In this work we address two problems in computational chemistry relevant to biomolecular modeling. In the first project, we consider the conformer space of melatonin as a a representative example of “real-life” flexible biomolecules. Geometries for all 52 unique conformers are optimized using spin-component scaled MP2, and then relative energies are obtained at the CCSD (T) level near the complete basis set limit. These are then used to validate a variety of DFT methods with and without empirical dispersion corrections, as well as some lower-level ab initio methods. Basis set convergence is found to be relatively slow due to internal C-H…O and C-H…N contacts. Absent dispersion corrections, many DFT functionals will transpose the two lowest conformers. Dispersion corrections resolve the problem for most functionals. Double hybrids yield particularly good performance, as does MP2.5. In the second project, we propose a simple DFT-based diagnostic for nondynamical correlation effects. Aλ= (1-TAE [ΧλC]/TAE[XC])/λ where TAE is the total atomization energy, XC the “pure” DFT exchange-correlation functional, and ΧλC the corresponding hybrid with 100λ% HF-type exchange. The diagnostic is a good predictor for sensitivity of energetics to the level of theory, unlike most of the wavefunction-based diagnostics. For GGA functionals, Aλ values approaching unity indicate severe non-dynamical correlation. The diagnostic is only weakly sensitive to the basis set (beyond polarized double zeta) and can be applied to problems beyond practical reach of wavefunction ab-initio methods required for other diagnostics.
Organic dyes are examined in photoelectrochemical systems wherein they engage in thermal (rather than photoexcited) electron donation into metal oxide semiconductors. These studies are intended to elucidate fundamental parameters of electron transfer in photoelectrochemical cells. Development of novel methods for the structure/property tuning of electroactive dyes and the preparation of nanostructured semiconductors have also been discovered in the course of the presented work. Acceptor sensitized polymer oxide solar cell devices were assembled and the impact of the acceptor dyes were studied. The optoelectronic tuning of boron-chelated azadipyrromethene dyes has been explored by the substitution of carbon substituents in place of fluoride atoms at boron. Stability of singlet exited state and level of reduction potential of these series of aza-BODIPY coumpounds were studied in order to employ them as electron-accepting sensitizers in solid state dye sensitized solar cells.
One of the central concerns of computational chemistry is that of efficiency (i.e. the development of methodologies which will yield increased accuracy of prediction without requiring additional computational resources – RAM, disk space, computing time). Though the equations of quantum mechanics are known, the solutions to these equations often require a great deal of computing power. This dissertation primarily concerns the theme of improved computational efficiency (i.e. the achievement of greater accuracy with reduced computational cost). Improvements in the efficiency of computational chemistry are explored first in terms of the correlation consistent composite approach (ccCA). The ccCA methodology was modified and this enhanced ccCA methodology was tested against the diverse G3/05 set of 454 energetic properties. As computational efficiency improves, molecules of increasing size may be studied and this dissertation explored the issues (differential correlation and size extensivity effects) associated with obtaining chemically accurate (within 1 kcal mol-1) enthalpies of formation for hydrocarbon molecules of escalating size. Two applied projects are also described; these projects concerned the theoretical prediction of a novel rare gas compound, FKrOH, and the mechanism of human glutathione synthetase’s (hGS) negative cooperativity. The final work examined the prospect for the parameterization of the modified embedded atom method (MEAM) potential using first principles calculations of dimer and trimer energies of nickel and carbon systems. This method of parameterization holds promise for increasing the accuracy of simulations for bulk properties within the field of materials science.
Computational chemistry has led to the greater understanding of the molecular world, from the interaction of molecules, to the composition of molecular species and materials. Of the families of computational chemistry approaches available, the main families of electronic structure methods that are capable of accurate and/or reliable predictions of energetic, structural, and spectroscopic properties are ab initio methods and density functional theory (DFT). The focus of this dissertation is to improve the accuracy of predictions and computational efficiency (with respect to memory, disk space, and computer processing time) of some computational chemistry methods, which, in turn, can extend the size of molecule that can be addressed, and, for other methods, DFT, in particular, gain greater insight into which DFT methods are more reliable than others. Much, though not all, of the focus of this dissertation is upon transition metal species – species for which much less method development has been targeted or insight about method performance has been well established. The ab initio approach that has been targeted in this work is the correlation consistent composite approach (ccCA), which has proven to be a robust, ab initio computational method for main group and first row transition metal-containing molecules yielding, on average, accurate thermodynamic properties, i.e., within 1 kcal/mol of experiment for main group species and within 3 kcal/mol of experiment for first row transition metal molecules. In order to make ccCA applicable to systems containing any element from the periodic table, development of the method for second row transition metals and heavier elements, including lower p-block (5p and 6p) elements was pursued. The resulting method, the relativistic pseudopotential variant of ccCA (rp-ccCA), and its application are detailed for second row transition metals and lower p-block elements. Because of the computational cost of ab initio methods, DFT is a popular choice …
Greater understanding and accurate predictions of structural, thermochemical, and spectroscopic properties of chemical compounds is critical for the advancements of not only basic science, but also in applications needed for the growth and health of the U.S. economy. This dissertation includes new ab initio composite approaches to predict accurate energetics of lanthanide-containing compounds including relativistic effects, and optimization of parameters for semi-empirical methods for transition metals. Studies of properties and energetics of chemical compounds through various computational methods are also the focus of this research, including the C-O bond cleavage of dimethyl ether by transition metal ions, the study of thermochemical and structural properties of small silicon containing compounds with the Multi-Reference correlation consistent Composite Approach, the development of a composite method for heavy element systems, spectroscopic of compounds containing noble gases and metals (ArxZn and ArxAg+ where x = 1, 2), and the effects due to Basis Set Superposition Error (BSSE) on these van der Waals complexes.
The efforts of my research have led to the successful construction of several instruments that have helped expand the field of microwave spectroscopy. The classic Balle-Flygare spectrometer has been modified to include two different sets of antenna to operate in the frequency ranges 6-18 GHz and 18-26 GHz, allowing it to function for a large range without having to break vacuum. This modified FTMW instrument houses two low noise amplifiers in the vacuum chamber to allow for the LNAs to be as close to the antenna as physically possible, improving sensitivity. A new innovative Balle-Flygare type spectrometer, the efficient low frequency FTMW, was conceived and built to operate at frequencies as low as 500 MHz through the use of highly curved mirrors. This is new for FTMW techniques that normally operate at 4 GHz or higher with only a few exceptions around 2 GHz. The chirped pulse FTMW spectrometer uses horn antennas to observe spectra that span 2 GHz versus the standard 1 MHz of a cavity technique. This instrument decreases the amount of time to obtain a large spectral region of relative correct intensity molecular transitions. A Nd:YAG laser ablation apparatus was attached to the classic Balle-Flygare and chirped pulse FTMW spectrometers. This allowed the study of heavy metal containing compounds. The instruments I constructed and the techniques I used have allowed the discovery of further insights into molecular chemistry. I have seen the effects of fluorinating an alkyl halide by determining the geometry of the carbon backbone of trans-1-iodoperfluoropropane and observing a ΔJ = 3 forbidden transition caused by a strong quadrupole coupling constant on this heavy molecule. The quadrupole coupling tensors of butyronitrile, a molecule observed in space, have been improved. The nuclear quadrupole coupling tensor of difluoroiodomethane was added to a list of variably fluorinated methyl …
The purpose of this study is to find out what students in the first chemistry course at the undergraduate level (general chemistry for science majors) know about the affordances of instrumentation used in the general chemistry laboratory and how their knowledge develops over time. Overall, students see the PASCO system as a useful and accurate measuring tool for general chemistry labs. They see the probeware as easy to use, portable, and able to interact with computers. Students find that the PASCO probeware system is useful in their general chemistry labs, more advanced chemistry labs, and in other science classes, and can be used in a variety of labs done in general chemistry. Students learn the affordances of the probeware through the lab manual, the laboratory teaching assistant, by trial and error, and from each other. The use of probeware systems provides lab instructors the opportunity to focus on the concepts illustrated by experiments and the opportunity to spend time discussing the results. In order to teach effectively, the instructor must know the correct name of the components involved, how to assemble and disassemble it correctly, how to troubleshoot the software, and must be able to replace broken or missing components quickly. The use of podcasts or Web-based videos should increase student understanding of affordances of the probeware.
