Thin film arrays of molecules or supramolecules are active subjects of investigation because of their potential value in electronics, chemical sensing, catalysis, and other areas. Scanning probe microscopes (SPMs), including scanning tunneling microscopes (STMs) and atomic force microscopes (AFMs) are commonly used for the characterization and metrology of thin film arrays. As opposed to transmission electron microscopy (TEM), SPMs have the advantage that they can often make observations of thin films in air or liquid, while TEM requires highly specialized techniques if the sample is to be in anything but vacuum. SPM is a surface imaging technique, while TEM typically images a 2D projection of a thin 3D sample. Additionally, variants of SPM can make observations of more than just topography; for instance, magnetic force microscopy measures nanoscale magnetic properties. Thin film arrays are typically two-dimensionally periodic. A perfect, infinite two-dimensionally periodic array is mathematically constrained to belong to one of only 17 possible 2D plane symmetry groups. Any real image is both finite and imperfect. Crystallographic Image Processing (CIP) is an algorithm that Fourier transforms a real image into a 2D array of complex numbers, the Fourier coefficients of the image intensity, and then uses the relationship between those coefficients to first ascertain the 2D plane symmetry group that the imperfect, finite image is most likely to possess, and then adjust those coefficients that are symmetry-related so as to perfect the symmetry. A Fourier synthesis of the symmetrized coefficients leads to a perfectly symmetric image in direct space (when accumulated rounding and calculation errors are ignored). The technique is, thus, an averaging technique over the direct space experimental data that were selected from the thin film array. The image must have periodicity in two dimensions in order for this technique to be applicable. CIP has been developed over the past 40 years by the electron crystallography community, which works with 2D projections from 3D samples. Any periodic sample, whether it is 2D or 3D has an "ideal structure" which is the structure absent any crystal defects. The ideal structure can be considered one average unit cell, propagated by translation into the whole sample. The "real structure" is an actual sample containing vacancies, dislocations, and other defects. Typically the goal of electron and other types of microscopy is examination of the real structure, as the ideal structure of a crystal is already known from X-ray crystallography. High resolution transmission electron microscope image based electron crystallography, on the other hand, reveals the ideal crystal structure by crystallographic averaging. The ideal structure of a 2D thin film cannot be easily in a spatially selective fashion examined by grazing incidence X-ray or low energy electron diffraction based crystallography. SPMs straightforwardly observe thin films in direct space, but SPM accuracy is hampered by blunt or multiple tips and other unavoidable instrument errors. Especially since the film is often of a supramolecular system whose molecules are weakly bonded (via pi bonds, hydrogen bonds, etc.) both to the substrate and to each other, it is relatively easy for a molecule from the film to adhere to the scanning tip during the scan and become part of the tip during subsequent observation. If the thin film array has two-dimensional periodicity, CIP is a unique and effective tool both for image enhancement (determination of ideal structure) and for the quantification of overall instrument error. In addition, if a sample of known 2D periodicity is scanned, CIP can return information about the contribution of the instrument itself to the image. In this thesis we show how the technique is applied to images of two dimensionally periodic samples taken by SPMs. To the best of our knowledge, this has never been done before. Since 2D periodic thin film arrays have an ideal structure that is mathematically constrained to belong to one of the 17 plane symmetry groups, we can use CIP to determine that group and use it for a particularly effective averaging algorithm. We demonstrate that the use of this averaging algorithm removes noise and random error from images more effectively than translational averaging, also known as "lattice averaging" or "Fourier filtering". We also demonstrate the ability to correct systematic errors caused by hysteresis in the scanning process. These results have the effect of obtaining the ideal structure of the sample, averaging out the defects crystallographically, by providing an average unit cell which, when translated, represents the ideal structure. In addition, if one has recorded a scanning probe image of a 2D periodic sample of known symmetry, we demonstrate that it is possible to use the Fourier coefficients of the image transform to solve the inverse problem and calculate the point spread function (PSF) of the instrument. Any real scanning probe instrument departs from the ideal PSF of a Dirac delta function, and CIP allows us to quantify this departure as far as point symmetries are concerned. The result is a deconvolution of the "effective tip", which includes any blunt or multiple tip effects, as well as the effects caused by adhesion of a sample molecule to the scanning tip, or scanning irregularities unrelated to the physical tip. We also demonstrate that the PSF, once known, can be used on a second image taken by the same instrument under approximately the same experimental conditions to remove errors introduced during that second imaging process. The preponderance of two-dimensionally periodic samples as subjects of SPM observation makes the application of CIP to SPM images a valuable technique to extract a maximum amount of information from these images. The improved resolution of current SPMs creates images with more higher-order Fourier coefficients than earlier, "softer" images; these higher-order coefficients are especially amenable to CIP, which can then effectively magnify the resolution improvement created by better hardware. The improved resolution combined with the current interest in supramolecular structures (which although 3D usually start building on a 2D periodic surface) appears to provide an opportunity for CIP to significantly contribute to SPM image processing.

