Simulations of the Biodegradation of Citrate Based Polymers for Artificial Scaffolds Using Accelerated Reactive Molecular Dynamics

Dasgupta, Nabankur; Yilmaz, Dundar E.; van Duin, Adri C. T.

doi:10.1021/acs.jpcb.0c03008

Title: Simulations of the Biodegradation of Citrate Based Polymers for Artificial Scaffolds Using Accelerated Reactive Molecular Dynamics

Abstract

Here, we explore the reactivity and mechanical properties of poly(1,6-hexanediol-co-Citric acid) via ReaxFF molecular dynamics simulations. We implement an accelerated scheme within the ReaxFF framework to study the hydrolysis reaction of the polymer which is provided with sufficient amount of energy known as the restrain energy after a suitable pre-transition state configuration is obtained to overcome the activation energy barrier and the desired product is obtained. The validity of the ReaxFF force field is established by comparing the ReaxFF energy barriers of ester and ether hydrolysis with benchmark DFT values in literature. We perform chemical and mechanical degradation of polymer chain bundles at 300 K. We find that ester hydrolyzes faster than ether due to lower activation energy barrier of the reaction. The selectivity of the bond-boost scheme has been demonstrated by lowering the boost parameters of the accelerated simulation which almost stops the ether hydrolysis. Mechanical degradation of pre-hydrolyzed and intermittent hydrolyzed polymer bundles is performed along the longitudinal direction at two different strain rates. We find that the tensile modulus of the polymers are increases with increase in strain rates which shows that polymers show a strain dependent behavior. The tensile modulus of the Polyester-ether is higher thanmore »« less

Authors:

Dasgupta, Nabankur ^[1]; Yilmaz, Dundar E. ^[1]; van Duin, Adri C. T. ^[1]

Pennsylvania State Univ., University Park, PA (United States)

Publication Date:: Thu Jun 04 00:00:00 EDT 2020

Research Org.:: Univ. of Utah, Salt Lake City, UT (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1633054

Grant/Contract Number:: SC0019285

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

Additional Journal Information:: Journal Volume: 124; Journal Issue: 25; Journal ID: ISSN 1520-6106

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Dasgupta, Nabankur, Yilmaz, Dundar E., and van Duin, Adri C. T. Simulations of the Biodegradation of Citrate Based Polymers for Artificial Scaffolds Using Accelerated Reactive Molecular Dynamics.  United States: N. p., 2020. 
Web.  doi:10.1021/acs.jpcb.0c03008.

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                    Dasgupta, Nabankur, Yilmaz, Dundar E., & van Duin, Adri C. T. Simulations of the Biodegradation of Citrate Based Polymers for Artificial Scaffolds Using Accelerated Reactive Molecular Dynamics.  United States.  https://doi.org/10.1021/acs.jpcb.0c03008

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                    Dasgupta, Nabankur, Yilmaz, Dundar E., and van Duin, Adri C. T. Thu .  
"Simulations of the Biodegradation of Citrate Based Polymers for Artificial Scaffolds Using Accelerated Reactive Molecular Dynamics".  United States.  https://doi.org/10.1021/acs.jpcb.0c03008.  https://www.osti.gov/servlets/purl/1633054.

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@article{osti_1633054,

  title        = {Simulations of the Biodegradation of Citrate Based Polymers for Artificial Scaffolds Using Accelerated Reactive Molecular Dynamics},

  author       = {Dasgupta, Nabankur and Yilmaz, Dundar E. and van Duin, Adri C. T.},

