AD Becke

AM Li

B Miehlich

BS Chu

C Lahari

C Valderrama

CY Ma

DJ Malik

Duo-long Di

He-lin Ye

HH Huang

J Tomasi

M Cossi

MP Tsyurupa

MR Oberholzer

S Lou

SB Hawthorne

T Mineva

VA Rassolov

WH Gao

Xing-hui Zhang

XL Du

YF Liu

Yong-feng Liu

Crossref

ORIGINAL RESEARCHDFT study on hydrogen-bonding adsorption mechanism of rutinonto macroporous adsorption resins functionalized with amino,hydroxyl, and carboxyl groupsHe-lin Ye • Yong-feng Liu • Xing-hui Zhang •Duo-long DiReceived: 22 August 2012 / Accepted: 21 November 2012 / Published online: 7 December 2012 The Author(s) 2012. This article is published with open access at Springerlink.comAbstract The adsorption mechanism of a series of mac-roporous adsorption resins (p-(CH3NH)PhL (L = NH2,OH, COOH)) with rutin have been investigated usingdensity functional theory calculations at B3LYP/6-31G(d,p) level of theory. Solvent effects on these specieswere explored using calculations that included a polariz-able continuum model for the aqueous solvent. In thisarticle, the geometry structure, interaction energies and theinfrared spectra for the stable reactants and the adsorptioncomplexes were obtained and analyzed. The results showthat the hydrogen-bonding have been formed in theadsorption complexes. The higher interaction energy iscalculated for the carboxyl group, while the resin withamino group has the highest adsorption capacity for rutin.The adsorption complexes become more and more stable asincreasing the number of adsorbents. Our theoretical studyis in good explanation for the experimental results.Keywords Macroporous adsorption resins  Rutin Hydrogen-bonding adsorption  Density functional theoryIntroductionMacroporous adsorption resins (MARs) are synthetic por-ous crosslinked polymer beads, have been developed into akind of novel functional materials since 1950. They havebeen shown to be potentially powerful separation materialsand have been widely applied in many fields, such aschromatographic analysis [1], treatment [2], pharmaceuti-cal [3], food industries, and wastewater disposal [4].Except for the general advantage of that of the commonadsorbent, MARs possess many special characteristics suchas high mechanical strength, good acid and alkali resis-tance, porous availability, high surface area, and a longlifetime that make them more promising [5–7]. To gain agreater adsorption capacity and a higher adsorption selec-tivity for some specific organic compounds, chemicalmodification of MARs is often undertaken by introducingspecial functional groups into the matrix of the polymericadsorbents [8, 9]. Thus, investigation on the adsorptionfeatures of organic compounds on MARs is of greatimportance [10, 11]. However, theoretical research on theadsorption features of MARs lags far behind. Althoughthere are several reports about the adsorption feature ofMARs, and many of adsorption systems have beenobserved to exhibit multiphasic behavior [12–14]. But littlehas been done to determine the impacts of the pore sizedistribution and the functional groups of polymer resins. Tothe best of our knowledge, there are no detailed theoreticalstudies available on hydrogen-bonding adsorption mecha-nism of rutin onto MARs by density functional method.Recently, we have experimentally synthesized a series ofadsorption MARs with hydrogen-bonding groups, whichwere amino, hydroxyl, and carboxyl groups, respectively(Scheme 1). Adsorption feature of the synthetic resins withrespect to the purification effect was investigated systemicallyH. Ye  Y. Liu  D. Di (&)Key Laboratory of Chemistry of Northwestern Plant Resourcesand Key Laboratory for Natural Medicine of Gansu Province,Lanzhou Institute of Chemical