The purpose of this investigation (a quasi-experimental design called a non-equivalent design group (NEDG)) was to determine if allowing students in a science majors general Chemistry I course the choice in establishing the due dates that their homework was due to the instructor would improve course averages. This study covered two semesters with a total of 288 students participating with n = 158 in the fall and n = 130 in the spring. The students self-selected the homework group, VOICES, that best fit his/her needs which included (1) the instructor's homework schedule, (2) a student-customized schedule or a schedule that followed the exam schedule, or (3) all homework due by the last class day prior to the final exam. Online homework was assigned and graded with individual assignment and homework average grades collected and analyzed. No statistically significant differences were found among the VOICES groups with respect to final course average. Other results of this study replicated findings in the literature; namely, that there is a higher correlation between mathematics skills and course success. Course averages of students who had completed Calculus I or higher were statistically significantly higher than students with less completed mathematics coursework in all VOICES groups. Also, the percentage of successful students in the on-sequence semester (fall) was higher than the percentage of students in the off-sequence semester (spring). No differences were seen in any VOICES group's student demographics or high school chemistry preparation.
The regulations of many food products in the United States have been made and followed very well but unfortunately some products are not put under such rigorous standards as others. This leads to products being sold, that are thought to be healthy, but in reality contain unknown ingredients that may be hazardous to the consumers. With the use of several instrumentations and techniques the detection, characterization and identification of these unknown contaminates can be determined. Both the AZ-100 and the TE2000 inverted microscope were used for visual characterizations, image collection and to help guide the extraction. Direct analyte-probed nanoextraction (DAPNe) technique and nanospray ionization mass spectrometry (NSI-MS) was the technique used for examination and identification of all adulterants. A Raman imaging technique was than introduced and has proven to be a rapid, non-destructive and distinctive way to localize a specific adulterant. By compiling these techniques then applying them to the FDA supplied test samples three major adulterants were detected and identified.
Over the last 20 years, there has occurred an increase in the number, scope, and impact of nanomaterials projects. By leveraging the Surface Plasmon Resonance of metallic nanoparticles for labelling, sensing, and treatment, researchers have demonstrated the versatile utility of these nanomaterials in medicine. The literature provides evidence of use of simple, well-known chemistry for nanomaterials synthesis when the focus is new applications of nanomaterials. A case in point, is the synthesis of metallic nanoparticles, whereby HAuCl4, CuCl2, Cu(acac)2, and AgNO3 are typically employed as nanoparticle precursors. Unfortunately, the use of these precursors limits the number of applications available to these materials - particularly for AuNPs in medicine, where the byproducts of nanoparticle synthesis (most often surface-adsorbed reductants, toxic stabilizers, and growth directors) cause nanoparticles to fail clinical trials. Despite the several thousand publications detailing the advancements in nanoparticle therapeutics, as of 2017, there were only 50 FDA-approved nanoparticle formulations. Less than 10 were based on metallic nanoparticles. This is a problem because many of these nanoparticle therapeutics demonstrate potent cell killing ability and labeling of cells. A solution to this problem may be the use of weakly coordinated, monovalent metal complexes, which require only one electron to reduce them to their metallic state. Further, by designing nanoparticle syntheses around these monovalent complexes, we can employ weaker, environmentally friendly stabilizers. This strategy also forgoes the use of exogenous reducing agents, because the monovalent complexes can be reduced and stabilized by one reagent. Herein we investigate the use of Au(Me2S)Cl, [Cu(MeCN)4]BF4, and AgBF4 with green stabilizers to synthesize a variety of nanomaterials. We find that a range of sizes of spherical particles, as well as a range of sizes of gold triangular prisms can be synthesized by using techniques that follow this strategy.
Advances in computing capabilities have facilitated the application of quantum mechanical methods to increasingly larger and more complex chemical systems, including weakly interacting and biologically relevant species. One such ab initio-based composite methodology, the correlation consistent composite approach (ccCA), has been shown to be reliable for the prediction of enthalpies of formation and reaction energies of main group species in the gas phase to within 1 kcal mol-1, on average, of well-established experiment, without dependence on experimental parameterization or empirical corrections. In this collection of work, ccCA has been utilized to determine the proton affinities of deoxyribonucleosides within an ONIOM framework (ONIOM-ccCA) and to predict accurate enthalpies of formation for organophosphorus compounds. Despite the complexity of these systems, ccCA is shown to result in enthalpies of formation to within ~2 kcal mol-1 of experiment and predict reliable reaction energies for systems with little to no experimental data. New applications for the ccCA method have also been introduced, expanding the utility of ccCA to solvated systems and complexes with significant noncovalent interactions. By incorporating the SMD solvation model into the ccCA formulation, the Solv-ccCA method is able to predict the pKa values of nitrogen systems to within 0.7 pKa unit (less than 1.0 kcal mol-1), overall. A hydrogen bonding constant has also been developed for use with weakly interacting dimers and small cluster compounds, resulting in ccCA interaction energies for water clusters and dimers of the S66 set to within 1.0 kcal mol-1 of well-established theoretical values.
The continuously increasing demand for innovation in the miniaturization of microelectronics has driven the need for ever more precise fabrication strategies for device packaging, especially for printed circuit boards (PCBs). Subtractive copper etching is a fundamental step in the fabrication process, requiring very precise control of etch rate and etch factor. Changes in the etching chemical equilibrium have significant effects on etching behavior, and CuCl2 / HCl etching baths are typically monitored with several parameters including oxidation-reduction potential, conductivity, and specific gravity. However, the etch rate and etch factor can be difficult to control even under strict engineering controls of those monitoring parameters. The mechanism of acidic cupric chloride etching, regeneration and recovery is complex, and the current monitoring strategies can have difficulty controlling the interlocking chemical equilibria. A complimentary tool, thin-film UV-Vis spectroscopy, can be utilized to improve the current monitoring strategies, as UV-Vis is capable of identifying and predicting etching behavior that the current standard methodologies have difficulty predicting. Furthermore, as a chemically-sensitive probe, UV-Vis can investigate the complex changes to the chemical equilibrium and speciation of the etch bath, and can contribute overall to significant improvements in the control of the copper etching system in order to meet the demands of next-level design strategies.