  abstractNote = {Here, we explore the reactivity and mechanical properties of poly(1,6-hexanediol-co-Citric acid) via ReaxFF molecular dynamics simulations. We implement an accelerated scheme within the ReaxFF framework to study the hydrolysis reaction of the polymer which is provided with sufficient amount of energy known as the restrain energy after a suitable pre-transition state configuration is obtained to overcome the activation energy barrier and the desired product is obtained. The validity of the ReaxFF force field is established by comparing the ReaxFF energy barriers of ester and ether hydrolysis with benchmark DFT values in literature. We perform chemical and mechanical degradation of polymer chain bundles at 300 K. We find that ester hydrolyzes faster than ether due to lower activation energy barrier of the reaction. The selectivity of the bond-boost scheme has been demonstrated by lowering the boost parameters of the accelerated simulation which almost stops the ether hydrolysis. Mechanical degradation of pre-hydrolyzed and intermittent hydrolyzed polymer bundles is performed along the longitudinal direction at two different strain rates. We find that the tensile modulus of the polymers are increases with increase in strain rates which shows that polymers show a strain dependent behavior. The tensile modulus of the Polyester-ether is higher than Polyester yet reaches yield-stress faster than Polyester. This makes Polyester more ductile than Polyester-ether.},

  doi          = {10.1021/acs.jpcb.0c03008},

  journal      = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},

  number       = 25,

  volume       = 124,

  place        = {United States},

  year         = {Thu Jun 04 00:00:00 EDT 2020},

  month        = {Thu Jun 04 00:00:00 EDT 2020}

}

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Works referenced in this record:

Biomedical applications of biodegradable polymers
journal, May 2011

Ulery, Bret D.; Nair, Lakshmi S.; Laurencin, Cato T.
Journal of Polymer Science Part B: Polymer Physics, Vol. 49, Issue 12
DOI: 10.1002/polb.22259

Biodegradable polymers as biomaterials
journal, August 2007

Nair, Lakshmi S.; Laurencin, Cato T.
Progress in Polymer Science, Vol. 32, Issue 8-9
DOI: 10.1016/j.progpolymsci.2007.05.017

Biodegradable and bioactive porous polymer/inorganic composite scaffolds for bone tissue engineering
journal, June 2006

Rezwan, K.; Chen, Q. Z.; Blaker, J. J.
Biomaterials, Vol. 27, Issue 18, p. 3413-3431
DOI: 10.1016/j.biomaterials.2006.01.039

Polycaprolactone-based biomaterials for tissue engineering and drug delivery: Current scenario and challenges
journal, January 2016

Mondal, Debasish; Griffith, May; Venkatraman, Subbu S.
International Journal of Polymeric Materials and Polymeric Biomaterials, Vol. 65, Issue 5
DOI: 10.1080/00914037.2015.1103241

Polyester elastomers for soft tissue engineering
journal, January 2018

Ye, Hongye; Zhang, Kangyi; Kai, Dan
Chemical Society Reviews, Vol. 47, Issue 12
DOI: 10.1039/c8cs00161h

Citrate-Based Biomaterials and Their Applications in Regenerative Engineering
journal, July 2015

Tran, Richard T.; Yang, Jian; Ameer, Guillermo A.
Annual Review of Materials Research, Vol. 45, Issue 1
DOI: 10.1146/annurev-matsci-070214-020815

Chitosan-based biomaterials for tissue engineering
journal, April 2013

Croisier, Florence; Jérôme, Christine
European Polymer Journal, Vol. 49, Issue 4
DOI: 10.1016/j.eurpolymj.2012.12.009

Collagen-Based Biomaterials for Tissue Engineering Applications
journal, March 2010

Parenteau-Bareil, Rémi; Gauvin, Robert; Berthod, François
Materials, Vol. 3, Issue 3
DOI: 10.3390/ma3031863

Recent Advances in Polyanhydride Based Biomaterials
journal, April 2018

Basu, Arijit; Domb, Abraham J.
Advanced Materials, Vol. 30, Issue 41
DOI: 10.1002/adma.201706815

A review of photocrosslinked polyanhydrides:
journal, December 2000

Burkoth, Amy K.; Anseth, Kristi S.
Biomaterials, Vol. 21, Issue 23
DOI: 10.1016/s0142-9612(00)00107-1

Organotin Polyethers as Biomaterials
journal, October 2009

Carraher, Charles; Roner, Michael
Materials, Vol. 2, Issue 4
DOI: 10.3390/ma2041558