The research presented in this dissertation involves the synthesis, characterization, and application of novel anionic and cationic chiral molecular micelles in capillary electrophoresis (CE) for the separation of diverse chiral compounds. Chapter 1 presents brief overview of the surfactants, micelle polymer, CE and micellar electrokinetic chromatography (MEKC). Chapter 2 describes the simultaneous enantioseparation of eight single chiral center â-blockers using two novel leucine and isoleucine based polymeric surfactants. The simultaneous enantioseparation of multichiral center bearing â-blockers, nadolol and labetalol is described in chapter 3. A synergistic approach, using a combination of polysodium N-undecenoxycarbonyl-L-isoleucinate (poly-L-SUCIL) and sulfated â-CD showed dramatic enantioseparation of four stereoisomers of nadolol. On the other hand for labetalol, enantiomeric separation remains unaffected using the dual chiral selector system. Chapter 4 deals with the enantiomeric separation of the binaphthyl derivatives that was found to be influenced by pH, type and concentration of the background electrolyte as well as concentration of the polymeric surfactant. In chapter 5, characterization of five alkenoxy leucine-based surfactants with variations in chain length (C8-C11), polymerization concentration and degree of polymerization showed significant effects on the chiral resolution and efficiency of hydrophobic â-blockers. The synthesis and characterization of two positively charged amino acid derived chiral ionic liquids (ILs) and their corresponding polymers is presented in chapter 6. Chiral separation of two acidic analyte (difficult to resolve with anionic micelles) can be achieved with both monomers and polymers of ILs. In chapter 7, the synthesis and detailed characterization of three pH independent amino acids derived (L-leucinol, L-isoleucinol and L-valinol) sulfated chiral polymeric surfactants is presented. These chiral sulfated surfactants are thoroughly characterized and the morphological behavior of polymeric sulfated surfactants is revealed using cryogenic high-resolution electron microscopy. The work clearly demonstrates for the first time the superiority of chiral separation in MEKC coupled to mass spectrometry at low pH. Finally, in chapter 8, six amino acid derived chiral surfactants with carboxylate and sulfate head groups were compared for enantioseparation of broad range of structurally diverse racemic compounds at neutral and basic pH conditions.

Thesis (Ph. D.)--Ohio State University, 2006. / Title from first page of PDF file. Includes bibliographical references (p. 220-225).

M.Sc. / Donor-acceptor (D-A) systems consist of a donor covalently or non-covalently linked to an acceptor. The simplest D–A system consists of a donor linked to an acceptor and is called a dyad system. Photoactive dyad systems are molecular devices designed to perform through the separation of charge separation states and the conversion of solar energy to chemical energy in analogy to photosynthesis.1 These dyad systems consist of a donor which is usually a chromophore and an acceptor. The design of these systems is guided to mimic photo-induced electron transfer (PET) and charge separation (CS), which are fundamental processes of photosynthesis. In nature, photosynthetic units are often built from dyads consisting of pigments like chlorophyll (donors), non–covalently linked to quinones, (acceptors). The donor harvests light energy and transfers the energy to the nearby pigment molecules until it eventually reaches a special region of the chlorophyll macrocycle called the reaction centre where this light energy is then converted to electrochemical energy. Photoactive dyad systems act as artificial photosynthetic models as they reproduce photo–induced electron transfer and charge separation of natural photosynthesis. In this project, dyad systems were made by covalently linking zinc pheophorbide, a modified chlorophyll derivative to double–walled carbon nanotubes (DWCNTs). Zinc pheophorbide acts as the donor and DWCNTs as the acceptors. Chlorophyll was modified by cutting the phytol chain and inserting zinc as the central metal to yield zinc pheophorbide. This derivative is stable against irradiation, has a good range of acceptor wavelength and is also a good light harvester. DWCNTs are one dimensional nanowires with two concentric tubes. They readily accept electrons because they have an extended π electron system. These electrons are then transported efficiently under ballistic conditions. DWCNTs were synthesised by catalytic chemical vapour deposition (CCVD) of methane over Mg0.99Co0.075Mo0.025O catalyst. In dyad system 1, amidated zinc pheophorbide molecules were covalently attached to oxidised DWCNTs in the presence of N–ethyl–N’–(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) \ and N–hydroxysuccinnimide (NHS) as a catalysts. Dyad system 2 was synthesized by attaching zinc pheophorbide molecules to amidated DWCNTs using the same catalysts.

