L'objectif de ce travail est de réaliser des substrats pour l’effet SEIRA (surface enhanced IR absorption) pour mesurer de faibles volumes de gaz ambiants possédant une signature moléculaire de 3,3 μm à 5,1 μm en exploitant la forte amplification de champ électrique due à la résonance plasmon de surface localisés. A cette fin, nous avons démontré la modulation des résonances de plasmon de surface localisées MIR (LSPR) dans les nanocristaux de ZnO dopés (NCs) dopés à Ga ou Al ainsi que dans des nanofils (NWs) de ZnO dopés Ga (GZO) et dans des nanofils coeur/coquille de ZnO/GZO. En ce qui concerne l’accordabilité de MIR LSPR dans les NC, nous avons modulé la résonance plasmon de surface dans des NC de ZnO dopés Ga et Al, de 3 à 5 μm en faisant varier la teneur en Al et en Ga de 3 à 9 at.%. L’incorporation des dopants s’est révélée homogène jusqu’à 6%. Au-delà (9%), l’incorporation était fortement hétérogène, révélant que la limite de solubilité était atteinte. Les NC présentent une faible activation des impuretés. L'activation était aussi faible que 8%. Les LSPR présentaient également un fort élargissement (largeur-à-mi-hauteur FWHM). Pour accroitre l'activation des dopants, nous avons synthétisés les NC dans des conditions pauvres en O et en passivant les NC synthétisés dans des conditions riches en O (en les isolant dans des matrices telles que Al2O3 et SiO2). Nous avons ainsi augmenté l'activation de 8% à 20% pour les deux stratégies. De plus, l'incorporation des NC dans les matrices a réduit l'élargissement spectral de moitié (de 2200 cm-1 pour les NC déposés à 1100 cm-1 pour les NC noyés en matrice). En correspondance, les effets d’auto-assemblage des nanocristaux sur leur LSPR ont été modélisés par simulation FDTD. Cela a fourni des indications quant aux mécanismes responsable de l’élargissement inhomogènes des LSPR de nanocristaux de GZO. Outre les nanoparticules, nous avons étudié des nanofils ZnO dopés Ga (GZO) et coeur/coquille (ZnO/GZO) synthétisés par CVD d’organométalliques . La première conclusion importante est que le gallium produit un fort effet surfacatnt lors de la croissance MOCVD de GZO. Au lieu de former des nanofils de section hexagonale, l’introduction de Ga modifie nettement l’énergie de surface des faces latérales et conduit à al formation de structures de type « sapins de Noël ». Ce constat est aussi valable pour les coquilles de GZO déposées sur coeur de ZnO. Dans ce cas, les coquilles démouillent et forment des structures hiérarchiques en branches. Concernant les propriétés optiques de ces objets, les mesures de FTIR-photo acoustiques ont démontré une signature d’absorption reliée à la présence de Ga et pouvant être accordée selon la teneur en Ga. Cette absorption reproduit le comportement d’une résonance plasmon de surface. Cette résonance a pu être accordée de 1600 à 1900 cm-1. / The scope of this thesis is about developing SEIRA (surface enhanced IR absorption) platform to probe low volumes of environmental gases that possess molecular signature from 3.3 μm to 5.1 μm leveraging the high field amplification of localised surface plasmon resonance (LSPR). To realise SEIRA, we demonstrated tuning MIR LSPR in Al or Ga doped ZnO nanocrystals (NCs) as well as in GZO or core-shell (ZnO/GZO) nanowires (NWs). Regarding tuning MIR LSPR in NCs, we demonstrated tunable MIR LSPR in Ga and Al doped ZnO NCs from 3 to 5 μm varying the Al or Ga content from 3 to 9 at.%. The incorporation of dopant was homogeneous up to 6%. At 9% dopant concentration, the incorporation was inhomogeneous, revealing the solubility limit has been reached. However, the NCs exhibited low activation of impurities. The activation was as low as 8%. The LSPR were characterised by large broadening as well. In order to enhance the dopant activation, we synthesized the NCs in O-poor conditions as well as passivated the NCs fabricated in O-rich condictions (by isolating and embedding them in matrices such as Al2O3 and SiO2 matrices). Both strategies improved the dopant activation from 8% up to 20%. Moreover, for assemblies