Synthesis and characterization of biomimetic citrate-based biodegradable composites: BIOMIMETIC CITRATE-BASED BIODEGRADABLE COMPOSITES
journal, August 2013

Tran, Richard T.; Wang, Liang; Zhang, Chang
Journal of Biomedical Materials Research Part A, Vol. 102, Issue 8
DOI: 10.1002/jbm.a.34928

Synthesis and characterization of novel citric acid-based polyester elastomers
journal, March 2009

Djordjevic, Ivan; Choudhury, Namita Roy; Dutta, Naba K.
Polymer, Vol. 50, Issue 7
DOI: 10.1016/j.polymer.2009.01.045

Synthesis and characterization of citrate-based fluorescent small molecules and biodegradable polymers
journal, March 2017

Xie, Zhiwei; Kim, Jimin P.; Cai, Qing
Acta Biomaterialia, Vol. 50
DOI: 10.1016/j.actbio.2017.01.019

A citric acid-based hydroxyapatite composite for orthopedic implants
journal, December 2006

Qiu, Hongjin; Yang, Jian; Kodali, Pradeep
Biomaterials, Vol. 27, Issue 34
DOI: 10.1016/j.biomaterials.2006.07.042

Novel Citric Acid-Based Biodegradable Elastomers for Tissue Engineering
journal, March 2004

Yang, J.; Webb, A. R.; Ameer, G. A.
Advanced Materials, Vol. 16, Issue 6
DOI: 10.1002/adma.200306264

Citrate-based biodegradable injectable hydrogel composites for orthopedic applications
journal, January 2013

Gyawali, Dipendra; Nair, Parvathi; Kim, Harry K. W.
Biomater. Sci., Vol. 1, Issue 1
DOI: 10.1039/c2bm00026a

Development of osteopromotive poly (octamethylene citrate glycerophosphate) for enhanced bone regeneration
journal, July 2019

He, Yun; Li, Qiyao; Ma, Chuying
Acta Biomaterialia, Vol. 93
DOI: 10.1016/j.actbio.2019.03.050

Synthesis and evaluation of poly(diol citrate) biodegradable elastomers
journal, March 2006

Yang, Jian; Webb, Antonio R.; Pickerill, Samuel J.
Biomaterials, Vol. 27, Issue 9
DOI: 10.1016/j.biomaterials.2005.05.106

Analysis of degradation data of poly(l-lactide–co-l,d-lactide) and poly(l-lactide) obtained at elevated and physiological temperatures using mathematical models
journal, October 2010

Han, Xiaoxiao; Pan, Jingzhe; Buchanan, Fraser
Acta Biomaterialia, Vol. 6, Issue 10
DOI: 10.1016/j.actbio.2010.05.015

Mathematical modeling of degradation for bulk-erosive polymers: Applications in tissue engineering scaffolds and drug delivery systems
journal, March 2011

Chen, Yuhang; Zhou, Shiwei; Li, Qing
Acta Biomaterialia, Vol. 7, Issue 3
DOI: 10.1016/j.actbio.2010.09.038

A model for simultaneous crystallisation and biodegradation of biodegradable polymers
journal, January 2009

Han, Xiaoxiao; Pan, Jingzhe
Biomaterials, Vol. 30, Issue 3
DOI: 10.1016/j.biomaterials.2008.10.001

Coarse-grained molecular dynamics simulations of polymerization with forward and backward reactions
journal, June 2018

Krajniak, Jakub; Zhang, Zidan; Pandiyan, Sudharsan
Journal of Computational Chemistry, Vol. 39, Issue 22
DOI: 10.1002/jcc.25348

All-Atom Empirical Potential for Molecular Modeling and Dynamics Studies of Proteins ^†
journal, April 1998

MacKerell, A. D.; Bashford, D.; Bellott, M.
The Journal of Physical Chemistry B, Vol. 102, Issue 18
DOI: 10.1021/jp973084f

Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids
journal, January 1996

Jorgensen, William L.; Maxwell, David S.; Tirado-Rives, Julian
Journal of the American Chemical Society, Vol. 118, Issue 45
DOI: 10.1021/ja9621760

Molecular and Kinetic Models for High-Rate Thermal Degradation of Polyethylene
journal, February 2018

Lane, J. Matthew D.; Moore, Nathan W.
The Journal of Physical Chemistry A, Vol. 122, Issue 16
DOI: 10.1021/acs.jpca.7b11180

Molecular Dynamics Simulations on the Thermal Decomposition of Meta-Aramid Fibers
journal, June 2018

Yin, Fei; Tang, Chao; Wang, Qian
Polymers, Vol. 10, Issue 7
DOI: 10.3390/polym10070691

Investigating structure property relations of poly (p-phenylene terephthalamide) fibers via reactive molecular dynamics simulations
journal, October 2018

Yilmaz, Dundar E.; van Duin, Adri C. T.
Polymer, Vol. 154
DOI: 10.1016/j.polymer.2018.09.001

Accelerated ReaxFF Simulations for Describing the Reactive Cross-Linking of Polymers
journal, July 2018

Vashisth, Aniruddh; Ashraf, Chowdhury; Zhang, Weiwei
The Journal of Physical Chemistry A, Vol. 122, Issue 32
DOI: 10.1021/acs.jpca.8b03826

Revisiting the Mechanism of Neutral Hydrolysis of Esters: Water Autoionization Mechanisms with Acid or Base Initiation Pathways
journal, May 2013

da Silva, Poliana Lima; Guimarães, Luciana; Pliego, Josefredo R.
The Journal of Physical Chemistry B, Vol. 117, Issue 21
DOI: 10.1021/jp311504d

Reaction Paths of the Water-Assisted Neutral Hydrolysis of Ethyl Acetate
journal, July 2005

Yamabe, Shinichi; Tsuchida, Noriko; Hayashida, Yousuke
The Journal of Physical Chemistry A, Vol. 109, Issue 32
DOI: 10.1021/jp058029i

Energy Barriers for Alkaline Hydrolysis of Carboxylic Acid Esters in Aqueous Solution by Reaction Field Calculations
journal, August 2000

Zhan, Chang-Guo; Landry, Donald W.; Ornstein, Rick L.
The Journal of Physical Chemistry A, Vol. 104, Issue 32
DOI: 10.1021/jp001459i

An accurate theoretical study of energy barriers of alkaline hydrolysis of carboxylic esters
journal, March 2012

Wang, Huajing
Research on Chemical Intermediates, Vol. 38, Issue 9
DOI: 10.1007/s11164-012-0535-8

Molecular Dynamics Prediction of the Mechanism of Ester Hydrolysis in Water
journal, October 2008

Gunaydin, Hakan; Houk, K. N.
Journal of the American Chemical Society, Vol. 130, Issue 46
DOI: 10.1021/ja8050525

Nucleophile assisted hydrolysis of carbon–oxygen bonds in ethers
journal, July 2002

Polydore, Catherine; Roundhill, D. Max; Liu, Heng-Qian
Journal of Molecular Catalysis A: Chemical, Vol. 186, Issue 1-2
DOI: 10.1016/s1381-1169(02)00138-3

Molecular Dynamics Study of Acid-Catalyzed Hydrolysis of Dimethyl Ether in Aqueous Solution
journal, June 2011

Liang, Xiao; Montoya, Alejandro; Haynes, Brian S.
The Journal of Physical Chemistry B, Vol. 115, Issue 25
DOI: 10.1021/jp201951a

The Effect of the Primary Solvate Shell on the Mechanism of the Stöber Silica Synthesis. A Density Functional Investigation
journal, January 2009

Terleczky, Péter; Nyulászi, László
The Journal of Physical Chemistry A, Vol. 113, Issue 6
DOI: 10.1021/jp8067206

A second-generation reactive empirical bond order (REBO) potential energy expression for hydrocarbons
journal, January 2002

