skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Synthesis and Surface Spectroscopy of alpha-Pinene Isotopologues and Their Corresponding Secondary Organic Material

Abstract

Isotopologues of a-pinene were synthesized to probe the importance of the vinyl, bridgehead, methylene bridge, and the majority of the allylic methylene positions in the surface chemical composition of secondary organic aerosol material (SOM) derived from oxidation of a-pinene by ozone. Vibrational sum frequency generation (SFG) spectra of the ring-substituted isotopologues revealed up to 80% suppression of the SFG signal intensity positioned around 2930 cm-1 in the broad band that is emblematic of unlabeled ?-pinene. SFG spectra of SOM prepared from the ozonolysis of two isotopologues featuring a deuterated methylene bridge group show up to 40% less signal intensity than SOM prepared from methyl-substituted isotopologues, suggesting the presence of the dimethylcyclobutane ring at the SOM surface. The synthesis of isotopically labelled SOM and analysis of their surface-active constituents opens the door to studying the dynamics of gas-phase volatile organic compound (VOC) adsorption and reactivity at varying relative humidity, temperature, and consequently particle viscosity in a way that distinguishes the unlabeled gas-phase molecules from those in the particle phase. More broadly, expanding the range of isotopologues of terpene hydrocarbons that are not commercially available offers the atmospheric community new capabilities to elucidate mechanistic questions in aerosol formation and growth.

Authors:
 [1];  [2];  [1];  [3];  [4]; ORCiD logo [5];  [5]; ORCiD logo [5];  [2]; ORCiD logo [5];  [4];  [4];  [1];  [2]
  1. NORTHWESTERN UNIVERSITY
  2. Northwestern University
  3. UNIVERSITY PROGRAMS
  4. Harvard University
  5. BATTELLE (PACIFIC NW LAB)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1577055
Report Number(s):
PNNL-SA-143837
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 10; Journal Issue: 36
Country of Publication:
United States
Language:
English

Citation Formats

Upshur, Mary A., Vega, Marvin, Be, Ariana G., Chase, Hilary M., Zhang, Yue, Tuladhar, Aashish, Jessamy-Chase, Zizwe A., Fu, Li, Ebben, Carlena J., Wang, Zheming, Martin, Scot T., Martin, Scot T., Geiger, Franz M., and Thomson, Regan. Synthesis and Surface Spectroscopy of alpha-Pinene Isotopologues and Their Corresponding Secondary Organic Material. United States: N. p., 2019. Web. doi:10.1039/c9sc02399b.
Upshur, Mary A., Vega, Marvin, Be, Ariana G., Chase, Hilary M., Zhang, Yue, Tuladhar, Aashish, Jessamy-Chase, Zizwe A., Fu, Li, Ebben, Carlena J., Wang, Zheming, Martin, Scot T., Martin, Scot T., Geiger, Franz M., & Thomson, Regan. Synthesis and Surface Spectroscopy of alpha-Pinene Isotopologues and Their Corresponding Secondary Organic Material. United States. doi:10.1039/c9sc02399b.
Upshur, Mary A., Vega, Marvin, Be, Ariana G., Chase, Hilary M., Zhang, Yue, Tuladhar, Aashish, Jessamy-Chase, Zizwe A., Fu, Li, Ebben, Carlena J., Wang, Zheming, Martin, Scot T., Martin, Scot T., Geiger, Franz M., and Thomson, Regan. Sat . "Synthesis and Surface Spectroscopy of alpha-Pinene Isotopologues and Their Corresponding Secondary Organic Material". United States. doi:10.1039/c9sc02399b.
@article{osti_1577055,
title = {Synthesis and Surface Spectroscopy of alpha-Pinene Isotopologues and Their Corresponding Secondary Organic Material},
author = {Upshur, Mary A. and Vega, Marvin and Be, Ariana G. and Chase, Hilary M. and Zhang, Yue and Tuladhar, Aashish and Jessamy-Chase, Zizwe A. and Fu, Li and Ebben, Carlena J. and Wang, Zheming and Martin, Scot T. and Martin, Scot T. and Geiger, Franz M. and Thomson, Regan},
abstractNote = {Isotopologues of a-pinene were synthesized to probe the importance of the vinyl, bridgehead, methylene bridge, and the majority of the allylic methylene positions in the surface chemical composition of secondary organic aerosol material (SOM) derived from oxidation of a-pinene by ozone. Vibrational sum frequency generation (SFG) spectra of the ring-substituted isotopologues revealed up to 80% suppression of the SFG signal intensity positioned around 2930 cm-1 in the broad band that is emblematic of unlabeled ?-pinene. SFG spectra of SOM prepared from the ozonolysis of two isotopologues featuring a deuterated methylene bridge group show up to 40% less signal intensity than SOM prepared from methyl-substituted isotopologues, suggesting the presence of the dimethylcyclobutane ring at the SOM surface. The synthesis of isotopically labelled SOM and analysis of their surface-active constituents opens the door to studying the dynamics of gas-phase volatile organic compound (VOC) adsorption and reactivity at varying relative humidity, temperature, and consequently particle viscosity in a way that distinguishes the unlabeled gas-phase molecules from those in the particle phase. More broadly, expanding the range of isotopologues of terpene hydrocarbons that are not commercially available offers the atmospheric community new capabilities to elucidate mechanistic questions in aerosol formation and growth.},
doi = {10.1039/c9sc02399b},
journal = {Chemical Science},
number = 36,
volume = 10,
place = {United States},
year = {2019},
month = {9}
}

