Multi-photon absorption processes have received significant attention from the scientific community during the last decade, mainly because of their potential applications in optical limiting, data storage and biomedical fields. Perhaps, one of the most investigated processes studied so far has been two-photon absorption (2PA). These investigations have resulted in successful applications in all the fields mentioned above. However, 2PA present some limitations in the biomedical field when pumping at typical 2PA wavelengths. In order to overcome these limitations, three-photon absorption (3PA) process has been proposed. However, 3PA in organic molecules has a disadvantage, typical values of σ3' are small (10-81 cm6s2/photon2), therefore, 3PA excitation requires high irradiances to induce the promotion of electrons from the ground state to the final excited state. To overcome this obstacle, specific molecules that exhibit large 3PA cross-section must be designed. Thus far, there is a lack of systematic studies that correlate 3PA processes with the molecular structure of organic compounds. In order to fill the existent gap in 3PA molecular engineering, in this dissertation we have investigated the structure/property relationship for a new family of fluorene derivatives with very high three-photon absorption cross-sections. We demonstrated that the symmetric intramolecular charge transfer as well as the -electron conjugation length enhances the 3PA cross-section of fluorene derivatives. In addition, we showed that the withdrawing electron character of the attractor groups in a pull-pull geometry proved greater 3PA cross-section. After looking for alternative ways to enhance the effective σ3' of organic molecules, we investigated the enhancement of two- and three-photon absorption processes by means of Surface Plasmon. We demonstrated an enhancement of the effective two- and three-photon absorption cross-section of an organic compound of 480 and 30 folds, respectively. We proved that the enhancement is a direct consequence of the electric field enhancement at a metal/buffer interface. Next, motivated by the demands for new materials with enhanced nonlinear optical properties, we studied the 3PA of Hematoporphyrin IX and J-aggregate supramolecular systems. As a result, we were able to propose the use of 3PA in photodynamic therapy using Photofrin, the only drug approved by the FDA for PDT.