Brenner, Donald W.; Shenderova, Olga A.; Harrison, Judith A.
Journal of Physics: Condensed Matter, Vol. 14, Issue 4
DOI: 10.1088/0953-8984/14/4/312

A reactive potential for hydrocarbons with intermolecular interactions
journal, April 2000

Stuart, Steven J.; Tutein, Alan B.; Harrison, Judith A.
The Journal of Chemical Physics, Vol. 112, Issue 14
DOI: 10.1063/1.481208

The ReaxFF reactive force-field: development, applications and future directions
journal, March 2016

Senftle, Thomas P.; Hong, Sungwook; Islam, Md Mahbubul
npj Computational Materials, Vol. 2, Issue 1
DOI: 10.1038/npjcompumats.2015.11

Development of the ReaxFF Methodology for Electrolyte–Water Systems
journal, February 2019

Fedkin, Mark V.; Shin, Yun Kyung; Dasgupta, Nabankur
The Journal of Physical Chemistry A, Vol. 123, Issue 10
DOI: 10.1021/acs.jpca.8b10453

ReaxFF molecular dynamics simulations on the structure and dynamics of electrolyte water systems at ambient temperature
journal, February 2020

Dasgupta, Nabankur; Kyung Shin, Yun; Fedkin, Mark V.
Computational Materials Science, Vol. 172
DOI: 10.1016/j.commatsci.2019.109349

Extension of the ReaxFF Combustion Force Field toward Syngas Combustion and Initial Oxidation Kinetics
journal, January 2017

Ashraf, Chowdhury; van Duin, Adri C. T.
The Journal of Physical Chemistry A, Vol. 121, Issue 5
DOI: 10.1021/acs.jpca.6b12429

Tunable nanomechanics of protein disulfide bonds in redox microenvironments
journal, January 2012

Keten, Sinan; Chou, Chia-Ching; van Duin, Adri C. T.
Journal of the Mechanical Behavior of Biomedical Materials, Vol. 5, Issue 1
DOI: 10.1016/j.jmbbm.2011.08.017

Atomistic-scale insights into the crosslinking of polyethylene induced by peroxides
journal, November 2019

Akbarian, Dooman; Hamedi, Hossein; Damirchi, Behzad
Polymer, Vol. 183
DOI: 10.1016/j.polymer.2019.121901

Atomistic Scale Analysis of the Carbonization Process for C/H/O/N-Based Polymers with the ReaxFF Reactive Force Field
journal, May 2019

Kowalik, Malgorzata; Ashraf, Chowdhury; Damirchi, Behzad
The Journal of Physical Chemistry B, Vol. 123, Issue 25
DOI: 10.1021/acs.jpcb.9b04298

Reactions of Singly-Reduced Ethylene Carbonate in Lithium Battery Electrolytes: A Molecular Dynamics Simulation Study Using the ReaxFF
journal, December 2011

Bedrov, Dmitry; Smith, Grant D.; van Duin, Adri C. T.
The Journal of Physical Chemistry A, Vol. 116, Issue 11
DOI: 10.1021/jp210345b

Transition State Theory
journal, October 1981

Pechukas, P.
Annual Review of Physical Chemistry, Vol. 32, Issue 1
DOI: 10.1146/annurev.pc.32.100181.001111

Introduction to the Kinetic Monte Carlo Method
book, January 2007

Voter, Arthur F.
Radiation Effects in Solids
DOI: 10.1007/978-1-4020-5295-8_1

A New Insight into the Formation of Polymer Networks: A Kinetic Monte Carlo Simulation of the Cross-Linking Polymerization of S/DVB
journal, November 2013

Hamzehlou, Shaghayegh; Reyes, Yuri; Leiza, Jose R.
Macromolecules, Vol. 46, Issue 22
DOI: 10.1021/ma4016054

Polymer chain scission, oligomer production and diffusion: A two-scale model for degradation of bioresorbable polyesters
journal, February 2011