of NCs dispersed in matrices, the broadening (FWHM) of the LSPR was reduced by half (from 2200 cm-1 in as-deposited NCs to 1100 cm-1 in embedded NCs). Correspondingly, the effect of the self-assembly of the nanocrystals on their LSPR was modeled by FDTD simulation and provided hindsight into the mechanisms responsible for the heterogeneous broadening of the LSPR. Finally, we have studied Ga-doped ZnO (GZO) and core-shell (ZnO/GZO) NW synthesized by MOCVD. The first important conclusion is that Ga plays a major surfactant role during the MOCVD growth of GZO. Instead of leading to hexagonal NWs, the introduction of Ga during the synthesis led to faceted “Christmas-tree” like architectures. The same observation held for core-shell ZnO-GZO nanowires; in the latter case, the GZO shell resulted in a dewetting branched architecture. Regarding their optical properties, photo-acoustic FTIR measurements revealed an absorption feature related to the Ga content, likely to be assigned to a plasmonic effect. This resonance could be tuned from 1600 to 1900 cm.

This thesis focuses on the analytical properties of the acoustic vibrations and applications of metallic nanoparticles. With regard to the analytical properties of the acoustic vibrations, we focus on nanoparticle acoustic resonance enhanced four-wave mixing (FWM) as an in situ characterization technique for characterizing nanoparticles’ shape, size, and size distribution. The nonlinear optical response of metallic nanoparticles is resonantly driven by the electrostriction force which couples to the acoustic vibrations of nanoparticles. Information about nanoparticles’ shape, size, and size distribution can be obtained by analyzing the resonant peak position and linewidth in the FWM signal which carries the information about the vibrational modes. We characterize different nanoparticle solutions of different materials, shapes, and sizes using this FWM technique. Information obtained from the FWM characterization agrees well with the scanning electron microscopic examination, indicating the FWM technique can serve as an in situ nanoparticle characterization tool. We also demonstrate the FWM technique can be used for monitoring nanoparticle growth in situ. iii With regard to the applications of metallic nanoparticles, we focus on quantification of an exogenous cancer biomarker Acetyl Amantadine using surface-enhanced Raman scattering (SERS). Raman spectroscopy can provide unique fingerprint information of molecules, which can be used as a chemical detection and identification technique. The intrinsically weak Raman signal caused by the small scattering cross section presents a barrier for trace chemical detection. Localized surface plasmon resonance of metallic nanoparticles can provide large local field enhancement, which can be utilized to enhance the intrinsically weak Raman signal. In order to achieve higher local field enhancement, we focus on using the gap structures formed between nanoparticles instead of using discrete nanoparticles. Molecules should locate within the hot spots of the gap structures to experience the largest enhancement. This requires that molecules should be extracted from volume onto the metallic surface. Based on these guidelines, two SERS platforms are designed using gold nanoparticles (nanorods and nanospheres) combined with different surface functionalization techniques. The performance of these two platforms are characterized by investigating the sensitivity and limit of detection (LOD). 16 ng/mL and 0.4 ng/mL LODs are achieved for nanorod and nanosphere platforms, respectively. / Graduate