Effective light energy conversion into other forms of energy in metal and metal compound nanoparticles has been of great interest in past decades. Being illuminated by incident light, electrons in the nanoparticles can be excited to higher energy states followed by deposition of energy into other molecules around their surface and the lattices in the following relaxation process. Ultrafine nanoparticles are thus preferred in these processes due to their high specific surface areas. Moreover, the portion of excited electrons with higher energies is higher in smaller nanoparticles than in larger ones. However, the overall light power absorbed by nanoparticles is proportional to the square of particle size, which causes the ultrafine nanoparticles not to efficiently absorb the incident light, or to drive further chemical or physical processes.Light antennae materials are usually employed to enhance the light absorption of these ultrafine nanoparticles. Plasmonic nanoparticles, e.g., Ag, Au, Cu, and Al nanoparticles, enhance the light absorption of loaded nanoparticles mainly through strong electromagnetic fields generated near their surfaces and have been proven to be effective light antennae to benefit the light energy conversion of ultrafine nanoparticles. On the other hand, spherical dielectric particles, e.g., silicon dioxide nanospheres, represent a different type of light antennae with the advantages of low cost, simple synthesis, and negligible Ohmic loss when being illuminated. When the sizes of high geometric symmetry dielectric nanospheres are comparable with the wavelength of the incident light, Mie scattering can happen based on the difference in refractive index between the sphere and the surrounding medium, generating size-dependent scattering resonances at various wavelengths. At these wavelengths, strong electric fields can be created on the surface of dielectric spheres to enhance the light absorption of the nanoparticles loaded on the surface. Previous works have shown that silica nanospheres with a diameter of several hundreds of nanometers can effectively enhance the light absorption of ultrafine Pt nanoparticles and benefit photocatalytic reactions, e.g., selective oxidation of benzyl alcohol. Over the past few years, this concept has been broadened to other ultrafine nanoparticles to study their novel photo-to-chemical/physical properties. However, the availability and comprehensive understanding of the optical properties of this class of composite particles still need to be improved. These challenges limit the further development of these composite materials in new light energy conversion processes. This dissertation aims at studying this class of novel ultrafine nanoparticles/dielectric sphere composite particles synthesis and optical properties. In Chapter 2, a synthesis protocol of ultrafine ruthenium oxyhydroxide nanoparticles on the surface of silica nanospheres’ surfaces is introduced. Unlike the traditional synthesis of nanoparticles in solution followed by a loading process, the method developed in this chapter only requires the injection of aqueous ruthenium salt solution into a silica nanosphere dispersion. The obtained ultrafine nanoparticles with sizes of 2-3 nm are characterized to be ruthenium oxyhydroxide (RuOOH) nanoparticles. The silica nanospheres are crucial in stabilizing these ultrafine RuOOH nanoparticles and enhancing their light absorption. Due to the presence of ruthenium-oxygen bonds in the nanoparticles, the absorbed photons are converted to heat and transferred to the surrounding media with a photo-to-thermal conversion efficiency close to the unity. Experimental results have shown that heat can be effectively used in accelerating the reaction rate of selective oxidation of benzyl alcohol by molecular oxygen. Kinetics data also have shown that these ultrafine RuOOH nanoparticles are able to activate molecular oxygen adsorbed on their surfaces, which represents a novel property of these ultrafine RuOOH nanoparticles that is not observed in other traditional ruthenium catalysts. In Chapter 3, a more general synthesis method of ultrafine metal and metal oxyhydroxide nanoparticles on silica nanospheres is developed, inspired by the synthetic route in Chapter 2. Instead of functionalizing silica surfaces with silane agents with amino groups, the silica surfaces are selectively etched by an aqueous base to create a high density of surface hydroxyl groups. These hydroxyl groups can provide basic sites to stabilize metal ions in aqueous dispersion, which are nuclei for the further growth of larger metal oxyhydroxide nanoparticles. In this chapter, more than ten kinds of metal ions are loaded onto silica spheres, forming oxyhydroxide nanoparticles with average sizes below 5 nm. Some oxyhydroxide nanoparticles can be reduced by 5% H2/N2 to form metal nanoparticles with their ultrafine sizes maintained. The synthesis protocol is promising in preparation of bimetallic samples. The composition and optical absorption of all obtained composite particles are analyzed, demonstrating the practicability of utilizing the reported method to prepare high-quality light-absorbing composite particles. In Chapter 4, the optical absorption property of the composite particle is systematically studied. Using ultrafine Pt nanoparticles as the light absorbing material, the light absorptions of composite particles consisting of silica spheres with diameters from 100 to 1100 nm loaded with these Pt nanoparticles are studied. Through the combination of theoretical calculation based on Mie theory and the measured optical absorption spectra, the scattering resonance peaks are successfully located in each sample. It is also found that the photonic crystal effect and the general absorption of Pt nanoparticles can contribute to the light absorption spectra, especially at higher wavelengths. The relationship between the general absorption of Pt nanoparticles and the packing density of the powder is further studied. The successful deconvolution of several components in the absorption spectra can guide the further rational design of composite particles in optical-related applications. In Chapter 5, the composite particle system is further broadened to using high refractive index zinc sulfide nanospheres as a light antenna. The use of a higher refractive index light antenna is promising for obtaining higher light absorption enhancement in loaded ultrafine nanoparticles, even though the sample is dispersed in organic media with a high refractive index as well. After the successful loading of Pt nanoparticles to the surface of silica-coated zinc sulfide nanospheres, a protocol for analyzing their light absorption spectra in organic media is proposed. Size-dependent scattering resonance peaks are observed in bare zinc sulfide nanospheres and can be utilized to enhance the light absorption of Pt nanoparticles, even when the sample is sealed in high refractive index polymeric matrices. The composite particles are further employed in photothermal tests, the results prove that the better light absorption enhancement using zinc sulfide than silica nanospheres. The results introduced in this dissertation represent the first systematic and comprehensive study of ultrafine metal and metal oxyhydroxide nanoparticles loaded on the surface of dielectric light antenna particles. The conclusions open an avenue to further rational design of high-performance light-absorbing composite particles to be used in photo-to-thermal/chemical processes. / Chemistry

No description available.

No description available.