Han, Xiaoxiao; Pan, Jingzhe
Acta Biomaterialia, Vol. 7, Issue 2
DOI: 10.1016/j.actbio.2010.09.005

A method for accelerating the molecular dynamics simulation of infrequent events
journal, March 1997

Voter, Arthur F.
The Journal of Chemical Physics, Vol. 106, Issue 11
DOI: 10.1063/1.473503

Temperature-accelerated dynamics for simulation of infrequent events
journal, June 2000

So/rensen, Mads R.; Voter, Arthur F.
The Journal of Chemical Physics, Vol. 112, Issue 21
DOI: 10.1063/1.481576

Metadynamics: Metadynamics
journal, February 2011

Barducci, Alessandro; Bonomi, Massimiliano; Parrinello, Michele
Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 1, Issue 5
DOI: 10.1002/wcms.31

Accelerated molecular dynamics with the bond-boost method
journal, September 2003

Miron, Radu A.; Fichthorn, Kristen A.
The Journal of Chemical Physics, Vol. 119, Issue 12
DOI: 10.1063/1.1603722

Development of a ReaxFF Reactive Force Field for Interstitial Oxygen in Germanium and Its Application to GeO ₂ /Ge Interfaces
journal, December 2018

Nayir, Nadire; van Duin, Adri C. T.; Erkoc, Sakir
The Journal of Physical Chemistry C, Vol. 123, Issue 2
DOI: 10.1021/acs.jpcc.8b08862

Electronegativity Equalization Method: Parameterization and Validation for Large Sets of Organic, Organohalogene and Organometal Molecule
journal, July 2007

Varekova, Radka; Jirouskova, Zuzanna; Vanek, Jakub
International Journal of Molecular Sciences, Vol. 8, Issue 7
DOI: 10.3390/i8070572

Second-Generation ReaxFF Water Force Field: Improvements in the Description of Water Density and OH-Anion Diffusion
journal, June 2017

Zhang, Weiwei; van Duin, Adri C. T.
The Journal of Physical Chemistry B, Vol. 121, Issue 24
DOI: 10.1021/acs.jpcb.7b02548

Modeling failure mechanisms of poly(p-phenylene terephthalamide) fiber using reactive potentials
journal, November 2015

Yılmaz, Dündar E.
Computational Materials Science, Vol. 109
DOI: 10.1016/j.commatsci.2015.07.010

ReaxFF Reactive Force Field for Molecular Dynamics Simulations of Hydrocarbon Oxidation
journal, February 2008

Chenoweth, Kimberly; van Duin, Adri C. T.; Goddard, William A.
The Journal of Physical Chemistry A, Vol. 112, Issue 5
DOI: 10.1021/jp709896w

Effect of chemical structure on thermo-mechanical properties of epoxy polymers: Comparison of accelerated ReaxFF simulations and experiments
journal, December 2018

Vashisth, Aniruddh; Ashraf, Chowdhury; Bakis, Charles E.
Polymer, Vol. 158
DOI: 10.1016/j.polymer.2018.11.005

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Title: Simulations of the Biodegradation of Citrate Based Polymers for Artificial Scaffolds Using Accelerated Reactive Molecular Dynamics

Abstract

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A second-generation reactive empirical bond order (REBO) potential energy expression for hydrocarbons journal, January 2002

A reactive potential for hydrocarbons with intermolecular interactions journal, April 2000

The ReaxFF reactive force-field: development, applications and future directions journal, March 2016

Development of the ReaxFF Methodology for Electrolyte–Water Systems journal, February 2019

ReaxFF molecular dynamics simulations on the structure and dynamics of electrolyte water systems at ambient temperature journal, February 2020

Extension of the ReaxFF Combustion Force Field toward Syngas Combustion and Initial Oxidation Kinetics journal, January 2017

Tunable nanomechanics of protein disulfide bonds in redox microenvironments journal, January 2012

Atomistic-scale insights into the crosslinking of polyethylene induced by peroxides journal, November 2019

