Understanding the thermodynamic properties of multicomponent mixtures is of critical importance in many chemical and industrial applications. Experimental measurements become progressively difficult as the number of solution components increases -- producing the need for predictive models. Problems in development of predictive models arise if the mixture has one or more components that interact through molecular complexation or association. Experimental solubilities of anthracene and pyrene dissolved in binary systems containing one or more alcohols were measured in order to address this problem. Alcohols examined in this study were: 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol, and 1-octanol. In binary solvent mixtures containing only a single self-associating alcoholic solvent, the alkane cosolvents studied were: n-hexane, n-heptane, n-octane, 2,2,4-trimethylpentane, cyclohexane, methylcyclohexane, tert-butylcyclohexane. Predictive solubility equations were developed using mobile order theory. This approach differs from classical solution models by representing hydrogen bonding with a probability term rather than with expressions derived from stepwise equilibria or expressions to represent hypothetical solution aggregates. Results were compared with the predicted solubilities found from using expressions developed using the Kretschmer-Wiebe and Mecke-Kempter approaches for modeling associated solutions. It was found that the mobile order approach provided reasonably accurate predictions for the solute solubilities in the systems studied. The …

Aluminum was deposited onto both Teflon AF and Parylene AF surfaces by chemical vapor deposition of trimethylaluminum. This work shows that similar thin film (100 Angstroms) aluminum oxide adlayers form on both polymers at the low temperature dosing conditions used in the studies. Upon anneal to room temperature and above, defluorination of the polymer surfaces increased and resulted in fluorinated aluminum oxide adlayers; the adlayers were thermally stable to the highest temperatures tested (600 K). Angle-resolved spectra showed higher levels of fluorination toward the polymer/adlayer interface region. Copper films were also deposited at low temperature onto Teflon AF using a copper hexafluoroacetylacetonate-cyclooctadiene precursor. Annealing up to 600 K resulted in the loss of precursor ligands and a shift to metallic copper. As with aluminum adlayers, some polymer defluorination and resulting metal (copper) fluoride was detected. Parylene AF and polystyrene films surfaces were modified by directly dosing with water vapor passed across a hot tungsten filament. Oxygen incorporation into polystyrene occurred exclusively at aromatic carbon sites, whereas oxygen incorporation into parylene occurred in both aromatic and aliphatic sites. Oxygen x-ray photoelectron spectra of the modified polymers were comparable, indicating that similar reactions occurred. The surface oxygenation of parylene allowed enhanced reactivity …

The novel instrumentation of nanomanipulation coupled to nanospray mass spectrometry and its applications are presented. The nanomanipulator has the resolution of 10nm step sizes allowing for specific fine movement used to probe and characterize objects of interest. Nanospray mass spectrometry only needs a minimum sample volume of 300nl and a minimum sample size of 300attograms to analyze an analyte making it the ideal instrument to couple to nanomanipulation. The nanomanipulator is mounted to an inverted microscope and consists of 4 nano-positioners; these nano-positioners hold end-effectors and other tools used for manipulation. This original coupling has been used to enhance the current abilities of cellular probing and trace fiber analysis. Experiments have been performed to demonstrate the functionality of this instrument and its capabilities. Histidine and caffeine have been sampled directly from single fibers and analyzed. Lipid bodies from cotton seeds have been sampled indirectly and analyzed. The few applications demonstrated are only the beginning of nanomanipulation coupled to nanospray mass spectrometry and the possible applications are numerous especially with the ability to design and fabricate new end-effectors with unique abilities. Future study will be done to further the applications in direct cellular probing including toxicology studies and organelle analysis of …

Substitution of MeCN ligands in the activated cluster Os3(CO)10(MeCN)2 by the unsaturated diphosphine ligands (Z)-Ph2PCH=CHPPh2 (cDPPEn) or 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) proceeds rapidly at room temperature to furnish the ligand-bridged cluster 1,2-Os3(CO)10(P-P) (P-P represents cDPPEn or bpcd). Heating 1,2-Os3(CO)10(P-P) leads to the formation of the thermodynamically more stable chelating isomer 1,1-Os3(CO)10(P-P). Each compound of Os3(CO)10(P-P) has been characterized by x-ray diffraction, IR, 31P NMR and 1H NMR. Ligand isomerization kinetics have been investigated by UV-VIS and 31P NMR (for cDPPEn) or 1H NMR (for bpcd) spectroscopies. The isomerization mechanism is discussed based on the activation parameters and CO inhibition (for cDPPEn) or ligand trapping experiments (for bpcd). Thermolysis of 1,1-Os3(CO)10(bpcd) in refluxing toluene gives the hydrido cluster HOs3(CO)9[μ-(PPh2)C=C{PPh(C6H4)}C(O)CH2C(O)] and the benzyne cluster HOs3(CO)8(μ3-C6H4)[μ2,η1-PPhC=C(PPh2)C(O)CH2C(O)]. Photolysis of 1,1-Os3(CO)10(bpcd) using near UV light affords HOs3(CO)9[μ-(PPh2)C=C{PPh(C6H4)}C(O)CH2C(O)] as the sole product. HOs3(CO)8(μ3-C6H4)[μ2,η1-PPhC=C(PPh2)C(O)CH2C(O)] has been characterized in solution by IR and NMR spectroscopies. Furthermore its molecular structure has been determined by X-ray crystallography. Reversible C-H bond formation in HOs3(CO)9[μ-(PPh2)C=C{PPh(C6H4)}C(O)CH2C(O)] is demonstrated by ligand trapping studies to give 1,1-Os3(CO)9L(bpcd) (where L = CO, phosphine) via the unsaturated intermediate 1,1-Os3(CO)9(bpcd). The kinetics for reductive coupling in HOs3(CO)9[γ-(PPh2)C=C{PPh(C6H4)}C(O)CH2C(O)] and DOs3(CO)9[μ-(PPh2-d10)C=C{P(Ph-d5)(C6D4)}C(O)CH2C(O)] in the presence of PPh3 give rise to a kH/kD value …