Works referenced in this record:

Chemistry of secondary organic aerosol: Formation and evolution of low-volatility organics in the atmosphere
journal, May 2008


The Molecular Identification of Organic Compounds in the Atmosphere: State of the Art and Challenges
journal, February 2015

  • Nozière, Barbara; Kalberer, Markus; Claeys, Magda
  • Chemical Reviews, Vol. 115, Issue 10
  • DOI: 10.1021/cr5003485

Plant-derived Secondary Organic Material in the Air and Ecosystems
journal, September 2017


Atmospheric Aerosol Chemistry: Spectroscopic and Microscopic Advances
journal, November 2016


Organic aerosol and global climate modelling: a review
journal, January 2005

  • Kanakidou, M.; Seinfeld, J. H.; Pandis, S. N.
  • Atmospheric Chemistry and Physics, Vol. 5, Issue 4
  • DOI: 10.5194/acp-5-1053-2005

Analysis of Atmospheric Aerosols
journal, July 2008


Morphology of Liquid–Liquid Phase Separated Aerosols
journal, August 2015

  • Qiu, Yuqing; Molinero, Valeria
  • Journal of the American Chemical Society, Vol. 137, Issue 33
  • DOI: 10.1021/jacs.5b05579

Vibrational Sum Frequency Generation Spectroscopy of Secondary Organic Material Produced by Condensational Growth from α-Pinene Ozonolysis
journal, August 2013

  • Shrestha, Mona; Zhang, Yue; Ebben, Carlena J.
  • The Journal of Physical Chemistry A, Vol. 117, Issue 35
  • DOI: 10.1021/jp405065d

Physical Properties of Aerosol Internally Mixed With Soot Particles in a Biogenically Dominated Environment in California
journal, October 2018

  • Sharma, Noopur; China, Swarup; Bhandari, Janarjan
  • Geophysical Research Letters, Vol. 45, Issue 20
  • DOI: 10.1029/2018GL079404

Cloud Activation Potentials for Atmospheric α-Pinene and β-Caryophyllene Ozonolysis Products
journal, July 2017


Observation of Organic Molecules at the Aerosol Surface
journal, May 2016


On Surface Order and Disorder of α-Pinene-Derived Secondary Organic Material
journal, November 2014

  • Shrestha, Mona; Zhang, Yue; Upshur, Mary Alice
  • The Journal of Physical Chemistry A, Vol. 119, Issue 19
  • DOI: 10.1021/jp510780e

Towards the identification of molecular constituents associated with the surfaces of isoprene-derived secondary organic aerosol (SOA) particles
journal, January 2014

  • Ebben, C. J.; Strick, B. F.; Upshur, M. A.
  • Atmospheric Chemistry and Physics, Vol. 14, Issue 5
  • DOI: 10.5194/acp-14-2303-2014

Atmospheric β-Caryophyllene-Derived Ozonolysis Products at Interfaces
journal, December 2018


