Abstract
Sodium carboxymethyl cellulose (SCMC) with different degrees of substitution (DS) possesses structural characteristics and physicochemical properties that are important in broad areas of industrial applications. This reported work investigated the structural characteristics, including the effective length (L ef), the radius of gyration (R g), and the hydrodynamic radius (R H), and the physicochemical properties, including intrinsic viscosity ([η]) and salt tolerance, of SCMC with a DS more than 1.0 in NaCl solution using molecular dynamics (MD) simulations. In the MD simulations, the DS of SCMC varied from 1.2 to 2.8, and the NaCl concentration varied from 0 to 1.4 mol/L. MD simulation results showed that with the increment of NaCl concentration, the L ef (or R g or R H) of SCMC decreased; with the increment of the DS, the L ef of SCMC increased. Also, the variation tendency of [η] in the NaCl solution was consistent with its L ef (or R g or R H). It was noted that the salt tolerance (represented by D) of SCMC increased as the DS increased. In addition, the sharp variation of the D value of SCMC occurred in the range of DS of 1.6 to 2.0, which agreed with the reported experimental results. Radial distribution function analyses showed that the Na+ cations had a stronger interaction with the carboxyl groups in SCMC with lower DS when it was present in a salt solution of higher concentration, which also reasonably explained the variation of L ef, R g, R H, [η], and D of SCMC in NaCl solution.
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References
Adamczyk Z, Jachimska B, Jasiński T, Warszyński P, Wasilewska M (2009) Structure of poly (sodium 4-styrenesulfonate) (PSS) in electrolyte solutions: theoretical modeling and measurements. Colloid Surf A 343:96–103. doi:10.1016/j.colsurfa.2009.01.035
Aerts J (2000) Prediction of intrinsic viscosities of mixed hyperbranched–linear polymers. Comput Theor Polym Sci 10:73–81. doi:10.1016/S1089-3156(99)00035-5
Annamalai N, Thavasi R, Vijayalakshmi S, Balasubramanian T (2011) A novel thermostable and halostable carboxymethylcellulase from marine bacterium Bacillus licheniformisAU01. World J Microbol Biotechnol 27:2111–2115. doi:10.1007/s11274-011-0674-x
Arinaitwe E, Pawlik M (2014) Dilute solution properties of carboxymethyl celluloses of various molecular weights and degrees of substitution. Carbohydr Polym 99:423–431. doi:10.1016/j.carbpol.2013.08.030
Azamat J, Khataee A, Joo SW (2015) Molecular dynamics simulation of trihalomethanes separation from water by functionalized nanoporous graphene under induced pressure. Chem Eng Sci 127:285–292. doi:10.1016/j.ces.2015.01.048
Barré L, Sébastien S, Palermo T (2008) Solution properties of asphaltenes. Langmuir 24:3709–3717. doi:10.1021/la702611s
Bell KY, Leboeuf EJ (2012) Mechanistic investigation of non-ideal sorption behavior in natural organic matter. 1. Vapor phase equilibrium. Environ Sci Technol 46:6689–6697. doi:10.1021/es204726p
Bizzarri AR, Cannistraro S (2002) Molecular dynamics of water at the protein-solvent interface. J Phys Chem B 106:6617–6633. doi:10.1021/jp020100m
Chakraborty T, Chakraborty I, Ghosh S (2006) Sodium carboxymethylcellulose CTAB interaction a detailed thermodynamic study of polymer surfactant interaction with opposite charge. Langmuir 22:9905–9913. doi:10.1021/la0621214
