Physicochemical Properties of Pinic, Pinonic, Norpinic, and Norpinonic Acids as Relevant α-Pinene Oxidation Products

Abstract

Here, the study is focused on the synthesis and determination of physicochemical properties of four α-pinene secondary organic aerosol (SOA) products: cis-pinic acid, cispinonic acid, cis-norpinic acid, and cis-norpinonic acid. These encompass their thermal properties, solid−liquid phase equilibria, and dissociation constant (pK a ). Thermal properties, including the melting temperature, enthalpy of fusion, temperature, and enthalpy of the phase transitions, were measured with the differential scanning calorimetry technique. These SOA components exhibit relatively high melting temperatures from 364.32 K for cis-pinic acid to 440.68 K for cis-norpinic acid. The enthalpies of fusion vary from 14.75 kJ•mol −1 for cis-norpinic acid to 30.35 kJ•mol −1 for cis-pinonic acid. The solubility in water was determined with the dynamic method (solid−liquid phase equilibria method), and then experimental results were interpreted and correlated using three different mathematical models: Wilson, non-random two-liquid model, and universal quasichemical equations. The results of the correlation indicate that the Wilson equation appears to work the best for all investigated compounds, giving rise to the lowest value of a standard deviation. cis-Norpinic acid and cis-pinic acid (dicarboxylic acids) show better solubility in the aqueous solution than cis-norpinonic acid and cis-pinonic acid (monocarboxylic acids), which affect the multiphase chemistry of α-pinene SOA processes. For cis-pinonic acid and cis-norpinonic acid, also pH-profile solubility was determined. The intrinsic solubility (S 0 ) for cis-norpinonic acid was measured to be 0.05 mmol•dm −3 , while for cis-pinonic acid, it was found to be 0.043 mmol•dm −3 . The acidity constants (pK a ) at 298 and 310 K using the Bates−Schwarzenbach spectrophotometric method were determined. The pK a values at 298.15 K for cis-norpinonic acid and cis-pinonic acid were found to be 4.56 and 5.19, respectively, whereas at 310.15 K, pK a values were found to be −4. 76 and 5.25, respectively.

Toxicological Responses of α-Pinene-Derived Secondary Organic Aerosol and Its Molecular Tracers in Human Lung Cell Lines

“…MBTCA (3-methyl-1,2,3-butanetricarboxylic acid, 99% purity) and cis -pinic acid (99.5% purity) were synthesized in our laboratory, as described previously. , α-Pinene (>99% purity), cis -pinonic acid (98% purity), dimethyl sulfoxide (DMSO, MolBio-Grade), Dulbecco’s phosphate-buffered saline (PBS), methanol (ChromaSolv-Grade), and 0.1% acetic acid were purchased from Sigma-Aldrich (Merck, Poland). High-purity methanol (optima LC/MS grade) was purchased from Fisher Chemical (U.S.A.).…”

“…Detailed operating procedures (e.g., mass calibration, tuning, voltages, etc.) of the RPLC/ESI-HR-QTOFMS method have been previously published. − The same mobile phases and gradient elution program were employed for RPLC/ESI-HR-QTOFMS analysis operated in the positive ion mode in order to aid in the detection of additional α-pinene SOA constituents, including organic peroxides (hydroxyhydroperoxides). The injection volume used for positive ion mode was 10 μL.…”

Structural Characterisation of Dimeric Esters in α-Pinene Secondary Organic Aerosol Using N2 and CO2 Ion Mobility Mass Spectrometry

“…A standard compound of terpenylic acid was synthesised following a method described in Claeys et al, 2009 [37]. The synthesis methods of cis-pinic acid and cis-norpinic acid can be found in Kołodziejczyk et al, 2019 [38].…”

Supplementary material to "The Role of Organic Acids in New Particle Formation from Methanesulfonic Acid and Methylamine"

“…[1] (Khwaja, 1995) ; [2] (Haynes et al, 2016) ; [3] (Ho et al, 2007) ; [4] (Ho et al, 2010) ; [5] (Kavouras et al, 1998) ; [6] (Kolodziejczyk et al, 2019) ; [7] (Chen and Finlayson-Pitts, 2017) ; [8] (NIST Database, 2013). (MSA)2(MA)1 2.50 × 10 0 1.26 × 10 -1 4.01 × 10 -3 7.20 × 10 -5…”