Physics, Chinese Academyof Sciences, Lanzhou 730000, People’s Republic of Chinae-mail: didl@licp.cas.cnH. Ye  Y. LiuGraduate University of the Chinese Academy of Sciences,Beijing 100049, People’s Republic of ChinaX. ZhangCollege of Chemical Engineering, Gansu Lianhe University,Lanzhou 730010, People’s Republic of China123Struct Chem (2013) 24:1443–1449DOI 10.1007/s11224-012-0174-0by employing rutin as the adsorbate. The experimental resultsshowed that MARs with amino group have the higheradsorption capacity and the adsorption selectivity. In thisarticle, we present a hybrid DFT(B3LYP) study for theadsorption mechanism of rutin onto MARs functionalizedwith amino, hydroxyl, and carboxyl groups. The MARs arethe molecule of p-(CH3NH)PhL (L = NH2, OH, COOH) asmodel system. With this theoretical study, we hope to obtaina detailed understanding of adsorption mechanism and pre-dict the trends of adsorption capacity for MARs with thedifferent groups. Meanwhile, we expect to find out moreabout the factors that control the interaction energies of thisimportant reaction and further investigate the effects of sol-vent of the reaction systems.Computational methodsAll of the geometries of the model complexes were fullyoptimized using the density functional theory (DFT)method based on the hybrid of Becke’s three-parameterexchange functional and the Lee, Yang, and Parr correla-tion functional (B3LYP) [15, 16]. The 6-31G basis set[17, 18] with polarization (d) and (p) was used for all of theatoms. Frequency calculations at the same level of theoryhave been achieved to identify each optimized station-ary point as either minima (the number of imaginaryfrequencies [NIMAG = 0]) and to evaluate the zero-pointenergy (ZPE) corrections, which are included in all relativeenergies. The thermodynamic functions, including freeenergies, were calculated at 298.15 K and 1 atm. In con-sideration of the solvent effects on the reactions of interest,we applied a continuum medium to do the full geometrysolvation energy calculations for all of the species, usingUAHF radii on the polarizable continuum model (PCM).The PCM calculations [19–21] were done at the B3LYP/PCM/6-31G(d,p) level of theory. H2O was used as thesolvent, corresponding to the experimental conditions, andthe dielectric constant was assumed to be 78.39 for bulkaqueous solution. All calculations reported here have beencarried out with Gaussian 03 program package [22].Results and discussionIn the first part of this section, we present results from ourcalculations on the adsorption process of rutin to the differentMARs p-(CH3NH)PhL (L = NH2, OH, COOH). The influ-ence of the number of rutin upon the adsorption energies andstructures is investigated in the second part. The optimizedstationary structures of the reactants and the adsorptioncomplexes are depicted schematically in Figs. 1, 2, andTable 1 with selected key geometry parameters (bondlengths and bond angles). The total energies with ZPECH2Cl + NH2H2N CH2 NH NH2CH2Cl + OHH2N CH2 NH OHCH2Cl + COOHH2N CH2 NH COOH(a)(c)(b)Scheme 1 The preparationmethod for macroporousadsorption resins modified withamino benzene compoundsH3O5O2 O4H2O3H1O8HH7O11H6O10HH5O9 H O12HO13HH10O16HHHO14H8HO7O1HH9O15H4O6C2C3C4C5H3C NH N1H3C NH O17H11H3C NH C6H11H12O17O18H11CABRutinC1Fig. 1 The structures of p-(CH3NH)PhL (L = NH2, OH, COOH) and the optimized minimum energy geometry of rutin1444 Struct Chem (2013) 24:1443–1449123corrections and the relative energies to the starting materialsare listed in Table 2.Adsorption mechanism of rutin onto p-(CH3NH)PhL(L = NH2, OH, COOH)Figure 1 shows the optimized geometry of rutin and thestructures of p-(CH3NH)PhL (L = NH2, OH, COOH). Themain geometry parameters are