Chia PX, Tan LJ, Huang CMY, Chan EWC, Wong SYW (2015) Hydrogel beads from sugar cane bagasse and palm kernel cake, and the viability of encapsulated Lactobacillus acidophilus. e-Polymers 15:411–418. doi:10.1515/epoly-2015-0133
Cho JY, Heuzey MC, Bégin A, Carreau PJ (2006) Viscoelastic properties of chitosan solutions: effect of concentration and ionic strength. J Food Eng 74:500–515. doi:10.1016/j.jfoodeng.2005.01.047
Coffey DG, Bell DA, Henderson A (1995) Cellulose and cellulose derivatives. Marcel Dekker, New York
Dalakoglou GK, Karatasos K, Lyulin SV, Lyulin AV (2008) Brownian dynamics simulations of complexes of hyperbranched polymers with linear polyelectrolytes: effects of the strength of electrostatic interactions on static properties. Mater Sci Eng B 152:114–118. doi:10.1016/j.mseb.2008.06.012
de Britto D, Assis OBG (2009) Thermal degradation of carboxymethylcellulose in different salty forms. Thermochim Acta 494:115–122. doi:10.1016/j.tca.2009.04.028
Derecskei B, Derecskei-Kovacs A (2006) Molecular dynamic studies of the compatibility of some cellulose derivatives with selected ionic liquids. Mol Simul 32:109–115. doi:10.1080/08927020600669627
Drew PM, Adolf DB (2005) Intrinsic viscosity of dendrimers via equilibrium molecular dynamics. Soft Matter 1:146. doi:10.1039/B501658D
Eriksson KE, Hollmark BH (1969) Kinetic studies of the action of cellulase upon sodium carboxymethyl cellulose. Arch Biochem Biophys 133:233–237. doi:10.1016/0003-9861(69)90450-0
Hansson T, Oostenbrink C, van Gunsteren WF (2002) Molecular dynamics simulations. Curr Opin Struct Biol 12:190–196. doi:10.1016/S0959-440X(02)00308-1
Hebeish AA, El-Rafie MH, Abdel-Mohdy FA, Abdel-Halim ES, Emam HE (2010) Carboxymethyl cellulose for green synthesis and stabilization of silver nanoparticles. Carbohydr Polym 82:933–941. doi:10.1016/j.carbpol.2010.06.020
Heinze T, Koshella A (2005) Carboxymethyl ethers of cellulose and starch—a review. Macromol Symp 223:13–39. doi:10.1002/masy.200550502
Heinze T, Pfeiffer K (1999) Studies on the synthesis and characterization of carboxymethylcellulose. Angew Makromol Chem 266:37–45. doi:10.1002/(SICI)1522-9505(19990501)266:1<37:AID-APMC37>3.0.CO;2-Z
Heinze T, Erler U, Nehls I, Klemn D (1994a) Determination of the substituent pattern of heterogeneously and homogeneously synthesized carboxymethyl cellulose by using high-performance liquid chromatography. Angew Makromol Chem 215:93–106. doi:10.1002/apmc.1994.052150108
Heinze T, Heinze U, Klemm D (1994b) Viscosity behaviour of multivalent metal ion containing carboxymethyl cellulose solutions. Angew Makromol Chem 220:123–132. doi:10.1002/apmc.1994.052200111
Ho FFL, Klosiewicz DW (1980) Proton nuclear magnetic resonance spectrometry for determination of substituents and their distribution in carboxymethylcellulose. Anal Chem 52:913–916. doi:10.1021/ac50056a032
Horner S, Puls J, Saake B, Klohr E, Thielking H (1999) Enzyme-aided characterization of carboxymethyl cellulose. Carbohydr Polym 40:1–7. doi:10.1016/S0144-8617(99)00046-6
Jachimska B, Jasiński T, Warszyński P, Adamczyk Z (2010) Conformations of poly(allylamine hydrochloride) in electrolyte solutions: experimental measurements and theoretical modeling. Colloid Surf A 355:7–15. doi:10.1016/j.colsurfa.2009.11.012
Jiang LY, Li YB, Wang XJ, Zhang L, Wen JQ, Gong M (2008) Preparation and properties of nano-hydroxyapatite/chitosan/carboxymethyl cellulose composite scaffold. Carbohydr Polym 74:680–684. doi:10.1016/j.carbpol.2008.04.035