Nanoparticles, simple yet groundbreaking objects have led to the discovery of invaluable information due to their physiological, chemical, and physical properties, have become a hot topic in various fields of study including but not limited to chemistry, biology, and physics. In the work presented here, demonstrations of various applications of chemical free nanoparticles are explored, from the determination of a non-invasive method for the study of the exposome via using soft-landing ion mobility (SLIM) deposited nanoparticles as a matrix-assisted laser desorption/ionization (MALDI-MS) matrix replacement, to the direct SLIM-exposure of nanoparticles onto living organisms. While there is plenty of published work in soft-landing at operating pressures of 1 Torr, the work presented here shows how this technology can be operated at the less common ambient pressure. The ease of construction of this instrument allows for various modifications to be performed for a wide array of applications, furthermore the flexibility in metallic sample, operating pressure, and deposition time only open doors to many other future applications. The work presented will also show that our ambient SLIM system is also able to be operated for toxicological studies, as the operation at ambient pressure opens the door to new applications where vacuum conditions are not desired.
Density functional theory is an efficient and useful method of solving single-reference computational chemistry problems, however it struggles with multi-reference systems. Modifications have been developed in order to improve the capabilities of density functional theory. In this work, density functional theory has been successfully applied to solve multi-reference systems with large amounts of non-dynamical correlation by use of modifications. It has also been successfully applied for geometry optimizations for lanthanide trifluorides.
Phosphorescent transition metal complexes make up an important group of compounds that continues to attract intense research owing to their intrinsic bioimaging applications that arise from bright emissions, relatively long excited state lifetimes, and large stokes shifts. Now for biomaging assay a model organism is required which must meet certain criteria for practical applications. The organism needs to be small, with a high turn-over of progeny (high fecundity), a short lifecycle, and low maintenance and assay costs. Our model organism C. elegans met all the criteria. The ideal phosphor has low toxicity in the model organism. In this work the strongly phosphorescent platinum (II) pyrophosphito-complex was tested for biological applications as a potential in vivo hypoxia sensor. The suitability of the phosphor was derived from its water solubility, bright phosphorescence at room temperature, and long excited state lifetime (~ 10 µs). The applications branched off to include testing of C. elegans survival when treated with the phosphor, which included lifespan and fecundity assays, toxicity assays including the determination of the LC50, and recovery after paraquat poisoning. Quenching experiments were performed using some well knows oxygen derivatives, and the quenching mechanisms were derived from Stern-Volmer plots. Reaction stoichiometries were derived from Job plots, while percent scavenging (or antioxidant) activities were determined graphically. The high photochemical reactivity of the complex was clearly manifested in these reactions.
The growth of single and multilayer BN films on several substrates was investigated. A typical atomic layer deposition (ALD) process was demonstrated on Si(111) substrate with a growth rate of 1.1 Å/cycle which showed good agreement with the literature value and a near stoichiometric B/N ratio. Boron nitride films were also deposited by ALD on Cu poly crystal and Cu(111) single crystal substrates for the first time, and a growth rate of ~1ML/ALD cycle was obtained with a B/N ratio of ~2. The realization of a h-BN/Cu heterojunction was the first step towards a graphene/h-BN/Cu structure which has potential application in gateable interconnects.
Carbon nanostructure based functional hybrid molecules hold promise in solarenergy harvesting. Research presented in this dissertation systematically investigates building of various donor-acceptor nanohybrid systems utilizing enriched single walled carbon nanotube and graphene with redox and photoactive molecules such as fullerene, porphyrin, and phthalocyanine. Design, synthesis, and characterization of the donor-acceptor hybrid systems have been carefully performed via supramolecular binding strategies. Various spectroscopic studies have provided ample information in terms of establishment of the formation of donor-acceptor hybrids and their extent of interaction in solution and eventual rate of photoinduced electron and/or energy transfer. Electrochemical studies enabled construction of energy level diagram revealing energetic details of the possible different photochemical events supported by computational studies carried out to establish the HOMO-LUMO levels in the donor acceptor systems. Transient absorption studies confirmed formation of charge separated species in the donor-acceptor systems which have been supported by electron mediation experiments. Based on the photoelectrochemical studies, IPCE of 8% was reported for enriched SWCNT(7,6)-ZnP donor-acceptor systems. In summary, the present investigation on the various nanocarbon sensitized donor-acceptor hybrids substantiates tremendous prospect, that could very well become the next generation of materials in building efficient solar energy harvesting devices andphotocatalyst.
Experimental data were obtained for the computation of mole fraction solubilities of three dichloronitrobenzenes in organic solvents at 25oC, and solubility ratios were obtained from this data. Abraham model equations were developed for solutes in tributyl phosphate that describe experimental values to within 0.15 log units, and correlations were made to describe solute partitioning in systems that contain either "wet" or "dry" tributyl phosphate. Abraham model correlations have also been developed for solute transfer into anhydrous diisopropyl ether, and these correlations fit in well with those for other ethers. Abraham correlations for the solvation of enthalpy have been derived from experimental and literature data for mesitylene, p-xylene, chlorobenzene, and 1,2-dichlorobenzene at 298.15 K. In addition, the enthalpy contribution of hydrogen bonding between these solutes and acidic solvents were predicted by these correlations and were in agreement with an established method. Residual plots corresponding to Abraham models developed in all of these studies were analyzed for trends in error between experimental and calculated values.
A novel application of ionic liquid as a charge carrier for the analysis and detection of neutral organometallic complexes using a mass spectrometer has been presented. The mass spectrometer detects only charged compounds which raise a difficulty in analyzing a neutral molecule that lacks a basic site to associate with charge. Therefore, an effective way of providing charge has always been an area of keen interest in the field of mass spectrometry. Ionic liquids have a very fascinating property of forming a cation-? interaction with other molecules to give a charged complex. In order to take advantage of this, it is important to know the geometric structure of the complex. Advanced methodologies like hydrogen-deuterium exchange and computational calculations have been used assisting in better understanding of the structure of the ionic liquid complexes.
Experimental data for the logarithm of the gas-to-ionic liquid partition coefficient (log K) have been compiled from the published literature for over 40 ionic liquids over a wide temperature range. Temperature independent correlations based on the Gibbs free energy equation utilizing known Abraham solvation model parameters have been derived for the prediction of log K for 12 ionic liquids to within a standard deviation of 0.114 log units over a temperature range of over 60 K. Temperature independent log K correlations have also been derived from correlations of molar enthalpies of solvation and molar entropies of solvation, each within standard deviations of 4.044 kJ mol-1 and 5.338 J mol-1 K-1, respectively. In addition, molar enthalpies of solvation and molar entropies of solvation can be predicted from the Abraham coefficients in the temperature independent log K correlations to within similar standard deviations. Temperature independent, ion specific coefficients have been determined for 26 cations and 15 anions for the prediction of log K over a temperature range of at least 60 K to within a standard deviation of 0.159 log units.
