The Continuous Electrodeposition of Manganese

The object of this research was to produce a workable electrolytic cell for the continuous deposition of manganese from aqueous sulphate solutions and determine the critical factors in its oper­ation.

Capillary jet instability under the influence of gravity

The focus of this paper is on the effect of gravity stretching on disturbed capillary jet instability. Break-up and droplet formation under low flows are simulated using finite difference solution of a one-dimensional approximation of disturbed capillary jet instability chosen from the work by Eggers and Dupont (J. Fluid Mech. 155 (1994) 289). Experiments were conducted using water and aqueous glycerol solutions to compare with simulations. We use a gravity parameter, G, which quantifies gravity stretching by relating flow velocity, orifice size and acceleration and is the reciprocal of the Fronde number. The optimum disturbance frequency Omega(opt) was found to be inversely proportional to G. However, this relationship appears to be complex for the range of G's investigated. At low G, the relationship between Omega(opt) and G appears to be linear but takes on a weakly decaying like trend as G increases. As flows are lowered, the satellite-free regime decreases, although experimental observation found that merging of main and satellite drops sometimes offset this effect to result in monodispersed droplet trains post break-up. Viscosity did not significantly affect the relationship between the disturbance frequency and G, although satellite drops could be seen more clearly close to the upper limit for instability at high G's. It is possible to define regimes of satellite formation under low flows by considering local wavenumbers at the point of instability. (C) 2004 Elsevier Ltd. All rights reserved.

Drug/Water interactions in hydrogel matrices

The primary aim of this research has been the investigation of the role of water structuring effects in the widely different extents of irritancy displayed by certain antibiotics. The compounds involved were members of the Lincomycin group of antibiotics. The aqueous solution behaviour of these co~pounds was studied using techniques such as vapour pressure osmometry end differential scanning calorimetry (D.S.C.). The effects of the antibiotics on water structure in hydrogel membrane preparations In which the equilibrium water content (E.W.C.) and constituent amounts of freezing and non-freezing water ware varied were also investigated using D.S.C. The permeability of water swollen hydrogel preparations to aqueous antibiotic solutions as well as other solutes were studied. A series of hydrogel preparations into which the antibiotics had been incorporated during polymerisation were developed and used in studies of the effects of the antibiotics end their water structure modifications on the permeation of a range of solutes.

Optical chemsensors utilizing long-period fiber gratings UV-inscribed in D-fiber with enhanced sensitivity through cladding etching

A novel implementation of an optical chemsensor device is reported based on long-period fiber grating structures ultraviolet-inscribed in D-fiber, with sensitivity enhancement by cladding etching. The results of a comparative study using D-fiber devices and similar structures in standard optical fiber reveal that the D-fiber devices offer substantially greater sensitivity both with and without etching. Based on a calibrated response to changes in refractive index, the grating devices have been used to measure the concentrations of aqueous sugar solutions, demonstrating the potential capability to detect concentration changes as small as 0.2%.

Simultaneous measurement of temperature and external refractive index by use of a hybrid grating in D fiber with enhanced sensitivity by HF etching

We propose a dual-parameter optical sensor device achieved by UV inscription of a hybrid long-period grating-fiber Bragg grating structure in D fiber. The hybrid configuration permits the detection of the temperature from the latter's response and measurement of the external refractive index from the former's response. In addition, the host D fiber permits effective modification of the device's sensitivity by cladding etching. The grating sensor has been used to measure the concentrations of aqueous sugar solutions, demonstrating its potential capability to detect concentration changes as small as 0.01%.

Optical sensor based on hybrid LPG/FBG in D-fiber for simultaneous refractive index and temperature measurement

A dual-parameter optical sensor has been realized by UV-writing a long-period and a Bragg grating structure in D-fiber. The hybrid configuration permits the detection of the temperature from the latter and measuring the external refractive index from the former responses, respectively. The employment of the D-fiber allows as effective modification and enhancement of the device sensitivity by cladding etching. The grating sensor has been used to measure the concentrations of aqueous sugar solutions, demonstrating the potential capability to detect concentration changes as small as 0.01%.

Optical chemsensors utilizing long-period fiber gratings UV-inscribed in D-fiber with enhanced sensitivity through cladding etching

A novel implementation of an optical chemsensor device is reported based on long-period fiber grating structures ultraviolet-inscribed in D-fiber, with sensitivity enhancement by cladding etching. The results of a comparative study using D-fiber devices and similar structures in standard optical fiber reveal that the D-fiber devices offer substantially greater sensitivity both with and without etching. Based on a calibrated response to changes in refractive index, the grating devices have been used to measure the concentrations of aqueous sugar solutions, demonstrating the potential capability to detect concentration changes as small as 0.2%.