Jorgensen WL, Jenson C (1998) Temperature dependence of TIP3P, SPC, and TIP4P water from NPT Monte Carlo simulations: seeking temperatures of maximum density. J Comput Chem 19:1179–1186. doi:10.1002/(SICI)1096-987X(19980730)19:10<1179:AID-JCC6>3.0.CO;2-J
Kawakami K, Ihara T, Nishioka T, Kitsuki T, Suzuki Y (2006) Salt tolerance of an aqueous solution of a novel amphiphilic polysaccharide derivative. Langmuir 22:3337–3343. doi:10.1021/la052877n
Khaled KF (2008) Molecular simulation, quantum chemical calculations and electrochemical studies for inhibition of mild steel by triazoles. Electrochim Acta 53:3484–3492. doi:10.1016/j.electacta.2007.12.030
Klemm D, Heinze T, Wagenknecht W (1996) Properties of regioselectively substituted anionic cellulose polyelectrolytes. Ber Bunsenges Phys Chem 100:730–733. doi:10.1002/bbpc.19961000609
Lai LS, Tung J, Lin PS (2000) Solution properties of hsian-tsao (Mesona procumbens Hemsl) leaf gum. Food Hydrocoll 14:287–294. doi:10.1016/j.foodhyd.2016.10.008
Le TC, Todd BD, Daivis PJ, Uhlherr A (2009) Structural properties of hyperbranched polymers in the melt under shear via nonequilibrium molecular dynamics simulation. J Chem Phys 130:074901. doi:10.1063/1.3077006
Lee BR, Oh ES (2013) Effect of molecular weight and degree of substitution of a sodium-carboxymethyl cellulose binder on Li4Ti5O12 anodic performance. J Phys Chem C 117:4404–4409. doi:10.1021/jp311678p
Levine BG, Stone JE, Kohlmeyer A (2011) Fast analysis of molecular dynamics trajectories with graphics processing units—radial distribution function histogramming. J Comput Phys 230:3556–3569. doi:10.1016/j.jcp.2011.01.048
Li WZ, Wang JL (2012) Interactions between lignin and urea researched by molecular simulation. Mol Simul 38:1048–1054. doi:10.1080/08927022.2012.688968
Li YM, Xu GY, Luan YX, Yuan SL, Zhang ZQ (2005) Studies on the interaction between tetradecyl dimethyl betaine and sodium carboxymethyl cellulose by DPD simulations. Colloid Surf A 257–258:385–390. doi:10.1016/j.colsurfa.2004.10.120
Li J, Lewis RB, Dahn JR (2007) Sodium carboxymethyl cellulose a potential binder for si negative electrodes for Li-ion batteries. Electrochem Solid State Lett 10:A17–A20. doi:10.1149/1.2398725
Li WZ, Wang JL, Xu DJ, Zhang S (2014) Study on adsorption and desorption of urea in lignosulfonate with molecular simulations. Comput Theor Chem 1033:60–66. doi:10.1016/j.comptc.2014.01.032
Li WZ, Zhang S, Zhao YY, Huang SY, Zhao JS (2017a) Molecular docking and molecular dynamics simulation analyses of urea with ammoniated and ammoxidized lignin. J Mol Gr Model 71:58–69. doi:10.1016/j.jmgm.2016.11.005
Li WZ, Zhao YY, Huang SY, Zhang S, Zhang L (2017b) Development and evaluation of an automatically adjusting coarse-grained force field for a β-O-4 type lignin from atomistic simulations. Model Simul Mater Sci Eng 25:015001. doi:10.1088/0965-0393/25/1/015001
Mazeau K, Wyszomirski M (2012) Modelling of Congo red adsorption on the hydrophobic surface of cellulose using molecular dynamics. Cellulose 19:1495–1506. doi:10.1007/s10570-012-9757-6
McNew CP, LeBoeuf EJ (2015) The role of attached phase soil and sediment organic matter physicochemical properties on fullerene (nC60) attachment. Chemosphere 139:609–616. doi:10.1016/j.chemosphere.2014.12.070
