Technical Note: Real-Time Diagnosis of the Hygroscopic Growth Micro-Dynamics of Nanoparticles with Two-Dimensional Correlation Infrared Spectroscopy

Nanoparticles can absorb water to grow up and this will affect the light scattering behavior, cloud condensation nuclei properties, lifetime, and chemical reactivity of these particles. Current techniques usually assume the shapes of nanoparticles to be spherical in calculation of aerosol liquid water content (ALWC), which may result in large uncertainties when the shapes of nanoparticles show large deviations to the spherical assumptions. Furthermore, current techniques are also difficult to identify the intermolecular chemical interactions of phase transition micro-dynamics during nanoparticle deliquescence process because their limited temporal resolutions are unable to capture the complex femtosecond-level intermediate states. In this study, the hygroscopic growth properties of nanoparticles with electrical mobility diameter of approximately 100 nm and their phase transition interaction dynamics on molecular scale are characterized on real time by using the Fourier transform infrared (FTIR) and the two-dimensional correlation infrared (2D-IR) spectroscopic techniques. With the FTIR spectroscopy, we develop a novel real-time method for ALWC by constructing the absorption spectra of liquid water, and realized real-time measurements of water content and dry nanoparticle mass to characterize the hygroscopic growth factors (GF) which show discrepancies to the extended aerosol inorganics model (E-AIM). We further explore the difference that the deliquescence points of sodium nitrate (SN) and oxalic acid (OA) compounds are lower than that of AS by using the 2D-IR spectroscopic analysis technique. We also identify the occurrence sequential order of the hydration interactions and investigate the dynamic deliquescence process of the functional groups for AS and its mixture compounds. Both SN and OA compounds lower the deliquescence point of AS, but only AN can change the hydrolysis reaction mechanism for AS in AS/AN and AS/OA mixtures. This study can not only provide important information with respect to the difference in phase transition point under different conditions, but also improve current understanding of the chemical interaction mechanism between nanoparticles (particularly for organic particles) and medium, which is of great significance for haze control across China.

The Polarization Dependence of 2D IR Cross-Peaks Distinguishes Parallel-Stranded and Antiparallel-Stranded DNA G-quadruplexes

Guanine-rich nucleic acid sequences have a tendency to form four-stranded non-canonical motifs known as G-quadruplexes. These motifs may adopt a wide range of structures characterized by size, strand orientation, guanine base conformation, and fold topology. Using three K+-bound model systems, we show that vibrational coupling between guanine C6=O and ring modes varies between parallel-stranded and antiparallel-stranded G-quadruplexes, and that such structures can be distinguished by comparison of polarization dependent cross-peaks in their two-dimensional infrared (2D IR) spectra. Combined with previously defined vibrational frequency trends, this analysis reveals key features of a 30-nucleotide unimolecular variant of the Bcl-2 proximal promoter that are consistent with its reported structure. This study shows that 2D IR spectroscopy is a convenient method for analyzing G-quadruplex structures that can be applied to complex sequences where traditional high-resolution methods are limited by solubility and disorder.