Simultaneous measurement of temperature and external refractive index by use of a hybrid grating in D fiber with enhanced sensitivity by HF etching

We propose a dual-parameter optical sensor device achieved by UV inscription of a hybrid long-period grating-fiber Bragg grating structure in D fiber. The hybrid configuration permits the detection of the temperature from the latter's response and measurement of the external refractive index from the former's response. In addition, the host D fiber permits effective modification of the device's sensitivity by cladding etching. The grating sensor has been used to measure the concentrations of aqueous sugar solutions, demonstrating its potential capability to detect concentration changes as small as 0.01%.

Optical sensor based on hybrid LPG/FBG in D-fiber for simultaneous refractive index and temperature measurement

A dual-parameter optical sensor has been realized by UV-writing a long-period and a Bragg grating structure in D-fiber. The hybrid configuration permits the detection of the temperature from the latter and measuring the external refractive index from the former responses, respectively. The employment of the D-fiber allows as effective modification and enhancement of the device sensitivity by cladding etching. The grating sensor has been used to measure the concentrations of aqueous sugar solutions, demonstrating the potential capability to detect concentration changes as small as 0.01%.

Analysis of bio-derived platform chemicals in ionic liquid media by desorption/ionization mass spectrometry

In this work, desorption/ionization mass spectrometry was employed for the analysis of sugars and small platform chemicals that are common intermediates in biomass transformation reactions. Specifically, matrix-assisted laser desorption/ionization (MALDI) and desorption electrospray ionization (DESI) mass spectrometric techniques were employed as alternatives to traditional chromatographic methods. Ionic liquid matrices (ILMs) were designed based on traditional solid MALDI matrices (2,5-dihydroxybenzoic acid (DHB) and α-cyano-4-hydroxycinnamic acid (CHCA)) and 1,3-dialkylimidazolium ionic liquids ([BMIM]Cl, [EMIM]Cl, and [EMIM]OAc) that have been employed as reaction media for biomass transformation reactions such as the conversion of carbohydrates to valuable platform chemicals. Although two new ILMs were synthesized ([EMIM][DHB] and [EMIM][CHCA] from [EMIM]OAc), chloride-containing ILs did not react with matrices and resulted in mixtures of IL and matrix in solution. Compared to the parent solid matrices, much less matrix interference was observed in the low mass region of the mass spectrum (< 500 Da) using each of the IL-matrices. Furthermore, the formation of a true ILM (i.e. a new ion pair) does not appear to be necessary for analyte ionization. MALDI sample preparation techniques were optimized based on the compatibility with analyte, IL and matrix. ILMs and IL-matrix mixtures of DHB allowed for qualitative analysis of glucose, fructose, sucrose and N-acetyl-D-glucosamine. Analogous CHCA-containing ILMs did not result in appreciable analyte signals under similar conditions. Small platform compounds such as 5-hydroxymethylfurfural (HMF) and levulinic acid were not detected by direct analysis using MALDI-MS. Furthermore, sugar analyte signals were only detected at relatively high matrix:IL:analyte ratios (1:1:1) due to significant matrix and analyte suppression by the IL ions. Therefore, chemical modification of analytes with glycidyltrimethylammonium chloride (GTMA) was employed to extend this method to quantitative applications. Derivatization was accomplished in aqueous IL solutions with fair reaction efficiencies (36.9 – 48.4 % glucose conversion). Calibration curves of derivatized glucose-GTMA yielded good linearity in all solvent systems tested, with decreased % RSDs of analyte ion signals in IL solutions as compared to purely aqueous systems (1.2 – 7.2 % and 4.2 – 8.7 %, respectively). Derivatization resulted in a substantial increase in sensitivity for MALDI-MS analyses: glucose was reliably detected at IL:analyte ratios of 100:1 (as compared to 1:1 prior to derivatization). Screening of all test analytes resulted in appreciable analyte signals in MALDI-MS spectra, including both HMF and levulinic acid. Using appropriate internal standards, calibration curves were constructed and this method was employed for monitoring a model dehydration reaction of fructose to HMF in [BMIM]Cl. Calibration curves showed wide dynamic ranges (LOD – 100 ng fructose/μg [BMIM]Cl, LOD – 75 ng HMF/μg [BMIM]Cl) with correlation coefficients of 0.9973 (fructose) and 0.9931 (HMF). LODs were estimated from the calibration data to be 7.2 ng fructose/μg [BMIM]Cl and 7.5 ng HMF/μg [BMIM]Cl, however relatively high S/N ratios at these concentrations indicate that these values are likely overestimated. Application of this method allowed for the rapid acquisition of quantitative data without the need for prior separation of analyte and IL. Finally, small molecule platform chemicals HMF and levulinic acid were qualitatively analyzed by DESI-MS. Both HMF and levulinic acid were easily ionized and the corresponding molecular ions were easily detected in the presence of 10 – 100 times IL, without the need for chemical modification prior to analysis. DESI-MS analysis of ILs in positive and negative ion modes resulted in few ions in the low mass region, showing great potential for the analysis of small molecules in IL media.