Solutions of poly(2-ethyl-2-oxazoline) and poly(2-methyl-2-oxazoline) in water and several alcohols were characterized by light scattering and cloud point measurements. The second virial coefficients in water were found to decrease with increasing temperature, reflecting lower critical solution behavior, which is consistent with the cloud point measurements. The temperature dependence of the second virial coefficients revealed that specific interactions between polymer and water dominated the free energy of mixing. The Flory-Huggins x parameter determined from light scattering was in the range 0.48 - 0.49 in water and 0.32 - 0.41 in ethanol. The Kuhn length for PEOX was determined to be 0.77 nm which corresponds to less than two monomer units, indicating relatively flexible chains of PEOX. The segmental adsorption energy, x_s^po, of PEOX was measured using a desorption/displacement technique. PEOX was desorbed from silica with five low molecular weight organic displacers in two solvents - water and ethanol - to obtain values of the critical volume fraction of the displacer at which desorption was complete, Φ_cr. The high adsorption energy parameters are consistent with the polymer adsorbing principally by hydrogen bonding between the carbonyl groups on the polymer and surface silanol groups. The difference in adsorption energies in water and ethanol reflect specific solvent effects that may be related to the formation of hydrogen bond bridges between PEOX and silanol groups in water. Adsorption of PEOX from water, alcohols and chlorobenzene onto silica was investigated by measuring PEOX adsorption isotherms using a depletion method. A linear relationship of the plateau adsorption amount, Γ_p vs. log (molecular weight) was obtained, which agreed qualitatively with the Scheutjens-Fleer (S-F) mean field adsorption theory. The values of Γ_p, varied significantly with solvent type as well as with pH and electrolyte concentration in water. These variations in Γ_p, were due to changes of the polymer solvency and the silanol density on the silica particles. Competitive adsorption experiments of PEOX with various polymers were performed, including poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO) poly(vinyl methyl ether) (PVME), and poly(dimethyl siloxane) (PDMS). PEOX showed a higher affinity to the silica surface than other polymers. This suggested that PEOX had good potential for serving as an anchor block for diblock copolymer stabilizers for metal oxides in water. The solubility of homopolymers PEOX, PEO, PPO, PVME, and PDMS and copolymers PEOX-PDMS and PEOX-PVME was investigated in water, alcohols, and chlorobenzene using static light scattering (SLS). The steric stabilization effect of silica dispersions in chlorobenzene by PEOX-PDMS was measured by dynamic light scattering (DLS). The stability was qualitatively related to the average particle hydrodynamic diameter against time. The adsorbed amount and layer thickness of diblock copolymer poly(dimethyl amino ethyl methacrylate-b-n-butyl methacrylate) (DMAEM-BMA) on silica surfaces from isopropanol was measured. The linear dependence of the adsorbed amount and thickness with respect to the tail block length was obtained. This is consistent with the Marques-Joanny model. / Ph. D.

Thesis: Ph. D., Massachusetts Institute of Technology, Department of Chemistry, 1976 / Vita. / Includes bibliographical references. / Ph. D. / Ph. D. Massachusetts Institute of Technology, Department of Chemistry

Bio-optical variability of surface waters in Northeastern Gulf of Mexico (NEGOM) was examined using satellite and in situ data. Relatively high chlorophyll-a concentration (chl>=1 mg m-3) and high colored dissolved organic mater (ag443>=0.1 m-1) were generally observed inshore, near major river mouths, and in plumes of Mississippi River water that extended offshore during the three consecutive summer seasons (1998, 1999, and 2000). River discharge dominated chlorophyll-a concentration variability inshore, particularly near major river mouths. Strong interannual variability in chlorophyll-a concentration was observed inshore from Escambia to Tampa Bay region during the winter to spring transition, which was different in 1998 compared to the winter to spring transition in 1999 and 2000. This was related to higher fresh water discharge during the 1997-1998 El Niño-Southern Oscillation event as well as strong upwelling in spring 1998. The Mississippi plume extended >500 km southeast of the Mississippi delta and up to the Florida Keys was observed for the periods extending over 14 weeks between May and September every year of the study. In general, ag443 covaried linearly and inversely with salinity inshore during spring and fall, indicating conservative mixing. The NEGOM salinity-ag443 relationship of fall 1998, i.e., Salinity=36.59-29.86*ag443 (n=8771, r2=0.86; 0.01<=ag443<=0.52, 16 <=S<=36), served as the best predictor of NEGOM salinity based on in situ ag443 observations for spring and fall seasons from all years (<3% mean percentage errors; corresponding to <1.03 psu). This may help estimate salinity from satellite ocean color data, but further testing using data from multiple years is needed to improve such relationship. While river discharge was an important source of colored dissolved organic matter (CDOM), phytoplankton blooms also contributed to CDOM formation in the NEGOM. Using a pigment index of phytoplankton taxonomic groups, the variability in biomass proportion of microphytoplankton explained up to 76% of the variability of the average of normalized phytoplankton absorption coefficients (545, 625, and 673 nm). The clorophyll-specific absorption coefficient, a*ph(440), varies by a factor of 7 (0.02-0.15 m2mg-1). Particle size and pigment composition played important roles in determining a*ph(440) variability. This must be accounted for in chlorophyll-a concentration algorithms based on aph.