shown in Table 1. As onecan see from Fig. 1 and Table 1, the C1–O1, O1–H1, andO3–H1 bond lengths in rutin are 1.218, 1.804, and 0.953 A˚,respectively. The C2–O7–C3, C3–O8–C4, and C4–O12–C5bond angles are 121.2, 120.6, and 117.4, respectively.The MESP painted on the van der Waals surface is pre-sented in Fig. 3 for the MAR and rutin, which shows strongcharge separation in the systems, the oxygen and nitrogenatom are negatively charged while the rest of the molecule(hydrogen and carbon) is positively charged. These pic-tures also indicate that the H is donated to the O and N. Thestronger electronegativity of A–C structures was attributedto the largest micropore surface, where rutin can beintensively adsorbed by a micropore filling mechanism.The structures of the adsorption complexes with the mostrelevant geometry parameters are shown in Fig. 2 andTable 1.Inspection of Fig. 2 and Table 1 shows that the adsorptionprocess forms the new hydrogen-bonding in the structures ofA-rutin, B-rutin, and C-rutin, respectively. The O1–H11 andO8–H12 bond lengths are 2.549 and 2.287 A˚, respectively,in A-rutin, and the O1–H1 and C4–O8 bond lengths elon-gated by 0.007 A˚ (1.804 A˚ in rutin) and 0.011 A˚ (1.384 A˚ inrutin), respectively, upon going from the reactants to theadsorption complexes. The similar features of the geome-try parameters are also found for B-rutin and C-rutin, and thenew hydrogen-bonding of O1–H11 in B-rutin and theO1–H11 and O17–H1 bond distances in C-rutin are 2.077,1.890, and 2.227 A˚, respectively. These changes in the bondlengths and angles are attributed to form the more stableadsorption complexes. Meanwhile, Fig. 4 shows the IR2.5491.8112.2872.5142.0771.828 2.2271.8901.958A-rutin B-rutin C-rutin2.2213.0081.8212.0362.3092.0172.4112.4692.2722.0442.302A2-rutin A3-rutinFig. 2 The full optimized minimum energy geometries for rutin with A, B, and C, with selected structural parameters (bond lengths in A˚)Struct Chem (2013) 24:1443–1449 1445123Table 1 The partial bondlength (A˚) and bond angle () ofrutin, A, B, C, and theadsorption complexes atB3LYP/PCM/6-31G(d,p) levelParameters Rutin A B C A-rutin B-rutin C-rutinC1–O1 1.218 1.220 1.221 1.220C2–O7 1.352 1.357 1.353 1.354C3–O7 1.396 1.396 1.395 1.395C3–O8 1.385 1.384 1.385 1.383C4–O8 1.384 1.391 1.390 1.384C4–O12 1.387 1.376 1.381 1.384C5–O12 1.373 1.380 1.371 1.371N1–H11 0.995 0.995N1–H12 0.995 0.995O17–H11 0.941 0.945C6–O17 1.191 1.195C6–O18 1.329 1.318O18–H11 0.942 0.954O1–H1 1.804 1.811 1.828 1.958O3–H1 0.953 0.955 0.955 0.955O1–H11 2.549 2.077 1.890O8–H12 2.287O17–H1 2.227C2–O7–C3 121.2 121.0 120.8 120.8C3–O8–C4 120.6 120.3 120.1 119.9C4–O12–C5 117.4 118.7 118.9 118.5Fig. 3 The electrostatic potential mapped on to the van der Waals surface of a representative set of rutin and the macroporous adsorption resinTable 2 Interaction energies for the macroporous adsorption resin with rutinSystem EZPE (a.u.) Egastot (a.u.) DEgasrel (kcal mol-1) Esoltot (a.u.) DEsolrel (kcal mol-1)A-rutin 0.764111 -2,577.747484 -4.32 -2,578.602388 -8.92B-rutin 0.751420 -2,597.590740 -6.41 -2,598.423295 -9.75C-rutin 0.763164 -2,710.355016 -7.32 -2,711.204647 -11.21A2-rutin 0.939728 -2,957.386925 -9.55 -2,958.416132 -9.95A3-rutin 1.109843 -3,337.031674 -18.10 -3,338.238199 -10.69These values were calculated at the B3LYP/6-31G(d,p) level of theory, using the full geometry optimization at the B3LYP/PCM/6-31G(d,p)level of theory to model the effect of waterTotal energy Etot, zero-point energy EZPE, relative energy DErel1446 Struct Chem (2013) 24:1443–1449123spectrum for the stable structures of rutin and A-rutin,B-rutin, and C-rutin at B3LYP/6-31G(d,p) level.The interaction energies for the MARs with rutin areshown in Table 