ABSTRACT
The thermal unfolding of the copper redox protein azurin was studied in the presence of four different amino acid-based ionic liquids (ILs), all of which have tetramethylguanidium as cation. The anionic amino acid includes two with alcohol side chains, serine and threonine, and two with carboxylic acids, aspartate and glutamate. Control experiments showed that amino acids alone do not significantly change protein stability and pH changes anticipated by the amino acid nature have only minor effects on the protein. With the ILs, the protein is destabilized and the melting temperature is decreased. The two ILs with alcohol side chains strongly destabilize the protein while the two ILs with acid side chains have weaker effects. Unfolding enthalpy (ΔHunf°) and entropy (ΔSunf°) values, derived from fits of the unfolding data, show that some ILs increase ΔHunf°while others do not significantly change this value. All ILs, however, increase ΔSunf°. MD simulations of both the folded and unfolded protein conformations in the presence of the ILs provide insight into the different IL-protein interactions and how they affect the ΔHunf° values. The simulations also confirm that the ILs increase the unfolded state entropies which can explain the increased ΔSunf° values.
Subject(s)
Amino Acids/chemistry , Azurin/chemistry , Entropy , Ionic Liquids/chemistry , Methylguanidine/analogs & derivatives , Methylguanidine/chemistry , Transition Temperature , Anions/chemistry , Azurin/metabolism , Cations/chemistry , Hydrogen-Ion Concentration , Hydrophobic and Hydrophilic Interactions , Imidazoles/chemistry , Ionic Liquids/metabolism , Molecular Dynamics Simulation , Protein Stability , Protein Structure, Secondary , Protein UnfoldingABSTRACT
Physical and optical properties of biomass burning aerosols in Northeastern region, India analyzed based on measurements made during February 2002. Large spatial extent of Northeastern Region moist tropical to moist sub-tropical forests in India have high frequency of burning in annual dry seasons. Characterization of resultant trace gases and aerosols from biomass burning is important for the atmospheric radiative process. Aerosol optical depth (AOD) observed to be high during burning period compared to pre- and post-burning days. Peak period of biomass burning is highly correlated with measured AOD and total columnar water vapor. Size distribution of aerosols showed bimodal size distribution during burning day and unimodal size distribution during pre- and post-burning days. Size distribution retrievals from biomass burning aerosols show dominance of accumulation mode particles. Weighted mean radius is high (0.22 microm) during burning period. Columnar content of aerosols observed to be high during burning period in addition to the drastic reduction of visibility. During the burning day Anderson sampler measurements showed dominance of accumulation mode particles. The diurnal averaged values of surface shortwave aerosol radiative forcing af biomass burning aerosols varies from -59 to -87 Wm(-2) on different days. Measured and modeled solar irradiances are also discussed in the paper.