An investigation of binary fluid heat and mass transfer in ammonia-water absorption was conducted. Experiments were conducted on a horizontal-tube falling-film absorber consisting of four columns of six 9.5 mm (3/8 in) nominal OD, 0.292 m (11.5 in) long tubes, installed in an absorption heat pump. Measurements were recorded at both system and local levels within the absorber for a wide range of operating conditions (nominally, desorber solution outlet concentrations of 5 - 40% for three nominal absorber pressures of 150, 345 and 500 kPa, for solution flow rates of 0.019 - 0.034 kg/s.). Local measurements were supplemented by high-speed, high-resolution visualization of the flow over the tube banks. Using the measurements and observations from videos, heat and mass transfer rates, heat and vapor mass transfer coefficients for each test condition were determined at the component and local levels. For the range of experiments conducted, the overall film heat transfer coefficient varied from 923 to 2857 W/m²-K while the vapor and liquid mass transfer coefficients varied from 0.0026 to 0.25 m/s and from 5.51×10^-6 to 3.31×10^-5 m/s, respectively. Local measurements and insights from the video frames were used to obtain the contributions of falling-film and droplet modes to the total absorption rates. The local heat transfer coefficients varied from 78 to 6116 W/m²-K, while the local vapor and liquid mass transfer coefficients varied from -0.04 to 2.8 m/s and from -3.59×10^-5 (indicating local desorption in some cases) to 8.96×10^-5 m/s, respectively. The heat transfer coefficient was found to increase with solution Reynolds number, while the mass transfer coefficient was found to be primarily determined by the vapor and solution properties. Based on the observed trends, correlations were developed to predict heat and mass transfer coefficients valid for the range of experimental conditions tested. These correlations can be used to design horizontal tube falling-film absorbers for ammonia-water absorption systems.

M. Tech. Engineering Chemical. / Aims to investigate how the addition of impurities in a CO2 stream affects the adsorption capacity of CO2 on South African coals. To achieve this aim, the following objectives were carried out. 1. To measure the adsorption isotherms and adsorption capacities of pure CO2 and flue gas mixtures on various South African coals under in-seam conditions including pressures up to 88 bar and isothermal temperature of 35 &#x00BA%x;C; 2. To evaluate the effects of coal rank on the adsorption isotherms and adsorption capacities of pure CO2 and flue gas mixtures; 3. To do a comparative study to evaluate the effects of CO2 impurities on the adsorption capacity of pure CO2 on coal; 4. To study the degree of preferential sorption of the individual flue gas mixtures components on coal; 5. To determine the suitability of the Langmuir, Freundlich, and Temkin adsorption isotherm models in representing pure CO2 adsorption onto coal; and 6. To determine the suitability of Extended Langmuir (EL) adsorption models in representing the flue gas mixture adsorption onto coal.

<div>Laser-absorption spectroscopy (LAS) is widely used for providing non-intrusive and quantitative measurements of gas properties (such as temperature and absorbing species mole fraction) in combustion environments. However, challenges may arise from the line-of-sight nature of LAS diagnostics, which can limit their spatial resolution. Further, time-resolution of such techniques as scanned direct-absorption or wavelength-modulation spectroscopy is limited by the scanning speed of the laser and the optical bandwidth is often limited by a combination of a laser's intrinsic tunability and its scanning speed. The work presented in this dissertation investigated how recent advancements in mid-IR camera technology and lasers can be leveraged to expand the spatial, temporal, and spectral measurement capabilities of LAS diagnostics. Novel laser-absorption imaging and ultrafast laser-absorption spectroscopy diagnostics are presented in this dissertation. In addition, the high-pressure combustion chamber (HPCC) and high-pressure shock tube (HPST) were designed and built to enable the study of, among others, energetic material combustion, spectroscopy, non-equilibrium and chemistry using optical diagnostics.<br></div><div><br></div>