289
61. Wang D, Hakim SH, Alonso DM, Dumesic JA (2013) A highly selective route to linear alpha
olefins from biomass-derived lactones and unsaturated acids. Chem Commun 49:7040–7042
62. Gupta S, Arora R, Sinha N, Alam MI, Haider MA (2016) Mechanistic insights into the ringopening of biomass derived lactones. RSC Adv 6:12932–12942
63. Chia M, Schwartz TJ, Shanks BH, Dumesic JA (2012) Triacetic acid lactone as a potential
biorenewable platform chemical. Green Chem 14:1850–1853
64. Alam MI et al (2016) Development of 6-amyl-α-pyrone as a potential biomass-derived platform molecule. Green Chem 18:6399–6696
65. Khan TS, Gupta S, Bandodkar P, Alam MI, Haider MA (2018) On the role of oxocarbenium ions formed in Brønsted acidic condition on γ-Al2O3 surface in the ring-opening of
γ-valerolactone. Appl Catal A Gen 560:66–72
66. Awakawa T et al (2013) 4-Hydroxy-3-methyl-6-(1-methyl-2-oxoalkyl)pyran-2-one synthesis
by a type III polyketide synthase from Rhodospirillum centenum. Chembiochem 14:1006–1013
67. Gupta S, Alam MI, Khan TS, Sinha N, Haider MA (2016) On the mechanism of retro-DielsAlder reaction of partially saturated 2-pyrones to produce biorenewable chemicals. RSC Adv
6:60433–60445
68. Khan TS, Gupta S, Alam I, Haider MA (2016) Reactivity descriptor for the retro Diels – Alder
reaction of partially saturated 2-pyrones: DFT study on substituents and solvent e ffects. RSC
Adv 6:101697–101706
69. Shrivastav G, Khan TS, Agarwal M, Haider MA (2018) A Car-Parrinello molecular dynamics
simulation study of the retro Diels-Alder reaction for partially saturated 2-pyrones in water. J
Phys Chem C 122:11599–11607
70. He J et al (2017) Production of levoglucosenone and 5-hydroxymethylfurfural from cellulose
in polar aprotic solvent–water mixtures. Green Chem 19:3642–3653
71. Fowler FW, Katritzky AR, Rutherford RJD (1971) The correlation of solvent effects on physical and chemical properties. J Chem Soc B: 460–469
72. Mukherjee S, Vannice MA (2006) Solvent effects in liquid-phase reactions: I. Activity and
selectivity during citral hydrogenation on Pt/SiO2 and evaluation of mass transfer effects. J
Catal 243:108–130
73. Foresman JB, Keith TA, Wiberg KB, Snoonian J, Frisch MJ (1996) Solvent effects. 5. Influence
of cavity shape, truncation of electrostatics, and electron correlation on ab initio reaction field
calculations. J Phys Chem 100:16098–16104
74. Neurock M (2003) Perspectives on the first principles elucidation and the design of active sites.
J Catal 216:73–88
75. Walker TW et al (2018) Universal kinetic solvent effects in acid-catalyzed reactions of biomass-derived oxygenates. Energy Environ Sci 11:617–628
76. Chew AK et al (2020) Effect of mixed-solvent environments on the selectivity of acid-catalyzed dehydration reactions. ACS Catal 10:1679–1691
77. Overton JC, Zhu X, Mosier NS (2019) Molecular dynamics simulations and experimental verification to determine mechanism of cosolvents on increased 5-hydroxymethylfurfural yield
from glucose. ACS Sustain Chem Eng 7:12997–13003
78. Varghese JJ, Mushrif SH (2019) Origins of complex solvent effects on chemical reactivity and
computational tools to investigate them: a review. React Chem Eng 4:165–206
79. Patri AS et al (2019) A multifunctional cosolvent pair reveals molecular principles of biomass
deconstruction. J Am Chem Soc 141:12545–12557
80. Mellmer MA et al (2019) Effects of chloride ions in acid-catalyzed biomass dehydration reactions in polar aprotic solvents. Nat Commun 10:1–10
81. Laio A, Gervasio FL (2008) Metadynamics: a method to simulate rare events and reconstruct
the free energy in biophysics, chemistry and material science. Rep Prog Phys 71:126601
82. Agarwal V, Dauenhauer PJ, Huber GW, Auerbach SM (2012) Ab initio dynamics of cellulose pyrolysis: nascent decomposition pathways at 327 and 600 °C. J Am Chem Soc
134:14958–14972
Understanding Biomass Chemistry Using Multiscale Molecular Modeling Approach
