Water clusters in amorphous pharmaceuticals.

Amorphous materials, although lacking the long-range translational and rotational order of crystalline and liquid crystalline materials, possess certain local (short-range) structure. This paper reviews the distribution of one particular component present in all amorphous pharmaceuticals, that is, water. Based on the current understanding of the structure of water, water molecules can exist in either unclustered form or as aggregates (clusters) of different sizes and geometries. Water clusters are reported in a range of amorphous systems including carbohydrates and their aqueous solutions, synthetic polymers, and proteins. Evidence of water clustering is obtained by various methods that include neutron and X-ray scattering, molecular dynamics simulation, water sorption isotherm, concentration dependence of the calorimetric Tg , dielectric relaxation, and nuclear magnetic resonance. A review of the published data suggests that clustering depends on water concentration, with unclustered water molecules existing at low water contents, whereas clusters form at intermediate water contents. The transition from water clusters to unclustered water molecules can be expected to change water dependence of pharmaceutical properties, such as rates of degradation. We conclude that a mechanistic understanding of the impact of water on the stability of amorphous pharmaceuticals would require systematic studies of water distribution and clustering, while such investigations are lacking.

Improved atmospheric sampling of hexavalent chromium.

Hexavalent chromium (Cr(VI)) and trivalent chromium (Cr(III)) are the primary chromium oxidation states found in ambient atmospheric particulate matter. While Cr(III) is relatively nontoxic, Cr(VI) is toxic and exposure to Cr(VI) may lead to cancer, nasal damage, asthma, bronchitis, and pneumonitis. Accurate measurement of the ambient Cr(VI) concentrations is an environmental challenge since Cr(VI) can be reduced to Cr(III) and vice versa during sampling. In the present study, a new Cr(VI) sampler (Clarkson sampler) was designed, constructed, and field tested to improve the sampling of Cr(VI) in ambient air. The new Clarkson Cr(VI) sampler was based on the concept that deliquescence during sampling leads to aqueous phase reactions. Thus, the relative humidity of the sampled air was reduced below the deliquescence relative humidity (DRH) of the ambient particles. The new sampler was operated to collect total suspended particles (TSP), and compared side-by-side with the current National Air Toxics Trends Stations (NATTS) Cr(VI) sampler that is utilized in the US. Environmental Protection Agency (EPA) air toxics monitoring program. Side-by-side field testing of the samplers occurred in Elizabeth, NJ during the winter and summer of 2012. The average recovery values of Cr(VI) spikes after 24-hr sampling intervals during summer and winter sampling were 57 and 72%, respectively, for the Clarkson sampler while the corresponding average values for NATTS samplers were 46% for both summer and winter sampling, respectively. Preventing the ambient aerosol collected on the filters from deliquescing is a key to improving the sampling of Cr(VI).

Comparison of Experimental and Theoretical Heterogeneous Nucleation on Ultrafine Carbon Particles.

Using a modified turbulent mixing CNC, the heterogeneous nucleation of different compounds (working fluids) on nanometer sized carbon particles was examined. The working fluids were dibutyl phthalate, octadecane, octadecanol, and octadecanoic acid. Based on the particle size distributions measured with a scanning mobility particle sizer system, nucleation and consequent growth were examined with respect to different temperature and vapor pressure for each working fluid. Nucleation rates for all conditions were calculated from the fitted size distribution data by subtracting the residual nonactivated particle concentration for each condition. Experimental nucleation rates were compared to the calculated ones based on Fletcher's heterogeneous nucleation theory. This theory matches well with the experiments with octadecanol and octadecanoic acid, and at high supersaturation ratios for dibutyl phthalate. However, the theory shows discrepancies with the observed phenomena at low supersaturation for dibutyl phthalate, and especially for octadecane. Several possible hypotheses for the discrepancies and observed particle growth are discussed.