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Progress in Chemistry 2021, Vol. 33 Issue (10): 1721-1730 DOI: 10.7536/PC200841 Previous Articles   Next Articles

• Review •

Application of Langmuir Monolayers in the Investigation of Surface Properties of Sea Spray Aerosols

Shumin Cheng1, Lin Du1(), Xiuhui Zhang2, Maofa Ge3   

  1. 1 Environment Research Institute, Shandong University, Qingdao 266237, China
    2 Key Laboratory of Cluster Science, Ministry of Education of China, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China
    3 State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
  • Received: Revised: Online: Published:
  • Contact: Lin Du
  • Supported by:
    National Natural Science Foundation of China(21876098); National Natural Science Foundation of China(91644214)
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Aqueous aerosols coated by surface-active organics, such as sea spray aerosol(SSA), commonly possess inverse micelle structure with an aqueous core coated by a hydrophobic organic monolayer. The surface organization and chemical composition of organic films of SSAs have important influence on their physical, chemical and optical properties. Langmuir monolayers are monomolecular layers formed by the diffusion of long-chain surface-active organics with low volatility, such as fatty acids, fatty alcohols and phospholipids at the air-water interface. With Langmuir trough, the changes in surface pressure(π) along with decreasing molecular area(A) of single and mixed component monolayers at the air-water interface can be obtained. In addition, π-A isotherms provide information about the interfacial behavior of corresponding monolayers above an aqueous surface. Understanding the interfacial properties of monolayers will enable the prediction of the fate and behaviors of surfactants in the real-world SSA. This paper reviews the commonly used interfacial characterization techniques of atmospheric aerosols, established models for SSA based on Langmuir monolayer, and the implications of organic films on atmospheric behavior of SSA. Although the physical properties and morphological changes of SSA-related monolayers have been studied in depth, little attention has been paid to the interfacial changes induced by environmental factors such as reactive gases, irradiation and bioactive substances. These knowledge gaps shed light on future laboratory simulation and model research of SSA.

Contents

1 Introduction

2 Commonly used interfacial characterization techniques of atmospheric aerosols

3 Established models for SSA based on Langmuir monolayer

3.1 Single component monolayers

3.2 Mixed component monolayers

4 Implications of organic films on atmospheric behaviors of SSA

5 Conclusion and outlook

Key words: monolayer, sea spray aerosol(SSA), surface property, air-water interface, atmospheric behavior
Fig.1 Schematic representation of sea to air transfer of organics via sea spray aerosols[24]
Fig. 2 The π-A isotherm of stearic acid on pure water, molecular arrangements in different phases are shown by the cartoons
Table 1 Common analytical methods of Langmuir monolayer and their advantages and disadvantages
Analytical methods Representatives Provided information Advantages Disadvantages ref
Spectroscopic techniques IRRAS,Vibrational sum
frequency generation
(VSFG) spectroscopy,
Glancing-angle Raman
(GAR) spectroscopy		 Molecular structure, ionization
state, orientation of tail/head
groups, ion-molecule binding
interactions		 In-situ measurement, fast, non-destructive Signal intensity is
limited by orientation
of the interfacial
molecules		 16,21,23,37
Microscopic techniques BAM, AFM, Fluorescence
microscopy(FM),
Transmission electron
microscopy(TEM)		 Visual images of film morphologies,
domain formation, aggregation,
monolayer phases, phase-
coexistence		 High spatial
resolution		 Molecular information
is not available		 16,21,37
Fig. 3 Experimental setup showing the IRRAS as well as the Langmuir trough[69]
Fig. 4 The BAM images of palmitic acid monolayer on pure water show gaseous, liquid and solid films from left to right[21]
Fig. 5 IRRAS spectra of d31-Palmitic acid monolayers(20.5 Å2 per molecule) on CaCl2 subphases of(a) low Ca2+ concentration(0 ≤ [Ca2+] ≤ 1 mmol/L) and(b) high Ca2+ concentration(10 ≤ [Ca2+] ≤ 300 mmol/L)[23]
Fig. 6 Coadsorption of saccharides in phospholipid monolayers[43]
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