Miyamoto H, Yamane C, Ueda K (2013) Structural changes in the molecular sheets along (hk0) planes derived from cellulose Iβ by molecular dynamics simulations. Cellulose 20:1089–1098. doi:10.1007/s10570-013-9915-5
Mondal MIH, Yeasmin MS, Rahman MS (2015) Preparation of food grade carboxymethyl cellulose from corn husk agrowaste. Int J Biol Macromol 79:144–150. doi:10.1016/j.ijbiomac.2015.04.061
Moučka F, Nezbeda I, Smith WR (2015) Chemical potentials, activity coefficients, and solubility in aqueous NaCl solutions: prediction by polarizable force fields. J Chem Theory Comput 11:1756–1764. doi:10.1021/acs.jctc.5b00018
Pal K, Banthia AK, Majumdar DK (2006) Development of carboxymethyl cellulose acrylate for various biomedical applications. Biomed Mater 1:85–91. doi:10.1088/1748-6041/1/2/006
Pyun CW, Fixman M (1966) Perturbation theory of the intrinsic viscosity of polymer chains. J Chem Phys 44:2107–2115. doi:10.1063/1.1726988
Rappé AK, Goddard WA III (1991) Charge equilibration for molecular dynamics simulations. J Phys Chem 95:3358–3363. doi:10.1021/j100161a070
Reiser S, Horsch M, Hasse H (2016) Density of ethanolic alkali halide salt solutions by experiment and molecular simulation. Fluid Phase Equilib 408:141–150. doi:10.1016/j.fluid.2015.08.005
Reuben J, Conner HT (1983) Analysis of the carbon-13 NMR spectrum of hydrolyzed O-(carboxymethyl) cellulose: monomer composition and substitution patterns. Carbohydr Res 115:1–13. doi:10.1016/0008-6215(83)88129-4
Richards EL, Buzza D, Davies GR (2007) Monte Carlo simulation of random branching in hyperbranched polymers. Macromolecules 40:2210–2218. doi:10.1021/ma0700126
Rokhade AP, Agnihotri SA, Patil SA, Mallikarjuna NN, Kulkarni PV, Aminabhavi TM (2006) Semi-interpenetrating polymer network microspheres of gelatin and sodium carboxymethyl cellulose for controlled release of ketorolac tromethamine. Carbohydr Polym 65:243–252. doi:10.1016/j.carbpol.2006.01.013
Saake B, Horner S, Puls J, Heinze T, Koch W (2001) A new approach in the analysis of the substituent distribution of carboxymethyl celluloses. Cellulose 8:59–67. doi:10.1023/A:1016658307946
Shakun M, Heinze T, Radke W (2013) Determination of the DS distribution of non-degraded sodium carboxymethyl cellulose by gradient chromatography. Carbohydr Polym 98:943–950. doi:10.1016/j.carbpol.2013.06.066
Silva DA, de Paula RCM, Feitosa JPA, de Brito ACF, Maciel JS, Paula HCB (2004) Carboxymethylation of cashew tree exudate polysaccharide. Carbohydr Polym 58:163–171. doi:10.1016/j.carbpol.2004.06.034
Singh RK, Khatri OP (2012) A scanning electron microscope based new method for determining degree of substitution of sodium carboxymethyl cellulose. J Microsc 246:43–52. doi:10.1111/j.1365-2818.2011.03583.x
Song XY, Sun Y, Wu XR, Zeng FL (2011) Molecular dynamics simulation of a novel kind of polymer composite incorporated with polyhedral oligomeric silsesquioxane (POSS). Comput Mater Sci 50:3282–3289. doi:10.1016/j.commatsci.2011.06.009
Sousa SF, Fernandes PA, Ramos MJ (2006) Protein-ligand docking: current status and future challenges. Proteins 65:15–26. doi:10.1002/prot.21082
Tezuka Y, Tsuchiya Y, Shiomi T (1996) 13C NMR determination of substituent distribution in carboxymethylcellulose by use of its peresterified derivatives. Carbohydr Res 291:99–108. doi:10.1016/S0008-6215(96)00163-2