Surface enhanced Raman scattering (SERS) has achieved much attention since its conception in 1974. The analytical technique overcomes many difficulties associated with conventional Raman whilst also increasing sensitivity. However, the increased interest and work in the field has also identified flaws, many of which are centred on the irreproducibility of the SERS enhancement effect. The majority of the work described in this thesis focusses on the ‘optimisation’ of solid-state and solution based SERS systems. Optimisation plays a crucial role in maximising both enhancement effects and reproducibility. Here criteria are outlined for the synthesis of high performance solid-state SERS substrates and the synthesis of a range of substrates is assessed, each with associated pros and cons. The most successful substrate was synthesised by exploiting redox potentials which allow for the direct deposition of silver onto copper foil. The deposition times and temperatures were optimised sequentially to generate a high performance substrate capable of detecting Rhodamine 6G at trace levels. Reproducibility comparisons of the silver on copper (SoC) substrate were carried out against commercial substrates: Klarite and QSERS, multiple univariate and multivariate methods were used to assess the substrates performance. The results confirmed that the SoC substrate performed better than both the commercial substrates. The work also highlights the importance of using multiple data analysis methods in order to assess the performance of a solid-state SERS substrate. Deposition of the silver surface was also successful on British 2p coins allowing the for the detection and discrimination of illegal and legal drugs when coupled with multivariate data analysis methods such as PCA and PLS. Solution based SERS analyses were also carried out successfully using different optimisation strategies. The initial investigation involved careful control of the individual components of a SERS system (nanoparticles, aggregating agents and analyte) in order to establish a low limit of detection for the increasingly abused ‘legal high’ MDAI. The use of a reduced factorial design was then successfully employed to explore a greater number of SERS variables and define a low limit of detection for the class B drug mephedrone. The robust experimental design also allowed an insight into the importance of each of the individual components within a solution based SERS system. The final piece of work carried out was the SERS discrimination of antibiotics: ampicillin, ticarcillin and carbenicillin. Optimisation of the solution based experiment allowed the in-situ hydrolysis of the β-lactam moiety present in ampicillin rendering it pharmacologically inactive to be followed under acidic conditions at concentrations of 10 ppm.

Class of 2017 Abstract / Objectives: To determine if the addition of oral alvimopan, liposomal bupivacaine and intravenous acetaminophen as part of a comprehensive enhanced recovery after surgery (ERAS) program decreases length of stay, recovery time and narcotic/acetaminophen use without affecting colorectal surgery patient outcomes. Methods: Patients were compared before and after the implementation of alvimopan, liposomal bupivacaine and intravenous acetaminophen with an ERAS program. The primary outcome was hospital length of stay (measured in hours). Secondary outcomes included change in time to first meal, bowel sounds, and bowel movement (measured in hours), pain scores (visual analog scale 0-10), opioid use (measured in morphine equivalent milligrams), and acetaminophen use (measured in mg). Results: Thirty-seven individuals were included in the pre implementation population and fifty one patients were included in the post implementation population. The mean length of stay decreased from 124.3 hours to 100.2 hours (P equals 0.13) with the addition of the ERAS program with the three medications. The 24 hour morphine equivalent intervals for seventy-two hours following surgery decreased from 125.8 mg (day 1), 81.9 mg (day 2) and 44.5 mg (day 3) to 44.3 mg (day 1), 22.8 mg (day 2) and 13.2 mg (day 3) (P less than 0.005 for each one). Conclusions: The addition of alvimopan, liposomal bupivacaine and intravenous acetaminophen as part of a comprehensive ERAS program decreased length of stay but not significantly. However, the addition of these three medications with the ERAS program changes was associated with a statistically significant decrease in opioid use.