Predictive methods have been employed to characterize chemical separation mediums including solvents and absorbents. These studies included creating Abraham solvation parameter models for room-temperature ionic liquids (RTILs) utilizing novel ion-specific and group contribution methodologies, polydimethyl siloxane (PDMS) utilizing standard methodology, and the micelles cetyltrimethylammonium bromide (CTAB) and sodium dodecylsulfate (SDS) utilizing a combined experimental setup methodology with indicator variables. These predictive models allows for the characterization of both standard and new chemicals for use in chemical separations including gas chromatography (GC), solid phase microextraction (SPME), and micellar electrokinetic chromatography (MEKC). Gas-to-RTIL and water-to-RTIL predictive models were created with a standard deviation of 0.112 and 0.139 log units, respectively, for the ion-specific model and with a standard deviation of 0.155 and 0.177 log units, respectively, for the group contribution fragment method. Enthalpy of solvation for solutes dissolved into ionic liquids predictive models were created with ion-specific coefficients to within standard deviations of 1.7 kJ/mol. These models allow for the characterization of studied ionic liquids as well as prediction of solute-solvent properties of previously unstudied ionic liquids. Predictive models were created for the logarithm of solute's gas-to-fiber sorption and water-to-fiber sorption coefficient for polydimethyl siloxane for wet and dry conditions. These models were created to standard deviations of 0.198 and 0.122 logunits for gas-to-PDMS wet and dry, respectively, as well as 0.164 and 0.134 log units for water-to-PDMS wet and dry, respectively. These models are particularly useful in solid phase microextraction separations. Micelles were studied to create predictive models of the measured micelle-water partition coefficient as well as models of measured MEKC chromatographic retention factors for CTAB and SDS. The resultant predictive models were created with standard deviations of 0.190 log units for the logarithm of the mole fraction concentration of water-to-CTAB, 0.171 log units for the combined logarithms of both the …
As the miniaturization of functional devices in integrated circuit (IC) continues to scale down to sub-nanometer size, the process complexity increases and makes materials characterization difficult. One of our research effort demonstrates the development and application of novel Multiple Internal Reflection Infrared Spectroscopy (MIR-IR) as a sensitive (sub-5 nm) metrology tool to provide precise chemical bonding information that can effectively guide through the development of more efficient process control. In this work, we investigated the chemical bonding structure of thin fluorocarbon polymer films deposited on low-k dielectric nanostructures, using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Complemented by functional group specific chemical derivatization reactions, fluorocarbon film was established to contain fluorinated alkenes and carbonyl moieties embedded in a highly cross-linked, branched fluorocarbon structure and a model bonding structure was proposed for the first time. In addition, plasma induced damage to high aspect ratio trench low-k structures especially on the trench sidewalls was evaluated both qualitatively and quantitatively. Damage from different plasma processing was correlated with Si-OH formation and breakage of Si-CH3 bonds with increase in C=O functionality. In another endeavor, TiN hard mask defect formation after fluorocarbon plasma etch was characterized and investigated. Finding suggest the presence of water soluble amines that could possibly trigger the formation of TiN surface defect. An effective post etch treatment (PET) methods were applied for etch residue defect removal/suppression.
Boron carbide-aromatic composites, formed by plasma-enhanced co-deposition of carboranes and aromatic precursors, present enhanced electron-hole separation as neutron detector. This is achieved by aromatic coordination to the carborane icosahedra and results in improved neutron detection efficiency. Photoemission (XPS) and FTIR suggest that chemical bonding between B atoms in icosahedra and aromatic contents with preservation of π system during plasma process. XPS, UPS, density functional theory (DFT) calculations, and variable angle spectroscopic ellipsometery (VASE) demonstrate that for orthocarborane/pyridine and orthocarborane/aniline films, states near the valence band maximum are aromatic in character, while states near the conduction band minimum include those of either carborane or aromatic character. Thus, excitation across the band gap results in electrons and holes on carboranes and aromatics, respectively. Further such aromatic-carborane interaction dramatically shrinks the indirect band gap from 3 eV (PECVD orthocarborane) to ~ 1.6 eV (PECVD orthocarborane/pyridine) to ~1.0 eV (PECVD orthocarborane/aniline), with little variation in such properties with aromatic/orthocarborane stoichiometry. The narrowed band gap indicate the potential for greatly enhanced charge generation relative to PECVD orthocarborane films, as confirmed by zero-bias neutron voltaic studies. The results indicate that the enhanced electron-hole separation and band gap narrowing observed for aromatic/orthocarborane films relative to PECVD orthocarborane, has significant potential for a range of applications, including neutron detection, photovoltaics, and photocatalysis. Acknowledgements: This work was supported by the Defense Threat Reduction Agency (Grant No.HDTRA1-14-1-0041). James Hilfiker is also gratefully acknowledged for stimulating discussions.
This work focuses on finding the complete iodine and nitrogen nuclear electric quadrupole coupling tensors for fluoroiodoacetonitrile using chirped-pulse Fourier transform microwave spectroscopy. Fluoroiodoacetonitrile contains two hyperfine nuclei, iodine (I=5/2) and nitrogen (I=1) and the spectra were observed with great resolution. A total of 499 transitions were observed for this molecule. The a, b and c rotational constants were obtained. A study of chloropentafluoroacetone was also done using chirped-pulse Fourier transform microwave spectroscopy. The two chlorine isotopes for this molecule, Cl-35 and Cl-37 were observed and 326 and 170 transitions were recorded, respectively.
Computational chemistry has gained interest as a characterization tool to predict photoluminescence, reactivity and structural properties of organic and transition metal complexes. With the rise of methods including relativity, these studies have been expanded to the accurate modeling of luminescence spectra of complexes with considerable spin-orbit splitting due to heavy metal centers as well as the reaction pathways for these complexes to produce natural products such as hydrogen gas. These advances have led to the synthesis and utility of more effective catalysis as well as the development of more effective organic light emitting diodes (OLEDs) through the incorporation of organometallic complexes as emitters instead of typical organic emitters. In terms of significant scientific advancement presented in this work is in relation to the discovery of significant spin-orbit splitting in a gold(I) alkylphosphine complex, where the splitting results in the states that emit in different colors of the visible region of the electromagnetic spectrum. This work also reveals the discovery both computationally and experimentally, of a genuine polar-covalent bond between two-closed shell metals. This work highlights a complex with an incredibly short gold(I) – copper(I) intermetallic distance leading to a vibrational frequency and dissociation energy that is on par with those of other systems with single-bonded metal centers. Lastly, this work outlines a strategy for the production of hydrogen gas through the use of trinuclear cyclic coinage metal complexes as catalysis to split hydrohalic acids.
Photophysical properties of an array of various polyaromatic hydrocarbons were benchmarked with B3LYP, M06 and B97D methods coupled with Pople and CEP-31G(d) basis sets. Results from the benchmark show the importance of diffuse basis sets when modeling the electronic properties of highly conjugated systems and provide qualitative reliable accuracy with certain levels of theory. B97D and M06 are applied to modeling pyrene adducts governed by non-covalent interactions in both gaseous and condensed states to reproduce experimental spectra. DFT calculations with both B97D and M06 functionals show qualitatively and quantitatively that pyrene dimer is a stronger π–base as compared to its monomer. Binding energies coupled with MEP, PCA and Qzz results show that the difference in π-basicity of the monomer and dimer impacts the supramolecular chemistry involved in adducts formed with super π-acidic silver cyclometallic trimer (CTC). Non-covalent interactions between coinage metal CTCs and ammonia/phosphine substrates is reported. Interactions between these substrates and the facial plane of the π-rich gold CTC reveal a novel interaction, where the typical Lewis acid/base roles are reversed for the substrates. Adducts formed through this type of interaction define typical Lewis bases like ammonia and phosphine as Lewis acids, wherein the partially positive hydrogens coordinate to the metallo-aromatic center through dipole-quadrupole interactions. Interactions of ammonia at the side positions is shown to heavily impact the Lewis basicity of the CTC facial plane leading to similar interactions exhibited by the ammonia-gold CTC adducts. Structural and electronic properties of the adducts modeled are examined.