Flat dendrimers, consisting of a hexavalent aromatic core and rigid ethynyl units locked in place by ether connections were developed based upon the divergent synthetic method. Alternating functional groups were adopted on each site of the hexa-substituted benzene, in order to avoid undesired cyclization pathways. The flat structures of conjugated dendrimers would allow investigation on the discotic liquid crystal properties. In addition, these ethylnyl dendrimers are expected to show directed energy and electron transfer with a highly conjugated system, and thus are effective in the preparation of photoreactive materials such as electronic sensors or light harvesting materials. Conjugated polycyclic aromatic hydrocarbons, consisting of naphthalene, anthracene, pyrene, and phenanthrene groups connected via 1,3,5-triethynylbenzene cores, were synthesized. These molecules exhibited luminescence properties and the π-complexation with a mercury trifunctional lewis acid are expected to enhance the phosphorescence in the presence of the heavy metal due to the spin-orbit coupling. Besides, owing to the presence of heavy metal atom in the Au (I) complexes linked by s-bonded triethynyltriphenylene luminophore, the phosphorescence occurs from a metal-centered emission. The conjugated organic luminophores have been developed to produce excellent quantum efficiencies, brightness, and long lifetimes.

In recent years, advances in computer technology combined with new ab initio computational methods have allowed for dramatic improvement in the prediction of energetic properties. Unfortunately, even with these advances, the extensive computational cost, in terms of computer time, memory, and disk space of the sophisticated methods required to achieve chemical accuracy - defined as 1 kcal/mol from reliable experimental data effectively - limits the size of molecules [i.e. less than 10-15 non-hydrogen atoms] that can be studied. Several schemes were explored to help reduce the computational cost while still maintaining chemical accuracy. Specifically, a study was performed to assess the accuracy of ccCA to compute atomization energies, ionization potentials, electron affinities, proton affinities, and enthalpies of formation for third-row (Ga-Kr) containing molecules. Next, truncation of the correlation consistent basis sets for the hydrogen atom was examined as a possible means to reduce the computational cost of ab initio methods. It was determined that energetic properties could be extrapolated to the complete basis set (CBS) limit utilizing a series of truncated hydrogen basis sets that was within 1 kcal/mol of the extrapolation of the full correlation consistent basis sets. Basis set truncation for the hydrogen atom was then applied to …

Density functional (ca, BLYP, BPW91, B3LYP and B3PW91), MP2 and CCSD(T) methods in combination with LANL2DZ or cc-pVxZ-PP (where x=D(double), T(triple) Q(quadruple), and 5(quintuple)) basis sets have been employed in computing electronic transition energies of zinc and cadmium monomers. CCSD(T)/aug-cc-pV5Z-PP combination finds values that are 150 cm-1 from the experimental value for the zinc monomer and 240 cm-1 remove from the cadmium monomer excitation experimental value. These method/basis set combinations are also used to find spectroscopic values (re, De, we, wexe, Be , and Te) that rival experimental values for dimers and excimers. Examples of this can be seen with the CCSD(T)/aug-cc-pV5Z-PP combination phosphorescent emission results. The values found are within 120 cm-1 of the zinc emission energy and 290 cm-1 of the cadmium emission energy. While this combination rigorously models spectroscopic constants for monomers, dimers, and excimers, it does not efficiently model these constants for larger clusters with available modern computational resources. It is important to show spectroscopic trends (bonding, phosphorescent excitation and emissions) as clusters increase as the monomer and dimer emission energies do not model solid state metallophilic interactions and phosphorescence. The MP2/LANL2DZ combinations show qualitative cooperative bonding trends in group oligomers and extended excimers as size …