This study explored the critical features of temporal synchrony for the facilitation of prenatal perceptual learning with respect to unimodal stimulation using an animal model, the bobwhite quail. The following related hypotheses were examined: (1) the availability of temporal synchrony is a critical feature to facilitate prenatal perceptual learning, (2) a single temporally synchronous note is sufficient to facilitate prenatal perceptual learning, with respect to unimodal stimulation, and (3) in situations where embryos are exposed to a single temporally synchronous note, facilitated perceptual learning, with respect to unimodal stimulation, will be optimal when the temporally synchronous note occurs at the onset of the stimulation bout. To assess these hypotheses, two experiments were conducted in which quail embryos were exposed to various audio-visual configurations of a bobwhite maternal call and tested at 24 hr after hatching for evidence of facilitated prenatal perceptual learning with respect to unimodal stimulation. Experiment 1 explored if intermodal equivalence was sufficient to facilitate prenatal perceptual learning with respect to unimodal stimulation. A Bimodal Sequential Temporal Equivalence (BSTE) condition was created that provided embryos with sequential auditory and visual stimulation in which the same amodal properties (rate, duration, rhythm) were made available across modalities. Experiment 2 assessed: (a) whether a limited number of temporally synchronous notes are sufficient for facilitated prenatal perceptual learning with respect to unimodal stimulation, and (b) whether there is a relationship between timing of occurrence of a temporally synchronous note and the facilitation of prenatal perceptual learning. Results revealed that prenatal exposure to BSTE was not sufficient to facilitate perceptual learning. In contrast, a maternal call that contained a single temporally synchronous note was sufficient to facilitate embryos’ prenatal perceptual learning with respect to unimodal stimulation. Furthermore, the most salient prenatal condition was that which contained the synchronous note at the onset of the call burst. Embryos’ prenatal perceptual learning of the call was four times faster in this condition than when exposed to a unimodal call. Taken together, bobwhite quail embryos’ remarkable sensitivity to temporal synchrony suggests that this amodal property plays a key role in attention and learning during prenatal development.

Class of 2017 Abstract / Objectives: To determine if the addition of oral alvimopan, liposomal bupivacaine and intravenous acetaminophen as part of a comprehensive enhanced recovery after surgery (ERAS) program decreases length of stay, recovery time and narcotic/acetaminophen use without affecting colorectal surgery patient outcomes. Methods: Patients were compared before and after the implementation of alvimopan, liposomal bupivacaine and intravenous acetaminophen with an ERAS program. The primary outcome was hospital length of stay (measured in hours). Secondary outcomes included change in time to first meal, bowel sounds, and bowel movement (measured in hours), pain scores (visual analog scale 0-10), opioid use (measured in morphine equivalent milligrams), and acetaminophen use (measured in mg). Results: Thirty-seven individuals were included in the pre implementation population and fifty one patients were included in the post implementation population. The mean length of stay decreased from 124.3 hours to 100.2 hours (P equals 0.13) with the addition of the ERAS program with the three medications. The 24 hour morphine equivalent intervals for seventy-two hours following surgery decreased from 125.8 mg (day 1), 81.9 mg (day 2) and 44.5 mg (day 3) to 44.3 mg (day 1), 22.8 mg (day 2) and 13.2 mg (day 3) (P less than 0.005 for each one). Conclusions: The addition of alvimopan, liposomal bupivacaine and intravenous acetaminophen as part of a comprehensive ERAS program decreased length of stay but not significantly. However, the addition of these three medications with the ERAS program changes was associated with a statistically significant decrease in opioid use.