Genomic integrity is important for living cells' correct functioning and propagation. Deoxyribonucleic acid as a molecule is a subject to chemical reactions with agents that can come from environment as well as from internal metabolism processes. These reactions can induce damage to DNA and thus compromise the genetic information, and result in disease and death of an organism. To mitigate the damage to DNA, cells have evolved to have multiple DNA repair pathways. Presented here is a computational study of DNA repair genes. The structure of the Homo sapiens direct DNA repair gene ALKBH1 is predicted utilizing homology modeling methods and using AlkB and DBL proteins as templates. Analysis of the obtained structure and molecular dynamics simulations give insights into potentially functionally important residues of the protein. In particular, zinc finger domains are predicted, and lysines that could perform catalytic activities are investigated. Subsequent mutagenesis experiments revealed the effect of the residues predicted to form zinc fingers on activity of ALKBH1. Structure and dynamics of AlkD, a Bascillus cereus base excision DNA repair protein is also studied. This protein has been shown to bind DNA with large alkyl adducts and perform excision catalysis without base flipping which is characteristic to other enzymes in the same family. MD simulations of AlkD revealed that B helix, which interacts with DNA, has higher fluctuations when AlkD is not bound to DNA, and thus could have a role in binding and recognition of DNA. For the purpose of finding biomarkers and to further our understanding of a mode of action of DNA repair genes, statistical methods were applied to identify mutations that are linked to cancer phenotypes. Analysis was based on case-control studies of patients with cancers of prostate, breast, pancreas, lung as well as chronic lymphocytic leukemia from NCBI dbGAP database. Those mutations …
The scope of work in this dissertation has comprised several major investigations on applications and theoretical studies of ab initio quantum mechanics and density functional theory where those techniques were applied to the following: (i) investigation of the performance of density functionals for the computations of molecular properties of 3d transition metal containing systems; (ii) guidance for experimental groups for rational design of macrometallocyclic multinuclear complexes with superior π-acidity and π-basicity that are most suitable for p- and n-type semiconductors of metal-organic molecules and nanomaterials; (iii) investigation of the metallo-aromaticity of multi-nuclear metal complexes; (iv) investigation of the kinetics and thermodynamics of copper-mediated nitrene insertion into C-H and H-H bond; and (v) accurate computations of dissociation energies of hydrogen-bonded DNA duplex moieties utilizing the resolution of identity correlation consistent composite approach (RI-ccCA).
Computational chemistry lies at the intersection of chemistry, physics, mathematics, and computer science, and can be used to explain the behavior of atoms and molecules, as well as to augment experiment. In this work, computational chemistry methods are used to predict structural and energetic properties of small molecules, i.e. molecules with less than 60 atoms. Different aspects of computational chemistry are examined in this work. The importance of examining the converged orbitals obtained in an electronic structure calculation is explained. The ability to more completely describe the orbital space through the extrapolation of energies obtained at increasing quality of basis set is investigated with the use of the Sapporo-nZP-2012 family of basis set. The correlation consistent Composite Approach (ccCA) is utilized to compute the enthalpies of formation of a set of molecules and the accuracy is compared with the target method, CCSD(T,FC1)/aug-cc-pCV∞Z-DK. Both methodologies are able to produce computed enthalpies of formation that are typically within 1 kcal mol-1 of reliable experiment. This demonstrates that ccCA can be used instead of much more computationally intensive methods (in terms of memory, processors, and time required for a calculation) with the expectation of similar accuracy yet at a reduced computational cost. The enthalpies of formation for systems containing s-block elements have been computed using the multireference variant of ccCA (MR-ccCA), which is designed specifically for systems that require an explicit treatment of nondynamical correlation. Density functional theory (DFT) has been used for the prediction of the structural properties of a set of lanthanide trihalide molecules as well as the reaction energetics for the rearrangement of diphosphine ligands around a triosmium cluster.
This work discusses applications of computational simulations to enzymatic systems with a particular focus on the effects of various small perturbations on cancer and disease-related systems. First, we cover the development of carbohydrate-based PET imaging ligands for Galectin-3, which is a protein overexpressed in pancreatic cancer tumors. We uncover several structural features for the ligands that can be used to improve their binding and efficacy. Second, we discuss the AlkB family of enzymes. AlkB is the E. coli DNA repair protein for alkylation damage, and has human homologues with slightly different functions and substrates. Each has a conserved active site with a catalytic iron and a coordinating His...His...Asp triad. We have applied molecular dynamics (MD) to investigate the effect of a novel single nucleotide polymorphism for AlkBH7, which is correlated with prostate cancer and has an unknown function. We show that the mutation leads to active site distortion, which has been confirmed by experiments. Thirdly, we investigate the unfolding of hen egg white lysozyme in 90% ethanol solution and low pH, to show the initial steps of unfolding from a native-like state to the disease-associated beta-sheet structure. We compare to mass spectrometry experiments and also show differing pathways based on protonation state. Finally, we discuss three different DNA polymerase systems. DNA polymerases are the primary proteins that replicate DNA during cell division, and have various extra or specific functions. We look at a proofreading-deficient DNA polymerase III mutant, the effects of solvent on DNA polymerase IV's ability to bypass bulky DNA adducts, and a variety of mutations on DNA polymerase kappa.
This work discusses the C-H bond activation by transition metal complexes using various computational methods. First, we performed a DFT study of oxidative addition of methane to Ta(OC2H4)3A (where A may act as an ancillary ligand) to understand how A may affect the propensity of the complex to undergo oxidative addition. Among the A groups studied, they can be a Lewis acid (B or Al), a saturated, electron-precise moiety (CH or SiH), a σ-donor (N), or a σ-donor/π-acid (P). By varying A, we seek to understand how changing the electronic properties of A can affect the kinetics and thermodynamics of methane C–H activation by these complexes. For all A, the TS with H trans to A is favored kinetically over TS with CH3 trans to A. Upon moving from electron-deficient to electron-rich moieties (P and N), the computed C–H activation barrier for the kinetic product decreases significantly. Thus, changing A greatly influences the barrier for methane C–H oxidative addition by these complexes. Secondly, a computational study of oxidative addition (OA) of methane to M(OC2H4)3A (M = Ta, Re and A = ancillary ligand) was carried out using various computational methods. The purpose of this study was to understand how variation in A and M affects the kinetics and thermodynamics of OA. Results obtained from MP2 calculations revealed that for OA of CH4 to Re(OC2H4)3A, the order of ΔG‡ for a choice of ancillary ligand is B > Al > SiH > CH > N > P. Single point calculations for ΔG‡ obtained with CCSD(T) showed excellent agreement with those computed with MP2 methods. MCSCF calculations indicated that oxidative addition transition states are well described by a single electronic configuration, giving further confidence in the MP2 approach used for geometry optimization and ΔG‡ determination, and that the transition states are more …
Computational methods were employed to investigate catalytic processes. First, DFT calculations predicted the important geometry metrics of a copper–nitrene complex. MCSCF calculations supported the open-shell singlet state as the ground state of a monomeric copper nitrene, which was consistent with the diamagnetic character deduced from experimental observations. The calculations predicted an elusive terminal copper nitrene intermediate. Second, DFT methods were carried out to investigate the mechanism of C–F bond activation by a low-coordinate cobalt(I) complex. The computational models suggested that oxidative addition, which is very rare for 3d metals, was preferred. A π–adduct of PhF was predicted to be a plausible intermediate via calculations. Third, DFT calculations were performed to study ancillary ligand effects on C(sp3)–N bond forming reductive elimination from alkylpalladium(II) amido complexes with different phosphine supporting ligands. The dimerization study of alkylpalladium(II) amido complexes indicated an unique arrangement of dative and covalent Pd-N bonds within the core four-membered ring of bimetallic complexes. In conclusion, computational methods enrich the arsenal of methods available to study catalytic processes in conjunction with experiments.
