Functional properties of living cells depend on the thermodynamic variables such as temperature and pressure. A unique tool to investigate volume effects on structure and metabolism of the cell and biomolecules is pressure perturbation. We have developed a new setup that enables micro-spectroscopy and optical imaging of individual live cells at variable pressure from 0.1 to 400 MPa. Following characterization of the setup, pressure and temperature effects on the secondary structure of the peptide Poly-L-glutamic acid (PGA) in deuterated water buffer solution were investigated. The amide I band of PGA is sensitive to pressure and temperature, and by spectral deconvolution, we determined the relative contributions due to the ?-helix and random coil conformations. The population of ?-helix increases with increasing pressure. Pressure effects on single red blood cells and the intracellular protein hemoglobin were studied by micro-Raman spectroscopy. In particular, we observed a shift in the frequency of the iron-histidine vibrational band in both the intracellular hemoglobin and hemoglobin in solutions. The iron-histidine mode is a sensitive structural marker of the crucial iron-protein linkage in heme proteins. The pressure dependent shift suggests a conformational change of the heme environment. This finding was further supported by micro-absorption measurements at variable pressure. In additional experiments, Raman spectroscopy was employed to probe molecular changes that occurred in hemoglobin in erythrocytes infected with the malaria parasite Plasmodium falciparum. The spectra of infected cells indicated that hemoglobin degradation can be correlated with the stages of the parasite multiplication cycle. The research was further extended towards probing size and shape changes of individual cells with pressure. The lateral diameter in yeast cells was observed to decrease with pressure in a reversible way. These results suggest that transport of the intra-cellular water may play a significant role for volume changes. In summary, pressure changes were shown to induce conformational changes in proteins and shape changes in yeast cells. A Raman technique was developed to monitor the states of Plasmodium falciparum multiplication cycle within a red blood cell.

Functional properties of biological molecules and cells are affected by environmental parameters such as temperature and pressure. While Raman spectroscopy provides an intrinsic probe of molecular structural changes, the incorporation of a microscope enables studies of minuscule amounts of biological compounds with spatial resolution on a micron scale. We have developed a novel setup which combines a Raman microscope and a high pressure cell. A micro-capillary made out of fused silica simultaneously serves as the supporting body and the optical window of the pressure cell. The cell has been tested over the pressure range from 0.1 to 4 kbar. Raman spectra of less than 100 nanoliter amount of amino acid and protein solutions have been measured in the micro-capillary high pressure cell. It is also demonstrated that the setup is well suited for spectrally resolved fluorescence measurements at variable pressure.

No / Using fugacity coefficient of a cubic equation of state, Henry’s law constant of a solute in a solvent isincorporated into binary interaction parameter of the classical attractive parameter mixing rule. Thedeveloped equation is a function of temperature. The binary interaction parameter is evaluated by purecomponent critical properties and acentric factors of the solute and the solvent and the Henry’s lawconstant of the solute in the solvent. The developed model accurately describes the solubility of gasesincluding methane, ethane, nitrogen, carbon dioxide and hydrogen sulphide in heavy n-alkanes from lowto high pressure for wide range of temperature. The solubility of methane and carbon dioxide in wateris also predicted adequately.

Coal plays a significant role in electricity production worldwide and will into the foreseeable future. Technologies that improve efficiency and lower emissions are becoming more popular. High pressure reactors and oxyfuel combustion can offer these benefits. Designing new reactors effectively requires accurate single particle modeling. This work models a high-pressure, high-temperature, high-heating rate, entrained-flow, char oxidation data set to generate kinetic parameters. Different modeling methods were explored and a sensitivity analysis on char burnout was performed by varying parameters such as total pressure, O2 partial pressure, O2 and CO2 mole fractions, gas temperature, diameter, and pre-exponential factor. Pressure effects on char burnout modeling were found to be dependent on the set of kinetic parameters chosen. Using kinetic parameters from Hurt-Calo (2001) as opposed to values obtained from Niksa-Hurt (2003) yielded a trend seen in real data sets, that reaction order changes with temperature. Varying O2 mole fraction and partial pressure showed the most significant changes in char burnout. Varying diameter, total pressure, the pre-exponential factor, CO2 environment, and gas temperature all changed the char burnout extent as well. The effect of changing those parameters decreases in the order they are listed. Increasing any of these parameters resulted in an increase in char burnout except for particle diameter and CO2 mole fraction which led to a decrease. Char formation pressure affects reactivity, and a peak in reactivity is shown in this work at the 6 atm condition.

No description available.

No description available.

No description available.

No description available.

No description available.

No description available.