61. Wang D, Hakim SH, Alonso DM, Dumesic JA (2013) A highly selective route to linear alpha
olefins from biomass-derived lactones and unsaturated acids. Chem Commun 49:7040–7042
62. Gupta S, Arora R, Sinha N, Alam MI, Haider MA (2016) Mechanistic insights into the ringopening of biomass derived lactones. RSC Adv 6:12932–12942
63. Chia M, Schwartz TJ, Shanks BH, Dumesic JA (2012) Triacetic acid lactone as a potential
biorenewable platform chemical. Green Chem 14:1850–1853
64. Alam MI et al (2016) Development of 6-amyl-α-pyrone as a potential biomass-derived platform molecule. Green Chem 18:6399–6696
65. Khan TS, Gupta S, Bandodkar P, Alam MI, Haider MA (2018) On the role of oxocarbenium ions formed in Brønsted acidic condition on γ-Al2O3 surface in the ring-opening of
γ-valerolactone. Appl Catal A Gen 560:66–72
66. Awakawa T et al (2013) 4-Hydroxy-3-methyl-6-(1-methyl-2-oxoalkyl)pyran-2-one synthesis
by a type III polyketide synthase from Rhodospirillum centenum. Chembiochem 14:1006–1013
67. Gupta S, Alam MI, Khan TS, Sinha N, Haider MA (2016) On the mechanism of retro-DielsAlder reaction of partially saturated 2-pyrones to produce biorenewable chemicals. RSC Adv
6:60433–60445
68. Khan TS, Gupta S, Alam I, Haider MA (2016) Reactivity descriptor for the retro Diels – Alder
reaction of partially saturated 2-pyrones: DFT study on substituents and solvent e ffects. RSC
Adv 6:101697–101706
69. Shrivastav G, Khan TS, Agarwal M, Haider MA (2018) A Car-Parrinello molecular dynamics
simulation study of the retro Diels-Alder reaction for partially saturated 2-pyrones in water. J
Phys Chem C 122:11599–11607
70. He J et al (2017) Production of levoglucosenone and 5-hydroxymethylfurfural from cellulose
in polar aprotic solvent–water mixtures. Green Chem 19:3642–3653
71. Fowler FW, Katritzky AR, Rutherford RJD (1971) The correlation of solvent effects on physical and chemical properties. J Chem Soc B: 460–469
72. Mukherjee S, Vannice MA (2006) Solvent effects in liquid-phase reactions: I. Activity and
selectivity during citral hydrogenation on Pt/SiO2 and evaluation of mass transfer effects. J
Catal 243:108–130
73. Foresman JB, Keith TA, Wiberg KB, Snoonian J, Frisch MJ (1996) Solvent effects. 5. Influence
of cavity shape, truncation of electrostatics, and electron correlation on ab initio reaction field
calculations. J Phys Chem 100:16098–16104
74. Neurock M (2003) Perspectives on the first principles elucidation and the design of active sites.
J Catal 216:73–88
75. Walker TW et al (2018) Universal kinetic solvent effects in acid-catalyzed reactions of biomass-derived oxygenates. Energy Environ Sci 11:617–628
76. Chew AK et al (2020) Effect of mixed-solvent environments on the selectivity of acid-catalyzed dehydration reactions. ACS Catal 10:1679–1691
77. Overton JC, Zhu X, Mosier NS (2019) Molecular dynamics simulations and experimental verification to determine mechanism of cosolvents on increased 5-hydroxymethylfurfural yield
from glucose. ACS Sustain Chem Eng 7:12997–13003
78. Varghese JJ, Mushrif SH (2019) Origins of complex solvent effects on chemical reactivity and
computational tools to investigate them: a review. React Chem Eng 4:165–206
79. Patri AS et al (2019) A multifunctional cosolvent pair reveals molecular principles of biomass
deconstruction. J Am Chem Soc 141:12545–12557
80. Mellmer MA et al (2019) Effects of chloride ions in acid-catalyzed biomass dehydration reactions in polar aprotic solvents. Nat Commun 10:1–10
81. Laio A, Gervasio FL (2008) Metadynamics: a method to simulate rare events and reconstruct
the free energy in biophysics, chemistry and material science. Rep Prog Phys 71:126601
82. Agarwal V, Dauenhauer PJ, Huber GW, Auerbach SM (2012) Ab initio dynamics of cellulose pyrolysis: nascent decomposition pathways at 327 and 600 °C. J Am Chem Soc
134:14958–14972
Understanding Biomass Chemistry Using Multiscale Molecular Modeling Approach