Density Functional Theory (DFT) is an effective tool for studying diverse metal systems. Presented herein are studies of a variety of metal systems, which can be applied to accomplish transformations that are currently difficult/impossible to achieve. The specific topics studied utilizing DFT include: 1) C–H bond activation via an Earth-abundant transition metal complex, 2) C–H bond deprotonation via an alkali metal superbase, 3) and amination/aziridination reactions utilizing a CuI reagent. Using DFT, the transformation to methanol (CH3OH) from methane (CH4) was examined. The transition metal systems studied for this transformation included a model FeII complex. This first-row transition metal is an economical, Earth-abundant metal. The ligand set for this transformation includes a carbonyl ligand in one set of complexes as well as a phosphite ligand in another. The 3d Fe metal shows the ability to convert alkyls/aryls to their oxidized counterpart in an energetically favorable manner. Also, “superbasic” alkali metal amides were investigated to perform C—H bond cleavage. Toluene was the substrate of interest with Cs chosen to be the metal of interest because of the highly electropositive nature of this alkali metal. These highly electrophilic Cs metal systems allow for very favorable C—H bond scission with a toluene substrate. Finally, the amination and aziridination of C–H and C=C bonds, respectively, by a CuI reagent was studied. The mechanism was investigated using DFT calculations. Presently, these mechanisms involving the use of coinage metals are debated. Our DFT simulations shed some insight into how these transformations occur and ultimately how they can be manipulated.
Multiscale modeling is an effective tool for integrating different computational methods, creating a way of modeling diverse chemical and physical phenomena. Presented are studies on a variety of chemical problems at different computational scales and also the combination of different computational methods to study a single phenomenon. The methods used encompass density functional theory (DFT), molecular dynamics (MD) simulations and finite element analysis (FEA). The DFT studies were conducted both on the molecular level and using plane-wave methods. The particular topics studied using DFT are the rational catalyst design of complexes for C—H bond activation, oxidation of nickel surfaces and the calculation of interaction properties of carbon dioxide containing systems directed towards carbon dioxide sequestration studies. Second and third row (typically precious metals) transition metal complexes are known to possess certain electronic features that define their structure and reactivity, and which are usually not observed in their first-row (base metal) congeners. Can these electronic features be conferred onto first-row transition metals with the aid of non-innocent and/or very high-field ligands? Using DFT, the impact of these electronic features upon methane C—H bond activation was modeled using the dipyridylazaallyl (smif) supporting ligand for late, first-row transition metal (M) imide, oxo and carbene complexes (M = Fe, Co, Ni, Cu; E = O, NMe, CMe2). To promote a greater understanding of the process and nature of metal passivation, first-principles analysis of partially oxidized Ni(111) and Ni(311) surface and ultra-thin film NiO layers on Ni(111) was performed. A bimodal theoretical strategy that considers the oxidation process using either a fixed GGA functional for the description of all atoms in the system, or a perturbation approach, that perturbs the electronic structure of various Ni atoms in contact with oxygen by application of the GGA+U technique was applied. Binding energy of oxygen to the nickel …
Methane and dinitrogen are abundant precursors to numerous valuable chemicals such as methanol and ammonia, respectively. However, given the robustness of these substrates, catalytically circumventing the high temperatures and pressures required for such transformations has been a challenging task for chemists. In this work, computational studies of various transition metal catalysts for methane C-H activation and N2 activation have been carried out. For methane C-H activation, catalysts of the form LnM=E are studied, where Ln is the supporting ligand (dihydrophosphinoethane or β-diketiminate), E the activating ligand (O, NCH3, NCF3) at which C-H activation takes place, and M the late transition metal (Fe,Co,Ni,Cu). A hydrogen atom abstraction (HAA) / radical rebound (RR) mechanism is assumed for methane functionalization (CH4 à CH3EH). Since the best energetics are found for (β-diket)Ni=O and (β-diket)Cu=O catalysts, with or without CF3 substituents around the supporting ligand periphery, complete methane-to-methanol cycles were studied for such systems, for which N2O was used as oxygen atom transfer (OAT) reagent. Both monometallic and bimetallic OAT pathways are addressed. Monometallic Fe-N2 complexes of various supporting ligands (LnFe-N2) are studied at the beginning of the N2 activation chapter, where the effect of ligand on N2 activation in end-on vs. side-on N2 isomers is discussed. For (β-diket)Fe-N2 complexes, the additional influence of diketiminate donor atom (N(H) vs. S) is briefly addressed. The remainder of the chapter expands upon the treatment of β-diketiminate complexes. First, the activation and relative stabilities of side-bound and end-bound N2 isomers in monometallic ((β-diket)M-N2) and bimetallic ((β-diket)M-N2-M(β-diket)) first row transition metal complexes are addressed. Second, the thermodynamics of H/H+/H- addition to (β-diket)Fe-bound N2, followed by subsequent H additions up to release of ammonia, is discussed, for which two mechanisms (distal and alternating) are considered. Finally, the chapter concludes with partial distal and alternating mechanisms for H addition to N2 …
In this work, the possibility of Cu electrodeposition on Ru-Ta alloy thin films is explored. Ru and Ta were sputter deposited on Si substrate with different composition verified by RBS. Four point probe, XRD, TEM and AFM were used to study the properties of Ru-Ta thin films such as sheet resistance, crystallinity, grain size, etc. Cyclic voltammetry is used to study the Cu electrodeposition characteristics on Ru-Ta after various surface pretreatments. The results provide insights on the removal of Ta oxide such that it enables better Cu nucleation and adhesion. Bimetallic corrosion of Cu on modified Ru-Ta surface was studied in CMP related chemicals. In Cu interconnect fabrication process, the making of trenches and vias on low-k dielectric films involves the application of fluorocarbon plasma etch gases. Cu microdots deposited on Ru and Ta substrate were treated by fluorocarbon plasma etch gases such as CF4, CF4+O2, CH2F2, C4F8 and SF6 and investigated by using x-ray photoelectron spectroscopy, contact angle measurement and electrochemical techniques. Micropattern corrosion screening technique was used to measure the corrosion rate of plasma treated Cu. XPS results revealed different surface chemistry on Cu after treating with plasma etching. The fluorine/carbon ratio of the etching gases results in different extent of fluorocarbon polymer residues and affects the cleaning efficiency and Cu corrosion trends.
The design and fabrication of a novel soft landing instrument Soft Landing Ion Mobility (SLIM) is described here. Topics covered include history of soft landing, gas phase mobility theory, the design and fabrication of SLIM, as well as applications pertaining to soft landing. Principle applications devised for this instrument involved the gas phase separation and selection of an ionized component from a multicomponent gas phase mixture as combing technique to optimize coatings, catalyst, and a variety of alternative application in the sciences.