2. The A-rutin, B-rutin, and C-rutin are8.92, 9.75, and 11.21 kcal mol-1 stable than the corre-sponding preliminary reactants from the B3LYP/PCM/6-31G(d,p) calculations in water. The trend of the interactionenergies for the MAR is A-rutin (amino group) \ B-rutin(hydroxyl group) \ C-rutin (carboxyl group). That is tosay, forming hydrogen-bonding for one molecule MARwith carboxyl group is more stable than the amino andhydroxyl groups. We plotted the frontier molecular orbitals(HOMO and LUMO) for rutin and the adsorption com-plexes in Fig. 5. The frontier orbital energy level (DEg =ELUMO - EHOMO) of rutin is 0.10552 eV, while the DEg ofA-rutin, B-rutin, and C-rutin is 0.10031, 0.10334, and0.10560 eV, respectively. Especially, the DEg of A-rutinand B-rutin is lower than rutin because of the MAR. Theadsorption reaction occurs more easily for amino andhydroxyl groups.0100200300400500600700IntensityFrequency / cm -10100200300400500600IntensityFrequency / cm -1Rutin A-rutin02004006008001000IntensityFrequency / cm -1-1000 0 1000 2000 3000 4000 5000 -1000 0 1000 2000 3000 4000 5000-1000 0 1000 2000 3000 4000 5000 -1000 0 1000 2000 3000 4000 500002004006008001000120014001600IntensityFrequency / cm -1B-rutin C-rutinA C Fig. 4 The IR spectrum for the stable rutin, A-rutin, B-rutin, and C-rutin at B3LYP/6-31G(d,p) level and experimentStruct Chem (2013) 24:1443–1449 1447123Adsorption mechanism of rutinonto (p-(CH3NH)PhNH2)n(n = 1–3)The adsorption experimental results show that the greateradsorption capacity has been found for the MAR with aminogroup. This MAR contains numerous amino groups, whichcould form many of hydrogen-bonding with a rutin mole-cule. Here, we present a detailed computational investigationof the rutin by explicitly coordinating one, two, and three theresin with amino group to the O and H atoms. Figure 2depicts the optimized geometries found for rutin with(p-(CH3NH)PhNH2)n (n = 1–3, A-rutin to A3-rutin), andthe key geometrical parameters are given in Table 1. InA2-rutin and A3-rutin, the N atom of resin attack to the H atomof rutin and the H atom of amino group add to O atom of rutinthrough forming hydrogen-bonding. The new N–H and O–Hbond lengths are 2.017–3.008 A˚ in A2-rutin and A3-rutin.Examination of Table 2 shows the two p-(CH3NH)PhNH2molecules adsorption for rutin has a interaction energy of9.95 kcal mol-1 relative to the starting materials, which isdecreased significantly by 1.03 kcal mol-1 compared to thecorresponding one p-(CH3NH)PhNH2 adsorption. While theinteraction energy for three p-(CH3NH)PhNH2 becomes10.69 kcal mol-1 and this is decreased by 0.74 kcal mol-1compared to the analogous energy two p-(CH3NH)PhNH2(9.95 kcal mol-1). The adsorption complexes becomes morestable as the number of p-(CH3NH)PhNH2 goes from n = 1 ton = 3. Upon saturation of the rutin by coordination ofp-(CH3NH)PhNH2 molecules one by one, the interactionenergy of species would become relatively constant.Systematic comparisons of experimentfor the adsorption behaviorFigure 4 shows the IR spectra of the resins A (PPDA) andC (PANB). In the spectrum of A, there is an absorptionband in the vicinity of 3374.3 cm-1 that belongs to thestretching vibrations of the N–H bond. In addition, the C–Nstretching of the benzene ring and NH group are shown tobe at 1,024 cm-1. Two other characteristic peaks related tothe C=C stretching of phenyl group at 1605 and 1495 cm-1are much stronger than before reacting, and another twobands at 812.3 and 694 cm-1, which involve C–H out ofbending of CH group for mono-substitution of benzene.For the IR spectrum of p-aminobenzoic acid modifiedresin. A moderate C=O stretching band involved in form-aldehyde carbonyl groups comes forth at 1698.4 cm-1.Finally, a weak absorption band appears at 3394.5 cm-1,and this band is related to O–H stretching of hydroxylhydrogen .Comparing the adsorption capacity of flavonoids (rutin)on the three adsorbents by experiment method, we canunderstand that they follow the order A (–NH2) [ B(–OH) [ C (–COOH), and the MARs with amino group has-0.21441-0.31472-0.21475-0.31809HOMOLUMOHOMOLUMOHOMOLUMOEnergy-0.21442-0.32002Eg=0.10031ev Eg=0.10334ev Eg=0.10560evA-rutin B-rutin C-rutin-0.21375-0.31927HOMOLUMOEg=0.10552evRutinFig. 