Unanticipated Stickiness of α-Pinene
journal, February 2017

  • Chase, Hilary M.; Ho, Junming; Upshur, Mary Alice
  • The Journal of Physical Chemistry A, Vol. 121, Issue 17
  • DOI: 10.1021/acs.jpca.6b12653

Assessment of DFT for Computing Sum Frequency Generation Spectra of an Epoxydiol and a Deuterated Isotopologue at Fused Silica/Vapor Interfaces
journal, November 2015

  • Chase, Hilary M.; Rudshteyn, Benjamin; Psciuk, Brian T.
  • The Journal of Physical Chemistry B, Vol. 120, Issue 8
  • DOI: 10.1021/acs.jpcb.5b09769

Accurate Line Shapes from Sub-1 cm –1 Resolution Sum Frequency Generation Vibrational Spectroscopy of α-Pinene at Room Temperature
journal, February 2015

  • Mifflin, Amanda L.; Velarde, Luis; Ho, Junming
  • The Journal of Physical Chemistry A, Vol. 119, Issue 8
  • DOI: 10.1021/jp510700z

Climate-relevant physical properties of molecular constituents for isoprene-derived secondary organic aerosol material
journal, January 2014

  • Upshur, M. A.; Strick, B. F.; McNeill, V. F.
  • Atmospheric Chemistry and Physics, Vol. 14, Issue 19
  • DOI: 10.5194/acp-14-10731-2014

Stereochemical transfer to atmospheric aerosol particles accompanying the oxidation of biogenic volatile organic compounds: CHIRALITY MATTERS IN THE ATMOSPHERE
journal, August 2011

  • Ebben, Carlena J.; Zorn, Soeren R.; Lee, Seung-Bok
  • Geophysical Research Letters, Vol. 38, Issue 16
  • DOI: 10.1029/2011GL048599

Vibrational Mode Assignment of α-Pinene by Isotope Editing: One Down, Seventy-One To Go
journal, April 2016

  • Upshur, Mary Alice; Chase, Hilary M.; Strick, Benjamin F.
  • The Journal of Physical Chemistry A, Vol. 120, Issue 17
  • DOI: 10.1021/acs.jpca.6b01995

Contrasting organic aerosol particles from boreal and tropical forests during HUMPPA-COPEC-2010 and AMAZE-08 using coherent vibrational spectroscopy
journal, January 2011

  • Ebben, C. J.; Martinez, I. S.; Shrestha, M.
  • Atmospheric Chemistry and Physics, Vol. 11, Issue 20
  • DOI: 10.5194/acp-11-10317-2011

Organic Constituents on the Surfaces of Aerosol Particles from Southern Finland, Amazonia, and California Studied by Vibrational Sum Frequency Generation
journal, July 2012

  • Ebben, Carlena J.; Shrestha, Mona; Martinez, Imee S.
  • The Journal of Physical Chemistry A, Vol. 116, Issue 32
  • DOI: 10.1021/jp302631z

The total synthesis of (+-)-.alpha.- and (+-)-.beta.-pinene. A general route to bicyclic mono- and sesquiterpenes
journal, March 1976

  • Thomas, Mullapponmannil Thomas; Fallis, Alex G.
  • Journal of the American Chemical Society, Vol. 98, Issue 5
  • DOI: 10.1021/ja00421a029

The total synthesis of (±)α- and (±)β-pinene: A general route to bicyclo[3.1.1]heptanes
journal, January 1973


Sum Frequency Generation Spectroscopy and Molecular Dynamics Simulations Reveal a Rotationally Fluid Adsorption State of α-Pinene on Silica
journal, June 2016

  • Ho, Junming; Psciuk, Brian T.; Chase, Hilary M.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 23
  • DOI: 10.1021/acs.jpcc.6b03158

Beyond Local Group Modes in Vibrational Sum Frequency Generation
journal, March 2015

  • Chase, Hilary M.; Psciuk, Brian T.; Strick, Benjamin L.
  • The Journal of Physical Chemistry A, Vol. 119, Issue 14
  • DOI: 10.1021/acs.jpca.5b02208

Formation and occurrence of dimer esters of pinene oxidation products in atmospheric aerosols
journal, January 2013

