Dissociation constants of relevant secondary organic aerosol components in the atmosphere.

The presented studies focus on measuring the determination of the acidity constant (pKa) of relevant secondary organic aerosol components. For our research, we selected important oxidation products (mainly carboxylic acids) of the most abundant terpene compounds, such as α-pinene, ß-pinene, ß-caryophyllene, and δ-3-carene. The research covered the synthesis and determination of the acidity constant of selected compounds. We used three methods to measure the acidity constant, i.e., 1H NMR titration, pH-metric titration, Bates-Schwarzenbach spectrophotometric method. Moreover, the pKa values were calculated with Marvin 21.17.0 software to compare the experimentally derived values with those calculated from the chemical structure. pKa values measured with 1H NMR titration ranged from 3.51 ± 0.01 for terebic acid to 5.18 ± 0.06 for ß-norcaryophyllonic acid. Moreover, the data determined by the 1H NMR method revealed a good correlation with the data obtained with the commonly used potentiometric and UV-spectroscopic methods (R2 = 0.92). In contrast, the comparison with in silico results exhibits a relatively low correlation (R2Marvin = 0.66). We found that most of the values calculated with the Marvin Program are lower than experimental values obtained with pH-metric titration with an average difference of 0.44 pKa units. For di- and tricarboxylic acids, we obtained two and three pKa values, respectively. A good correlation with the literature values was observed, for example, Howell and Fisher (1958) used pH-metric titration and measured pKa1 and pKa2 to be 4.48 and 5.48, while our results are 4.24 ± 0.10 and 5.40 ± 0.02, respectively.

Expanding the range of graphene energy transfer with multilayer graphene.

The interaction between single emitters and graphene in the context of energy transfer has attracted significant attention due to its potential applications in fields such as biophysics and super-resolution microscopy. In this study, we investigate the influence of the number of graphene layers on graphene energy transfer (GET) by placing single dye molecules at defined distances from monolayer, bilayer, and trilayer graphene substrates. We employ DNA origami nanostructures as chemical adapters to position the dye molecules precisely. Fluorescence lifetime measurements and analysis reveal an additive effect of graphene layers on the energy transfer rate extending the working range of GET up to distances of approximately 50-60 nm. Moreover, we show that switching a DNA pointer strand between two positions on a DNA origami nanostructure at a height of >28 nm above graphene is substantially better visualized with multilayer graphene substrates suggesting enhanced capabilities for applications such as biosensing and super-resolution microscopy for larger systems and distances. This study provides insights into the influence of graphene layers on energy transfer dynamics and offers new possibilities for exploiting graphene's unique properties in various nanotechnological applications.

Physicochemical Properties of Terebic Acid, MBTCA, Diaterpenylic Acid Acetate, and Pinanediol as Relevant α-Pinene Oxidation Products.

The physicochemical properties and the synthesis of four α-pinene oxidation products, terebic acid, 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), diaterpenylic acid acetate (DTAA), and pinanediol, are presented in this study. The physicochemical properties encompass thermal properties, solubility in water, and dissociation constant (pK a) for the investigated compounds. It was found that terebic acid exhibits a relatively high melting temperature of 449.29 K, whereas pinanediol revealed a low melting temperature of 329.26 K. The solubility in water was determined with the dynamic method and the experimental results were correlated using three different mathematical models: Wilson, NRTL, and UNIQUAC equations. The results of the correlation indicate that the Wilson equation appears to work the best for terebic acid and pinanediol. The calculated standard deviation was for 3.79 for terebic acid and 1.25 for pinanediol. In contrast, UNIQUAC was the best mathematical model for DTAA and MBTCA. The calculated standard deviation was 0.57 for DTAA and 2.21 for MBTCA. The measured water solubility increased in the following order: pinanediol > DTAA ≥ MBTCA > terebic acid, which affects their multiphase aging chemistry in the atmosphere. Moreover, acidity constants (pK a) at 298, 303, and 308 K were determined for DTAA with the Bates-Schwarzenbach spectrophotometric method. The pK a values obtained at 298, 303, and 308 K were found to be 3.76, 3.85, and 3.88, respectively.

Correction to "Physicochemical Properties of Terebic Acid, MBTCA, Diaterpenylic Acid Acetate, and Pinanediol as Relevant α-Pinene Oxidation Products".

[This corrects the article DOI: 10.1021/acsomega.9b04231.].

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

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, cis-pinonic acid, cis-norpinic acid, and cis-norpinonic acid. These encompass their thermal properties, solid-liquid phase equilibria, and dissociation constant (pKa). 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 (S0) 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 (pKa) at 298 and 310 K using the Bates-Schwarzenbach spectrophotometric method were determined. The pKa 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, pKa values were found to be -4.76 and 5.25, respectively.