DES分离所得木质素进行结构表征。结果表明,二元DES分离木质素时,木质素溶出率由高到低依次为:酸性DES>中性DES>碱性DES,由FeCl_(3)-聚乙二醇400-氯化胆碱构成的三元DES,其木质素溶出率较高,分离毛竹木质素的最佳工艺条件为:温度130℃、时间3 h、质量比1∶15、加水质量比10%(相对于聚乙二醇400质量);在此工艺条件下,木质素溶出率可达96.36%。FeCl_(3)的引入增加了三元DES的氢键碱性,使其具有更强的氢键接受能力。拉曼光谱和傅里叶变换红外光谱分析表明,DES分离所得毛竹木质素的主要基本结构单元为愈创木基型和紫丁香基型,且结构完整性优于碱木质素。本研究结果可为DES高效清洁分离毛竹木质素提供参考。

弱碱性低共熔溶剂溶解角蛋白过程及氢键机制

利用低共熔溶剂(DES)较强的氢键拆解能力定向解构角蛋白分子间的次级键,结合还原剂和DES高效断裂二硫键的能力,建立了一种弱损溶解并提取鸡毛中角蛋白的方法。以氯化胆碱为氢键受体(HBA)、乙醇胺、乙二醇、乳酸等为氢键供体(HBD),设计合成了3类(碱性、中性和酸性)13种功能性的DES,考察了还原剂用量(以鸡毛质量为基准,下同)、温度、DES中水质量分数对角蛋白相对分子质量和提取率的影响,通过密度泛函(DFT)理论计算和溶剂显色参数分析了DES内部的氢键网络结构,研究了DES对鸡毛角蛋白的弱损溶解机制。结果表明,以乙醇胺为HBD,不添加还原剂,在n(乙醇胺)∶n(氯化胆碱)=2∶1、DES中不含水、温度65℃、0.5h的最优条件下,再生角蛋白提取率为31.8%,相对分子质量最高,为66000。以乙醇胺为HBD制备的DES具有还原性,作为碱性DES,其内部的氢键数量多,氢键作用小,氢键能低,可以打乱鸡毛内部的氢键网络,而不会对鸡毛二级结构造成太大破坏。

含5-(2-吡嗪基)-1 H-四氮唑配体的新型锶配合物的合成及固态荧光性质

锶配合物因其优异的催化活性和荧光性质吸引了众多研究者的兴趣。在溶剂热条件下,以氯化锶为金属源,以2-吡嗪基四氮唑(HL)、胡椒酸(HL_(1))为配体,以DMF-水体系为溶剂合成了新型的单核锶配合物{[Sr(L)_(2)]·2H_(2)O}_(n)(I),其结构通过EA、SXRD、PXRD、IR和TGA进行了表征。单晶X-射线衍射结果表明:配合物I结晶于单斜晶系P2_(1)/n空间群,Sr呈略微扭曲的八面体几何构型,而胡椒酸没有参与配位。单核分子之间通过O—H···N氢键相互作用连接形成二维超分子网络结构。固体荧光研究表明:Sr配合物具有良好的荧光性能,最大发射波长为450 nm(λ_(ex)=223 nm),进一步表明I是一种潜在的蓝光材料。

不同含氧官能团对煤润湿性影响的分子动力学模拟研究

为了探究不同含氧官能团对煤润湿性的影响规律,基于分子动力学(molecular dynamics,MD)理论,构建4个不同含氧官能团模拟系统(—COOH、—OH、—CO及—OCH 3),通过模拟接触角、分子相对体积分数、径向分布函数及相互作用能结果,详细分析含氧官能团对煤润湿性的影响规律。研究结果表明:模拟平衡后,在—COOH体系中水团簇的接触角为18.65°,相互作用能为-1049.19 kcal/mol,并形成371.64个氢键。在—OH体系中水团簇的接触角为25.37°,相互作用能为-563.83 kcal/mol,并形成178.03个氢键。在—CO体系中水团簇的接触角为30.10°,相互作用能为-444.25 kcal/mol,并形成58.34个氢键。在—OCH 3体系中水团簇的接触角为59.96°,相互作用能为-149.00 kcal/mol,并形成13.25个氢键。水团簇与不同含氧官能团体系的接触角越小,形成的氢键越多,相互作用能绝对值越大,对煤亲水性增强作用越好,这与分子相对体积分数和径向分布函数分析结果一致;不同含氧官能团对煤亲水性增强作用排序为—COOH>—OH>—CO>—OCH 3。研究结果可为研究煤表面润湿性及其应用提供相关参考。