Portable mass spectrometers provide a unique opportunity to obtain in situ measurements. This minimizes need for sample collection or in laboratory analysis. Membrane Inlet Mass Spectrometry (MIMS) utilizing a semi permeable membrane for selective rapid introduction for analysis. Polydimethylsiloxane membranes have been proven to be robust in selecting for aromatic chemistries. Advances in front end design have allowed for increased sensitivity, rapid sample analysis, and on line measurements. Applications of the membrane inlet technique have been applied to environmental detection of clandestine drug chemistries and pollutants. Emplacement of a mass spectrometer unit in a vehicle has allowed for large areas to be mapped, obtaining a rapid snapshot of the various concentrations and types of environmental pollutants present. Further refinements and miniaturization have allowed for a backpackable system for analysis in remote harsh environments. Inclusion of atmospheric dispersion modeling has yielded an analytical method of approximating upwind source locations, which has law enforcement, military, and environmental applications. The atmospheric dispersion theories have further been applied to an earth based separation, whereby chemical properties are used to approximate atmospheric mobility, and chemistries are further identified has a portable mass spectrometer is traversed closer to a point source.
The ability of gold(I) to activate many types of unsaturated bonds toward nucleophilic attack was not widely recognized until the early 2000s. One major challenge in gold catalysis is the control over regioselectivity when there are two or more possible products as a result of complicated mechanistic pathways. It is well know that the choice of ligand can have dramatic effects on which pathway is being followed but very rarely are the reasons for this selectivity understood. The synthesis of new acyclic diaminocarbenes was developed and a study of the ligand effects on the regioselectivity of a gold-catalyzed domino enyne cyclization hydroarylation reaction and a Nazarov cyclization was undertaken. New chiral acyclic diaminocarbenes were also developed and tested along side new C3-symmetric phosphite ligands in an asymmetric intramolecular hydroamination of allenes. Structure activity correlations were developed for the potential use in further rational ligand design. The synthesis of 6a,7-dihydro-5-amino-dibenzo[c,g]chromene derivatives via a gold-catalyzed domino reaction of alkynylbenzaldehydes in the presence of secondary amines was developed. These were sent to be screened for biological activity.
The two major topics studied in this dissertation are the gold(I) pyrazolate trimer {[Au(3-R,5-R’)Pz]3} complexes in aqueous chitosan polymer and phosphorescent polymeric nanoparticles based on platinum(II) based complex. The first topic is the synthesis, characterization and optical sensing application of gold(I) pyrazolate trimer complexes within aqueous chitosan polymer. A gold(I) pyrazolate trimer complex, {[Au(3-CH3,5-COOH)Pz]3}, shows high sensitivity and selectivity for silver ions in aqueous media, is discussed for optical sensing and solution-processed organic light emitting diodes (OLEDs) applications. Gold(I) pyrazolate trimer complexes are bright red emissive in polymeric solution and their emission color changes with respect to heavy metal ions, pH and dissolved carbon dioxide. These photophysical properties are very useful for designing the optical sensors. The phosphorescent polymeric nanoparticles are prepared with Pt-POP complex and polyacrylonitrile polymer. These particles show excellent photophysical properties and stable up to >3 years at room temperature. Such nanomaterials have potential applications in biomedical and polymeric OLEDs. The phosphorescent hybrid composites are also prepared with Pt-POP and biocompatible polymers, such as chitosan, poly-l-lysine, BSA, pnipam, and pdadmac. Photoluminescent enhancement of Pt-POP with such polymers is also involved in this study. These hybrid composites are promising materials for biomedical applications such as protein labeling and bioimaging.
This work involves synthesis and characterization of isotropic and anisotropic noble metal nanoparticles for applications ranging from antimicrobial uses to anticancer applications. These nanomaterials are stabilized in genuinely benign biomaterials ranging from polymers to cross linked proteins for targeted cancer treatments. The nanoparticles are found to have tunable optical properties.
Groundbreaking progress in molecule-based optoelectronic devices for lighting, display and energy-harvesting technologies demands highly efficient and easily processable functional materials with tunable properties governed by their molecular/supramolecular structure variations. To date, functional coordination compounds whose function is governed by non-covalent weak forces (e.g., metallophilic, dπ-acid/dπ-base stacking, halogen/halogen and/or d/π interactions) remain limited. This is unlike the situation for metal-free organic semiconductors, as most metal complexes incorporated in optoelectronic devices have their function determined by the properties of the monomeric molecular unit (e.g., Ir(III)-phenylpyridine complexes in organic light-emitting diodes (OLEDs) and Ru(II)-polypyridyl complexes in dye-sensitized solar cells (DSSCs)). This dissertation represents comprehensive results of both experimental and theoretical studies, descriptions of synthetic methods and possible application allied to monovalent coinage metal-based functional materials. The main emphasis is given to the design and synthesis of functional materials with preset material properties such as light-emitting materials, light-harvesting materials and conducting materials. In terms of advances in fundamental scientific phenomena, the major highlight of the work in this dissertation is the discovery of closed-shell polar-covalent metal-metal bonds manifested by ligand-unassisted d10-d10 covalent bonds between Cu(I) and Au(I) coinage metals in the ground electronic state (~2.87 Å; ~45 kcal/mol). Moreover, this dissertation also reports pairwise intermolecular aurophilic interactions of 3.066 Å for an Au(I) complex, representing the shortest ever reported pairwise intermolecular aurophilic distances among all coinage metal(I) cyclic trimetallic complexes to date; crystals of this complex also exhibit gigantic luminescence thermochromism of 10,200 cm-1 (violet to red). From applications prospective, the work herein presents monovalent coinage metal-based functional optoelectronic materials such as heterobimetallic complexes with near-unity photoluminescence quantum yield, metallic or semiconducting integrated donor-acceptor stacks and a new class of Au(III)-based black absorbers with cooperative intermolecular iodophilic (I…I) interactions that sensitize the harvesting of all UV, all visible, and a broad spectrum of near-IR …
A series of heteroleptic and homoleptic platinum(II) complexes has been synthesized and characterized towards their use in thin film devices such as organic light-emitting diodes (OLEDs) and organic thin film transistors (OTFTs). Pyridylpyrazolate- and pyridyltetrazolate-containing ligands were selected due to their structural rigidity and ease of functionalization. Single-crystal x-ray diffraction studies of two selected heteroleptic complexes show strong aggregation with preferential stacking into vertical columns with a varying degree of overlap of the neighboring square planar molecular units. It is shown that the close proximity of the molecules to one another in the stack increases semiconducting character, phosphorescence quantum yields, and shorter radiative lifetimes. The potential for these materials towards incorporation into high-efficiency doping free white OLEDs (DFW-OLEDs) for solid-state lighting and display applications has been realized and will be expanded upon by present and future embodiments of materials in this thesis.
This dissertation investigates the chemical ingenuity into the development of various photoactive supramolecular donor – acceptor systems to produce clean and carbon free energy for the next generation. The process is inspired by the principles learned from nature’s approach where the solar energy is converted into the chemical energy through the natural photosynthesis process. Owing to the importance and complexity of natural photosynthesis process, we have designed ideal donor-acceptor systems to investigate their light energy harvesting properties. This process involves two major steps: the first step is the absorption of light energy by antenna or donor systems to promote them to an excited electronic state. The second step involves, the transfer of excitation energy to the reaction center, which triggers an electron transfer process within the system. Based on this principle, the research is focused into the development of artificial photosynthesis systems to investigate dynamics of photo induced energy and electron transfer events. The derivatives of Porphyrins, Phthalocyanines, BODIPY, and SubPhthalocyanines etc have been widely used as the primary building blocks for designing photoactive and electroactive ensembles in this area because of their excellent and unique photophysical and photochemical properties. Meanwhile, the fullerene, mainly its readily available version C60 is typicaly used as an electron acceptor component because of its unique redox potential, symmetrical shape and low reorganization energy appropriate for improved charge separation behavior. The primary research motivation of the study is to achieve fast charge separation and slow charge recombination of the system by stabilizing the radical ion pairs which are formed from photo excitation, for maximum utility of solar energy. Besides Fullerene C60, this dissertation has also investigated the potential application of carbon nanomaterials (Carbon nanotubes and graphene) as primary building blocks for the study of the artificial photosynthesis process.