5 Spatial plots of the frontier molecular orbitals calculated for rutin, A-rutin, B-rutin, and C-rutin. The orbital energies are given in eV1448 Struct Chem (2013) 24:1443–1449123the highest equilibrium adsorption capacity at the equilib-rium concentration. From Table 2, we observed that thecomputed interaction energies for the adsorption is given inthe following order, p-(CH3NH)PhCOOH [ p-(CH3NH)PhOH [ p-(CH3NH)PhNH2. The result shows that thehydrogen-bonding of p-(CH3NH)PhCOOH with rutin isthe more stable compared to p-(CH3NH)PhOH andp-(CH3NH)PhNH2. While the adsorption capacity has beeninvestigated including of many of the factors controllingexcept for functional group, such as pore diameter, BETsurface area, pore volume, particle size, group amount,temperature, etc. In this article, we mainly present a detailedDFT computational investigation of the hydrogen-bondingadsorption mechanism for rutin onto p-(CH3NH)PhL(L = NH2, OH, COOH).ConclusionIn this article, we have carried out a theoretical investiga-tion at the DFT (B3LYP) level for the adsorption mecha-nism of rutin onto a series of MARs functionalized withamino, hydroxyl, and carboxyl groups. According to ourcalculations, the adsorption mechanism of rutin onto theresin is based on hydrogen-bonding. The interaction ener-gies for adsorption complexes are 8.92–11.21 kcal mol-1,and C-rutin is the more stable than A-rutin and B-rutin. Theadsorption experiments show that adsorption capacity ofA-rutin is the highest. We present a detailed computationalinvestigation of the rutin by explicitly coordinating one,two, and three A-rutin to the O and H atoms of rutin. Uponsaturation of the rutin by coordination of p-(CH3NH)PhNH2molecules one by one, the adsorption complexes becomesmore stable. Our computational results are in good expla-nation for the experimental observations, which has com-prehensive ramifications for the adsorbent synthesize,adsorption experimental design, and practical application.Acknowledgments This research project was financially supportedby the Hundred Talents Program of the Chinese Academy of Sciences(CAS) and the National Natural Sciences Foundation of China(NSFC, No. 20974116).Open Access This article is distributed under the terms of theCreative Commons Attribution License which permits any use, dis-tribution, and reproduction in any medium, provided the originalauthor(s) and the source are credited.References1. Tsyurupa MP, Maslova LA, Andreeva AI, Mrachkovskaya TA,Davankov VA (1995) React Polym 25:692. Malik DJ, Warwick GL, Venturi M, Streat M, Hellgardt K,Hoenich N, Dale JA (2004) Biomaterials 25:29333. Lahari C, Jasti LS, Fadnavis NW, Sontakke K, Ingavle G, DeokarS, Ponrathnam S (2010) Langmuir 26:10964. 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DFT study on hydrogen-bonding adsorption mechanism of rutin onto macroporous adsorption resins functionalized with amino, hydroxyl, and carboxyl groups

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DFT study on hydrogen-bonding adsorption mechanism of rutin onto macroporous adsorption resins functionalized with amino, hydroxyl, and carboxyl groups

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