acase@tulane.edu / The objective of this research is to study the surface/interfacial phenomena via video-microscopic observation and quantification inside a micro-channel or microcapillary, which can mimic the operating conditions of practical problems, such as ink-jet, lubricant oil neutralization and enhanced oil recovery. In the second chapter, a micropipette-in-microcapillary method is described for the surface tension measurement at high temperatures, which mimics the dimension and working environment of ink-jet print head. Temperature control within the confined space of a capillary was achieved by coating the outer surface of the housing microcapillary with an electrically conductive, transparent, tin-doped indium oxide (ITO) thin film as a heating jacket. The precision of this technique was discussed according to the comparisons of our results with published reference data for water, n-hexadecane, and n-decane at both room and elevated temperatures. Traditionally, the neutralization of sulfuric acid by engine oils has been the major focus, however, due to the introduce of biofuel or ethanol the acetic acid has become an important concern. In the third chapter, based on micropipette-in-square-channel video-microscopy setup, the neutralization reaction mechanism and reaction kinetics of acetic acid by fully formulated lubricant oil is discussed. It was found that the neutralization exists simultaneously on the oil-acid-interface and bulk-oil phase during the droplet shrinkage. Besides, FTIR and NMR analysis show the neutralization of acetic acid as an instantaneous process, and almost all of the dissolved acetic acid in the bulk is eventually neutralized. Due to the minor role of acetic acid dissolution compared to the interfacial reaction, an interface-reaction-rate-controlled kinetic mechanism is proposed as approximation to describe the neutralization process at different conditions. When glacial and diluted acetic acid droplets were neutralized in fully formulated lubricant oil, the experimentally measured shrinking radius agreed very well with the mathematical model. According to Arrhenius equation, the activation energy of neutralization reaction was determined to be constant and its range (Ea>21 kJ/mol) further validated the assumption of interface-controlled reaction kinetics. In the final chapter, an oil-soluble surfactant prepared by Eni S.p.A. was studied to enhance crude oil mobilization in cryolite-packed miniature bed, which provided a transparent porous media at the microscopic level. When the porous media was imbued with crude oil, the presence of the surfactant in the oil phase was able to improve the mobilization performance of crude oil by flushing. In order to deliver the oil-soluble surfactant and apply it to the removal of crude from porous media, an SDS solution was used to solubilize the surfactant, and the formation of SDS/Eni-Surfactant micellar solution was confirmed by Cryo-SEM images. Using the prepared micellar solutions in oil-removal tests on the packed bed, a very high effectiveness was demonstrated by image binarization, thus confirming the possibility to deliver liposoluble surfactants to the porous-media-trapped crude oil by means of hydrosoluble carriers. / 1 / Yufei Duan

In the framework of the quasi-static approximation (QSA), some theoretical studies were conducted within the local response approximation (LRA). In these studies, certain plasmonic and plexcitonic systems were proposed, and their spectroscopic properties investigated. The QSA allows us to study metal nanoparticles (MNPs) and inter-particle distances that are small compared to the wavelength of light in the medium surrounding the MNPs, while the LRA enables us to utilize the bulk dielectric response of the metal in consideration. We have studied the following properties in detail: localized surface plasmon resonances (LSPRs), plasmon-induced transparency (PIT), and plasmon-enhanced fluorescence (PEF), while exciton-induced transparency (EIT) has only been partly studied. LSPR and PIT are properties of plasmonic systems while PEF and EIT are properties of plexcitonic systems. Both PIT and EIT are forms of electromagnetically-induced transparency. We started by constructing a geometry-based theoretical model that predicts the LSPR formula of any member of a certain group of single MNPs, using the LSPR for the most complex MNP geometry in the group. The model shows that from the LSPR of a nanorice, one could predict the LSPRs of concentric nanoshells, solid and cavity nanorods and nanodisks, respectively, and solid and cavity nanospheres. These formulae serve as quick references for predicting LSPRs since they can easily be compared to LSPRs obtained from spectral analysis. Likewise, we studied LSPR in addition to PIT in a nanoegg-nanorod dimer. We proposed this dimer in order to investigate how the interplay between plasmon coupling and MNP sizes affects PIT in complex geometries such as nanoeggs. Our result shows that the formation of PIT dips — regions in the dimer spectra where little or no incident radiation is absorbed by the dimer — are strongly-dependent on the nanorod size, due to the dependence of the plasmon coupling strength on the half-length of the nanorod. We investigated the phenomenon of PEF using a nanoegg-emitter system and a nanorod-emitter system, respectively. Emitters are organic or inorganic materials whose radiative