Portable mass spectrometry has become an important analytical tool for chemical detection and identification outside of a lab setting. Many variations and applications have been developed to benefit various fields of science. Membrane inlet mass spectrometry is used to allow certain analytes to pass into the mass spectrometer without breaking vacuum or letting in large particulate matter. These two important analytical tools have been applied to the detection of harmful chemicals in the air. Earth-based separations and reverse gas stack modelling are useful mathematical tools that can be used to locate the source of a chemical release by back calculation. Earth-based separations studies the way different molecules will diffuse and separate through the air. Reverse gas stack modelling refers to the concentration differences of a chemical in relation to its distance from its source. These four analytical techniques can be combined to quickly and accurately locate various harmful chemical releases. The same system can be used for many applications and has been tested to detect harmful chemicals within and air-handling system. The monitoring of air-handling systems can greatly reduce the threat of harm to the building occupants by detecting hazardous chemicals and shutting off the air flow to minimize human exposure.
The Abraham solvation parameter model is a good approach for analyzing and predicting biological activities and partitioning coefficients. The general solvation equation has been used to predict the solute property (SP) behavior of drug compounds between biological barriers. Gas chromatography (GC) retention time can be used to predict molecular descriptors, such as E, S, A, B & L for existing and newly developed drug compounds. In this research, six columns of different stationary phases were used to predict the Abraham molecular descriptors more accurately. The six stationary phases used were 5% phenylmethyl polysiloxane, 6% cyanopropylphenyl 94% dimethylpolysiloxane, 5% diphenyl 95% dimethylpolysiloxane, 100% dimethylpolysiloxane, polyethylene glycol and 35% diphenyl 65% dimethylpolysiloxane. Retention times (RT) of 75 compounds have been measured and logarithm of experimental average retention time Ln(RTexp) are calculated. The Abraham solvation model is then applied to predict the process coefficients of these compounds using the literature values of the molecular descriptors (Acree Compilation descriptors). Six correlation equations are built up as a training set for each of the six columns. The six equations are then used to predict the molecular descriptors of the illegal drugs as a test set. This work shows the ability to extract molecular information from a new compound by utilizing commonly used GC columns available with the desired stationary phases. One can simply run the new compound in GC using these columns to get the retention time. Plugging in the retention time into the developed equations for each of the column will predict the molecular descriptors for the test compound and will give some information about the properties of the compound.
In this experiment, more than one hundred volatile organic compounds were analyzed with the gas chromatograph. Six capillary columns ZB wax plus, ZB 35, TR1MS, TR5, TG5MS and TG1301MS with different polarities have been used for separation of compounds and illicit drugs. The Abraham solvation model has five solute descriptors. The solute descriptors are E, S, A, B, L (or V). Based on the six stationary phases, six equations were constructed as a training set for each of the six columns. The six equations served to calculate the solute descriptors for a set of illicit drugs. Drugs studied are nicotine (S= 0.870, A= 0.000, B= 1.073), oxycodone(S= 2.564. A= 0.286, B= 1.706), methamphetamine (S= 0.297, A= 1.570, B= 1.009), heroin (S=2.224, A= 0.000, B= 2.136) and ketamine (S= 1.005, A= 0.000, B= 1.126). The solute property of Abraham solvation model is represented as a logarithm of retention time, thus the logarithm of experimental and calculated retention times is compared.
This dissertation focuses on the development, characterization, and analysis of luminescent materials and coatings for sensing applications, including CO2, heavy metals, and silver. Chapter 2 involves the use of a gold(I) pyrazolate trimer that is able to detect silver ions with an AgNP medium. Detection of silver is vital, because there is an influx of silver into our environment caused by the increased use of AgNP. Therefore, having a sensor that is able to differentiate between and detect only Ag ions is an important first step to solving the toxicity mystery of AgNPs. Chapter 3 focuses on the development of sensor coatings containing a Eu(III) based luminescent system for sensing dissolved CO2 without the aid of an absorption-based dye. It is well-known that monitoring CO2 levels in our environment is important since even at low concentrations it can cause adverse health effects to the human body. This work demonstrates a pH-sensitive Eu complex being used directly as a CO2 sensor without the aid of any other absorption-based dye. Chapter 4 explores the idea of developing a heavy metal sensor for lead and its ability to detect lead in wide concentration range upon changing the pH of the medium and the polymer matrix. Different heavy metals have toxicity at different concentrations, therefore, being able to change the dynamic range of the sensor is advantageous. This research is the first step towards developing a luminescent Pb sensor with a tunable dynamic range.
The focus of the following research was to provide an optimized particle stabilized foam of Laponite and Pluronic L62 in water by understanding (1) the Laponite-Pluronic interactions and properties for improved performance in a particle stabilized foam and (2) the interfacial properties between air and the Laponite-Pluronic complex. These studies were conducted using both bulk and interfacial rheology, XRD, sessile droplet, TGA and UV-vis. Two novel and simple techniques, lamella break point and capillary breakup extensional rheometry, were used to both understand the Laponite Pluronic L62 interaction and determine a different mechanism for foaming properties. Bulk rheological properties identified an optimal Laponite concentration of 2% with Pluronic L62 ranging from 2.5% and 6.5%, due to the ease of flow for the dispersion. The Pluronic L62 was observed to enhance the Laponite bulk rheological properties in solution. Additionally TGA showed a similar trend in thermal resistance to water with both addition of Laponite and Pluronic L62. XRD demonstrated that 0.25% Pluronic intercalated into Laponite from dried 2% Laponite films. XRD demonstrated that the Laponite matrix was saturated at 1% Pluronic L62. UV-vis demonstrated that a monolayer of Pluronic L62 is observed up to 0.65% Pluronic L62 onto Laponite. Interfacial rheology showed that Laponite enhances Pluronic L62 at the air-liquid interface by improving the storage modulus as low at 0.65% Pluronic L62 with 2% Laponite. The lamella breakpoint of Laponite with Pluronic films indicate strong film interaction due to higher increases in mass. Extensional rheology indicates that 2.5% to 6.5% Pluronic with 2% Laponite show the most filament resistance to stretching.
Within this educational endeavor instrumental development was explored through the investigation of microwave induce stable electromagnetic waves within a non-linear yttrium iron garnet ferromagnetic waveguide. The resulting magnetostatic surface waves were investigated as a possible method of rapid analytical evaluation of material composition. Initial analytical results indicate that the interaction seen between wave and material electric and magnetic fields will allow phase coherence recovery andanalysis leading to enhancement of analytical value. The ferromagnetic waveguide selected for this research was a high quality monocrystalline YIG (yttrium iron garnet) film. Magnetostatic spin waves (MSW) were produced within the YIG thin waveguide. Spin waves with desired character were used to analytically scan materials within the liquid and solid phase.
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