Atomistic Scale Analysis of the Carbonization Process for C/H/O/N-Based Polymers with the ReaxFF Reactive Force Field journal, May 2019

Reactions of Singly-Reduced Ethylene Carbonate in Lithium Battery Electrolytes: A Molecular Dynamics Simulation Study Using the ReaxFF journal, December 2011

Transition State Theory journal, October 1981

Introduction to the Kinetic Monte Carlo Method book, January 2007

A New Insight into the Formation of Polymer Networks: A Kinetic Monte Carlo Simulation of the Cross-Linking Polymerization of S/DVB journal, November 2013

Polymer chain scission, oligomer production and diffusion: A two-scale model for degradation of bioresorbable polyesters journal, February 2011

A method for accelerating the molecular dynamics simulation of infrequent events journal, March 1997

Temperature-accelerated dynamics for simulation of infrequent events journal, June 2000

Metadynamics: Metadynamics journal, February 2011

Accelerated molecular dynamics with the bond-boost method journal, September 2003

Development of a ReaxFF Reactive Force Field for Interstitial Oxygen in Germanium and Its Application to GeO 2 /Ge Interfaces journal, December 2018

Electronegativity Equalization Method: Parameterization and Validation for Large Sets of Organic, Organohalogene and Organometal Molecule journal, July 2007

Second-Generation ReaxFF Water Force Field: Improvements in the Description of Water Density and OH-Anion Diffusion journal, June 2017

Modeling failure mechanisms of poly(p-phenylene terephthalamide) fiber using reactive potentials journal, November 2015

ReaxFF Reactive Force Field for Molecular Dynamics Simulations of Hydrocarbon Oxidation journal, February 2008

Effect of chemical structure on thermo-mechanical properties of epoxy polymers: Comparison of accelerated ReaxFF simulations and experiments journal, December 2018

Biomedical applications of biodegradable polymers
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Biodegradable polymers as biomaterials
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Biodegradable and bioactive porous polymer/inorganic composite scaffolds for bone tissue engineering
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Polycaprolactone-based biomaterials for tissue engineering and drug delivery: Current scenario and challenges
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Citrate-Based Biomaterials and Their Applications in Regenerative Engineering
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Collagen-Based Biomaterials for Tissue Engineering Applications
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Recent Advances in Polyanhydride Based Biomaterials
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A review of photocrosslinked polyanhydrides:
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Organotin Polyethers as Biomaterials
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Synthesis and characterization of biomimetic citrate-based biodegradable composites: BIOMIMETIC CITRATE-BASED BIODEGRADABLE COMPOSITES
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Synthesis and characterization of novel citric acid-based polyester elastomers
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Synthesis and characterization of citrate-based fluorescent small molecules and biodegradable polymers
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A citric acid-based hydroxyapatite composite for orthopedic implants
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Novel Citric Acid-Based Biodegradable Elastomers for Tissue Engineering
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Citrate-based biodegradable injectable hydrogel composites for orthopedic applications
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Development of osteopromotive poly (octamethylene citrate glycerophosphate) for enhanced bone regeneration
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Synthesis and evaluation of poly(diol citrate) biodegradable elastomers
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Analysis of degradation data of poly(l-lactide–co-l,d-lactide) and poly(l-lactide) obtained at elevated and physiological temperatures using mathematical models
journal, October 2010

Mathematical modeling of degradation for bulk-erosive polymers: Applications in tissue engineering scaffolds and drug delivery systems
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A model for simultaneous crystallisation and biodegradation of biodegradable polymers
journal, January 2009

Coarse-grained molecular dynamics simulations of polymerization with forward and backward reactions
journal, June 2018

All-Atom Empirical Potential for Molecular Modeling and Dynamics Studies of Proteins ^†
journal, April 1998

Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids
journal, January 1996

Molecular and Kinetic Models for High-Rate Thermal Degradation of Polyethylene
journal, February 2018

Molecular Dynamics Simulations on the Thermal Decomposition of Meta-Aramid Fibers
journal, June 2018