This thesis concerns the application of aberration corrected scanning transmission electron microscopy (STEM) to the quantitative analysis of industrial Pd-Pt core-shell catalyst nanoparticles. High angle annular dark field imaging (HAADF), an incoherent imaging mode, is used to determine particle size distribution and particle morphology of various particle designs with differing amounts of Pt coverage. The limitations to imaging, discrete tomography and spectral analysis imposed by the sample’s sensitivity to the beam are also explored. Since scattered intensity in HAADF is strongly dependent on both thickness and composition, determining the three dimensional structure of a particle and its bimetallic composition in each atomic column requires further analysis. A quantitative method was developed to interpret single images, obtained from commercially available microscopes, by analysis of the cross sections of HAADF scattering from individual atomic columns. This technique uses thorough detector calibrations and full dynamical simulations in order to allow comparison between experimentally measured cross section to simulated ones and is shown to be robust to many experimental parameters. Potential difficulties in its applications are discussed. The cross section approach is tested on model materials before applying it to the identification of column compositions of core-shell nanoparticles. Energy dispersive X-ray analysis is then used to provide compositional sensitivity. The potential sources of error are discussed and steps towards optimisation of experimental parameters presented. Finally, a combination of HAADF cross section analysis and EDX spectrum imaging is used to investigate the core-shell nanoparticles and the results are correlated to findings regarding structure and catalyst activity from other techniques. The results show that analysis by cross section combined with EDX spectrum mapping shows great promise in elucidating the atom-by-atom composition of individual columns in a core-shell nanoparticle. However, there is a clear need for further investigation to solve the thickness / composition dualism.

Three-dimensional porous single crystals (PSCs) are a recent development in the growing world of mesoporous material. The mesoporosity allows for the material to retain their nanoproperties whilst being bulk in size. The current work concentrates on chromium oxide and cobalt oxide PSCs formed in the templates SBA-15 and KIT-6. HRTEM is the main technique used in this investigation, looking at the morphology and single crystallinity of these materials. A growth mechanism for the PSC material is proposed based on HRTEM observations. XRD studies revealed that the confinement effect, caused by the mesopores, reduces the temperature for both cobalt and chromium oxide crystallisation, as well as a different intermediate route from the metal nitrates. The properties of chromium oxide PSC are also investigated magnetically and catalytically. Some metal oxides in different templates are also presented, despite no PSC forming. HRTEM work on other nanomaterials, based on collaboration, is also presented.

The main problem addressed by this dissertation is the accurate and automated determination of electron microscope imaging conditions. This enables the restoration of the object wave, which confers direct structural information about the specimen, from sets of differently aberrated images. An important member in the imaging chain is the image recording device, in many cases now a charge-coupled device (CCD) camera. Previous characterisations of these cameras often relied on the unjustified assumption that the Modulation Transfer Function (MTF) also correctly describes the spatial frequency dependent attenuation of the electron shot noise. A new theory is therefore presented that distinguishes between signal and noise transfer. This facilitates the evaluation of both properties using a detailed Monte-Carlo simulation model for the electron and photon scattering in the scintillator of the camera. Furthermore, methods for the accurate experimental determination of the signal and noise transfer functions are presented. In agreement with the Monte-Carlo simulations, experimental results for commercially available CCD cameras show that the signal transfer is significantly poorer than the noise transfer. The centrepiece of this dissertation is the development of new methods for determining the relative aberrations in a set of images and the absolute symmetric aberrations in the restored wave. Both are based on the analysis of the phase information in the Fourier domain and give each Fourier component a weight independent of its strength. This makes the method suitable even for largely crystalline samples with little amorphous contamination, where conventional methods, such as automated diffractogram fitting, usually fail. The method is then extended to also cover the antisymmetric aberrations, using combined beam tilt and focal series. The applicability of the new method is demonstrated with object wave restorations from tilt and focal series of complex inorganic block oxides and of carbon nanotubes filled with one-dimensional inorganic crystals. The latter specimens allowed for the first time a direct comparison between the phase shift in the restored object wave of a specimen with precisely known thickness and the value predicted by simulations.

The main problem addressed by this dissertation is the accurate and automated determination of electron microscope imaging conditions. This enables the restoration of the object wave, which confers direct structural information about the specimen, from sets of differently aberrated images. An important member in the imaging chain is the image recording device, in many cases now a charge-coupled device (CCD) camera. Previous characterisations of these cameras often relied on the unjustified assumption that the Modulation Transfer Function (MTF) also correctly describes the spatial frequency dependent attenuation of the electron shot noise. A new theory is therefore presented that distinguishes between signal and noise transfer. This facilitates the evaluation of both properties using a detailed Monte-Carlo simulation model for the electron and photon scattering in the scintillator of the camera. Furthermore, methods for the accurate experimental determination of the signal and noise transfer functions are presented. In agreement with the Monte-Carlo simulations, experimental results for commercially available CCD cameras show that the signal transfer is significantly poorer than the noise transfer. The centrepiece of this dissertation is the development of new methods for determining the relative aberrations in a set of images and the absolute symmetric aberrations in the restored wave. Both are based on the analysis of the phase information in the Fourier domain and give each Fourier component a weight independent of its strength. This makes the method suitable even for largely crystalline samples with little amorphous contamination, where conventional methods, such as automated diffractogram fitting, usually fail. The method is then extended to also cover the antisymmetric aberrations, using combined beam tilt and focal series. The applicability of the new method is demonstrated with object wave restorations from tilt and focal series of complex inorganic block oxides and of carbon nanotubes filled with one-dimensional inorganic crystals. The latter specimens allowed for the first time a direct comparison between the phase shift in the restored object wave of a specimen with precisely known thickness and the value predicted by simulations.