  • Kristensen, K.; Enggrob, K. L.; King, S. M.
  • Atmospheric Chemistry and Physics, Vol. 13, Issue 7
  • DOI: 10.5194/acp-13-3763-2013

Thermodynamics of oligomer formation: implications for secondary organic aerosol formation and reactivity
journal, January 2013

  • DePalma, Joseph W.; Horan, Andrew J.; Hall IV, Wiley A.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 18
  • DOI: 10.1039/c3cp44586k

Formation of Oligomers in Secondary Organic Aerosol
journal, March 2004

  • Tolocka, Michael P.; Jang, Myoseon; Ginter, Joy M.
  • Environmental Science & Technology, Vol. 38, Issue 5
  • DOI: 10.1021/es035030r

An interfacial mechanism for cloud droplet formation on organic aerosols
journal, March 2016


Surfactants from the gas phase may promote cloud droplet formation
journal, February 2013

  • Sareen, N.; Schwier, A. N.; Lathem, T. L.
  • Proceedings of the National Academy of Sciences, Vol. 110, Issue 8
  • DOI: 10.1073/pnas.1204838110

Following Particle-Particle Mixing in Atmospheric Secondary Organic Aerosols by Using Isotopically Labeled Terpenes
journal, February 2018


Highly Oxygenated Multifunctional Compounds in α-Pinene Secondary Organic Aerosol
journal, May 2017

  • Zhang, Xuan; Lambe, Andrew T.; Upshur, Mary Alice
  • Environmental Science & Technology, Vol. 51, Issue 11
  • DOI: 10.1021/acs.est.6b06588

Modern Aspects of Isotopic Labellings in Terpene Biosynthesis: Modern Aspects of Isotopic Labellings in Terpene Biosynthesis
journal, May 2017


Plant-Derived Terpenes: A Feedstock for Specialty Biofuels
journal, March 2017


Synergistic O 3 + OH oxidation pathway to extremely low-volatility dimers revealed in β-pinene secondary organic aerosol
journal, August 2018

  • Kenseth, Christopher M.; Huang, Yuanlong; Zhao, Ran
  • Proceedings of the National Academy of Sciences, Vol. 115, Issue 33
  • DOI: 10.1073/pnas.1804671115

Convenient synthesis of deuterium labelled sesquiterpenes
journal, October 2016


Production and Measurement of Organic Particulate Matter in a Flow Tube Reactor
journal, January 2018

  • Zhang, Yue; Liu, Pengfei; Gong, Zhaoheng
  • Journal of Visualized Experiments, Issue 142
  • DOI: 10.3791/55684

Molecular Composition of Monoterpene Secondary Organic Aerosol at Low Mass Loading
journal, October 2010

  • Gao, Yuqian; Hall, Wiley A.; Johnston, Murray V.
  • Environmental Science & Technology, Vol. 44, Issue 20
  • DOI: 10.1021/es101861k

Changing shapes and implied viscosities of suspended submicron particles
journal, January 2015

  • Zhang, Y.; Sanchez, M. S.; Douet, C.
  • Atmospheric Chemistry and Physics, Vol. 15, Issue 14
  • DOI: 10.5194/acp-15-7819-2015

Displacement of Hexanol by the Hexanoic Acid Overoxidation Product in Alcohol Oxidation on a Model Supported Palladium Nanoparticle Catalyst
journal, November 2011

  • Buchbinder, Avram M.; Ray, Natalie A.; Lu, Junling
  • Journal of the American Chemical Society, Vol. 133, Issue 44
  • DOI: 10.1021/ja2067274

Surface Structure at Hexadecane and Halo-hexadecane Liquid/Vapor Interfaces
journal, July 2004

  • Esenturk, Okan; Walker, Robert A.
  • The Journal of Physical Chemistry B, Vol. 108, Issue 30
  • DOI: 10.1021/jp047984p

Heterogeneous Ozone Oxidation Reactions of 1-Pentene, Cyclopentene, Cyclohexene, and a Menthenol Derivative Studied by Sum Frequency Generation
journal, November 2008

  • Stokes, Grace Y.; Buchbinder, Avram M.; Gibbs-Davis, Julianne M.
  • The Journal of Physical Chemistry A, Vol. 112, Issue 46
  • DOI: 10.1021/jp803277s