Investigating structure property relations of poly (p-phenylene terephthalamide) fibers via reactive molecular dynamics simulations
journal, October 2018

Accelerated ReaxFF Simulations for Describing the Reactive Cross-Linking of Polymers
journal, July 2018

Revisiting the Mechanism of Neutral Hydrolysis of Esters: Water Autoionization Mechanisms with Acid or Base Initiation Pathways
journal, May 2013

Reaction Paths of the Water-Assisted Neutral Hydrolysis of Ethyl Acetate
journal, July 2005

Energy Barriers for Alkaline Hydrolysis of Carboxylic Acid Esters in Aqueous Solution by Reaction Field Calculations
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An accurate theoretical study of energy barriers of alkaline hydrolysis of carboxylic esters
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Molecular Dynamics Prediction of the Mechanism of Ester Hydrolysis in Water
journal, October 2008

Nucleophile assisted hydrolysis of carbon–oxygen bonds in ethers
journal, July 2002

Molecular Dynamics Study of Acid-Catalyzed Hydrolysis of Dimethyl Ether in Aqueous Solution
journal, June 2011

The Effect of the Primary Solvate Shell on the Mechanism of the Stöber Silica Synthesis. A Density Functional Investigation
journal, January 2009

A second-generation reactive empirical bond order (REBO) potential energy expression for hydrocarbons
journal, January 2002

A reactive potential for hydrocarbons with intermolecular interactions
journal, April 2000

The ReaxFF reactive force-field: development, applications and future directions
journal, March 2016

Development of the ReaxFF Methodology for Electrolyte–Water Systems
journal, February 2019

ReaxFF molecular dynamics simulations on the structure and dynamics of electrolyte water systems at ambient temperature
journal, February 2020

Extension of the ReaxFF Combustion Force Field toward Syngas Combustion and Initial Oxidation Kinetics
journal, January 2017

Tunable nanomechanics of protein disulfide bonds in redox microenvironments
journal, January 2012

Atomistic-scale insights into the crosslinking of polyethylene induced by peroxides
journal, November 2019

Atomistic Scale Analysis of the Carbonization Process for C/H/O/N-Based Polymers with the ReaxFF Reactive Force Field
journal, May 2019

Reactions of Singly-Reduced Ethylene Carbonate in Lithium Battery Electrolytes: A Molecular Dynamics Simulation Study Using the ReaxFF
journal, December 2011

Transition State Theory
journal, October 1981

Introduction to the Kinetic Monte Carlo Method
book, January 2007

A New Insight into the Formation of Polymer Networks: A Kinetic Monte Carlo Simulation of the Cross-Linking Polymerization of S/DVB
journal, November 2013

Polymer chain scission, oligomer production and diffusion: A two-scale model for degradation of bioresorbable polyesters
journal, February 2011

A method for accelerating the molecular dynamics simulation of infrequent events
journal, March 1997

Temperature-accelerated dynamics for simulation of infrequent events
journal, June 2000

Metadynamics: Metadynamics
journal, February 2011

Accelerated molecular dynamics with the bond-boost method
journal, September 2003

Development of a ReaxFF Reactive Force Field for Interstitial Oxygen in Germanium and Its Application to GeO ₂ /Ge Interfaces
journal, December 2018

Electronegativity Equalization Method: Parameterization and Validation for Large Sets of Organic, Organohalogene and Organometal Molecule
journal, July 2007

Second-Generation ReaxFF Water Force Field: Improvements in the Description of Water Density and OH-Anion Diffusion
journal, June 2017

Modeling failure mechanisms of poly(p-phenylene terephthalamide) fiber using reactive potentials
journal, November 2015

ReaxFF Reactive Force Field for Molecular Dynamics Simulations of Hydrocarbon Oxidation
journal, February 2008

Effect of chemical structure on thermo-mechanical properties of epoxy polymers: Comparison of accelerated ReaxFF simulations and experiments
journal, December 2018