decay rates increase dramatically when placed near a MNP subjected to plasmon excitation. Our theoretical results show that the choice of the MNP-emitter system to use depends on both the intrinsic quantum yield of the emitter and the antenna efficiency of the MNP. Theory shows that PEF is more substantial when the former is very low, and it will always occur if the latter is greater than the former. A nanorod-emitter system should serve as the preferred choice, due to the relatively easier synthesis of nanorods compared to nanoeggs, and the large longitudinal polarizability of nanorods as a result of the lightning rod effect. However, our theoretical model also shows that a nanoegg-emitter system can rival the PEF parameters obtained in a nanorod-emitter system, due to an increase in the Purcell factor of the emitter with increasing core-offset of the nanoegg, resulting from the presence of dipole-active modes in the nanoegg. / Thesis (PhD (Physics))--University of Pretoria, 2020. / University of Pretoria / National Research Foundation (NRF) / Physics / PhD (Physics) / Unrestricted

Thesis (Ph.D.)--Boston University / The large electromagnetic field enhancement provided by nanostructured noble metal surfaces forms the foundation for a series of enabling optical analytical techniques, such as surface enhanced Raman spectroscopy (SERS), surface enhanced IR absorption spectroscopy (SEIRA), surface enhanced fluorescent microscopy (SEF), to name only a few. Critical sensing applications have, however, other substrate requirements than mere peak signal enhancement. The substrate needs to be reliable, provide reproducible signal enhancements, and be amenable to a combination with microfluidic chips or other integrated sensor platforms. These needs motivate the development of engineerable SERS substrate "chips" with defined near- and far-field responses. In this dissertation, two types of rationally designed SERS substrates - nanoparticle cluster arrays (NCAs) and SERS stamp - will be introduced and characterized. NCAs were fabricated through a newly developed template guided self-assembly fabrication approach, in which chemically synthesized nanoparticles are integrated into predefined patterns using a hybrid top-down/bottom-up approach. Since this method relies on chemically defined building blocks, it can overcome the resolution limit of conventional lithographical methods and facilitates higher structural complexity. NCAs sustain near-field interactions within individual clusters as well as between entire neighboring clusters and create a multi-scale cascaded E-field enhancement throughout the entire array. SERS stamps were generated using an oblique angle metal deposition on a lithographically defined piston. When mounted on a nanopositioning stage, the SERS stamps were enabled to contact biological surfaces with pristine nanostructured metal surfaces for a label-free spectroscopic characterization. The developed engineered substrates were applied and tested in critical sensing applications, including the ultratrace detection of explosive vapors, the rapid discrimination of bacterial pathogens, and the label-free monitoring of the enzymatic degradation of pericellular matrices of cancer cells.

In this dissertation I examine the properties and origins of the most energetic component of Mercury's atmosphere and how it couples to the planet's magnetosphere and space environment. Mercury' s atmosphere consists of particles liberated from its surface that follow ballistic, collisionless trajectories under the influence of gravity and solar radiation pressure. This tenuous atmosphere can be classified as an exosphere where the exobase boundary is the planet's surface. To explain how this exosphere is sustained, a number of theories have been presented: (1) thermal evaporation from the hot surface; (2) photo-desorption of surface materials by UV solar radiation; (3) sputtering by plasma surface interactions; and (4) vaporization of the surface by micro-meteorite impacts. Using a 3-dimensional numerical model, I determine the role each source has in populating the exosphere. New observations of Mercury's escaping atmosphere are presented using novel imaging techniques in which sodium acts as a tracer to identify atmospheric sources. I discuss the implications of these measurements for our understanding of the physical processes at work in the exosphere, and provide a foundation for modeling such processes. For the first time, this work quantifies the variability in the loss of Mercury's sodium as a seasonal effect. My observations show that atmospheric escape can, at times, exceed 10^24 Na atoms s^-1, nearly twice the highest rate previously reported. By forward modeling Mercury's atmospheric escape, I place new constraints on the source properties and eliminate the prevailing theory that the escaping tail is sputtered from the surface by solar wind ions. The MESSENGER spacecraft has recently discovered that sodium is distributed unevenly over the surface and that the magnetosphere is offset from the planet's center. Using the first model to include these effects, I demonstrate the magnetosphere's influence upon exospheric sources by simulating asymmetries observed in the escaping atmosphere. I conclude that the exosphere is sustained by a combination of micro-meteorite impact vaporization and photo-desorption that is locally enhanced by precipitating ions.