Tong K, Song X, Sun S, Xu Y, Yu J (2014) Molecular dynamics study of linear and comb-like polyelectrolytes in aqueous solution: effect of Ca2+ ions. Mol Phys 112:2176–2183. doi:10.1080/00268976.2014.893036
Vogt S, Klemn D, Heinze T (1996) Effective esterification of carboxymethyl cellulose in a new non-aqueous swelling system. Polym Bull 36:549–555. doi:10.1007/BF00342445
Wang H, Zeng XF, Wang WC, Cao DP (2015) Selective capture of trace sulfur gas by porous covalent-organic materials. Chem Eng Sci 135:373–380. doi:10.1016/j.ces.2015.02.015
Wu XW, Moon RJ, Martini A (2013) Crystalline cellulose elastic modulus predicted by atomistic models of uniform deformation and nanoscale indentation. Cellulose 20:43–55. doi:10.1007/s10570-012-9823-0
Yao L, Chen PK, Ding B, Luo JH, Jiang B, Zhou G (2012) Molecular design of modified polyacrylamide for the salt tolerance. J Mol Model 18:4529–4545. doi:10.1007/s00894-012-1447-7
Yao YT, Alderson KL, Alderson A (2016) Modeling of negative Poisson’s ratio (auxetic) crystalline cellulose Iβ. Cellulose 23:3429–3448. doi:10.1007/s10570-016-1069-9
Yarovsky I, Evans E (2002) Computer simulation of structure and properties of crosslinked polymers: application to epoxy resins. Polymer 43:963–969. doi:10.1016/s0032-3861(01)00634-6
Yeasmin MS, Mondal MIH (2015) Syntesis of highly substituted carboxymethyl cellulose depending on cellulose particle size. Int J Biol Macromol 80:725–731. doi:10.1016/j.ijbiomac.2015.07.040
Yeh IC, Hummer G (2004) System-size dependence of diffusion coefficients and viscosities from molecular dynamics simulations with periodic boundary conditions. J Phys Chem 108:15873–15879. doi:10.1021/jp0477147
Zemljič LF, Stenius P, Laine J, Stana-Kleinschek K (2008) Topochemical modification of cotton fibres with carboxymethyl cellulose. Cellulose 15:315–321. doi:10.1007/s10570-007-9175-3
Zhang L, LeBoeuf EJ (2009) A molecular dynamics study of natural organic matter: 1. Lignin, kerogen and soot. Org Geochem 40:1132–1142. doi:10.1016/j.orggeochem.2009.08.002
Zhang J, Zhang LM, Li ZM (2000) Synthesis and aqueous solution properties of hydrophobically modified graft copolymer of sodium carboxymethylcellulose with acrylamide and dimethyloctyl (2-methacryloxyethyl) ammonium bromide. J Appl Polym Sci 78:537–542. doi:10.1002/1097-4628(20001017)78:3<537:AID-APP80>3.0.CO;2-W
Zhang YL, Tan ND, Zhao PW (2016) Non-covalent marriage of β-cyclodextrin-polyethylene glycol and functional polyacrylamide via host–guest interaction: construction, characterization and performances. RSC Adv 6:59718–59727. doi:10.1039/c6ra07102c
Zimm BH (1948) The scattering of light and the radial distribution function of high polymer solutions. J Chem Phys 16:1093–1099. doi:10.1063/1.1746738
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This work was financially supported by the National Natural Science Foundation of China (Grant No. 30871988) and the Jiangsu Provincial Science and Technology Project (Grant No. BK2014147110).
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Li, W., Huang, S., Xu, D. et al. Molecular dynamics simulations of the characteristics of sodium carboxymethyl cellulose with different degrees of substitution in a salt solution. Cellulose 24, 3619–3633 (2017). https://doi.org/10.1007/s10570-017-1364-0
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DOI: https://doi.org/10.1007/s10570-017-1364-0