Chitosan gel film bandages: correlating structure, composition, and antimicrobial properties

Chitosan gel films were successfully obtained by evaporation cast from chitosan solutions in aqueous acidic solutions of organic acids (lactic and acetic acid) as gel film bandages, with a range of additives that directly influence film morphology and porosity. We show that the structure and composition of a wide range of 128 thin gel films, is correlated to the antimicrobial properties, their biocompatibility and resistance to biodegradation. Infrared spectroscopy and solid-state 13C nuclear magnetic resonance spectroscopy was used to correlate film molecular structure and composition to good antimicrobial properties against 10 of the most prevalent Gram positive and Gram negative bacteria. Chitosan gel films reduce the number of colonies after 24 h of incubation by factors of ∼105–107 CFU/mL, compared with controls. For each of these films, the structure and preparation condition has a direct relationship to antimicrobial activity and effectiveness. These gel film bandages also show excellent stability against biodegradation with lysozyme under physiological conditions (5% weight loss over a period of 1 month, 2% in the first week), allowing use during the entire healing process. These chitosan thin films and subsequent derivatives hold potential as low-cost, dissolvable bandages, or second skin, with antimicrobial properties that prohibit the most relevant intrahospital bacteria that infest burn injuries.

Rheology and Microfluidic flows of a cationic surfactant and hydrotropic salt mixture

Thesis (Ph.D.)--University of Washington, 2016-08

MICROFLUIDIC ASSAY PERFORMANCE ENHANCEMENT USING POROUS VOLUMETRIC DETECTION ELEMENTS FOR IMPEDEMETRIC AND OPTICAL SENSING

Microfluidic technologies have great potential to help create automated, cost-effective, portable devices for rapid point of care (POC) diagnostics in diverse patient settings. Unfortunately commercialization is currently constrained by the materials, reagents, and instrumentation required and detection element performance. While most microfluidic studies utilize planar detection elements, this dissertation demonstrates the utility of porous volumetric detection elements to improve detection sensitivity and reduce assay times. Impedemetric immunoassays were performed utilizing silver enhanced gold nanoparticle immunoconjugates (AuIgGs) and porous polymer monolith or silica bead bed detection elements within a thermoplastic microchannel. For a direct assay with 10 µm spaced electrodes the detection limit was 0.13 fM AuIgG with a 3 log dynamic range. The same assay was performed with electrode spacing of 15, 40, and 100 µm with no significant difference between configurations. For a sandwich assay the detection limit was10 ng/mL with a 4 log dynamic range. While most impedemetric assays rely on expensive high resolution electrodes to enhance planar senor performance, this study demonstrates the employment of porous volumetric detection elements to achieve similar performance using lower resolution electrodes and shorter incubation times. Optical immunoassays were performed using porous volumetric capture elements perfused with refractive index matching solutions to limit light scattering and enhance signal. First, fluorescence signal enhancement was demonstrated with a porous polymer monolith within a silica capillary. Next, transmission enhancement of a direct assay was demonstrated by infusing aqueous sucrose solutions through silica bead beds with captured silver enhanced AuIgGs yielding a detection limit of 0.1 ng/mL and a 5 log dynamic range. Finally, ex situ functionalized porous silica monolith segments were integrated into thermoplastic channels for a reflectance based sandwich assay yielding a detection limit of 1 ng/mL and a 5 log dynamic range. The simple techniques for optical signal enhancement and ex situ element integration enable development of sensitive, multiplexed microfluidic sensors. Collectively the demonstrated experiments validate the use of porous volumetric detection elements to enhance impedemetric and optical microfluidic assays. The techniques rely on commercial reagents, materials compatible with manufacturing, and measurement instrumentation adaptable to POC diagnostics.

Calculation of Activity Coefficients of Uni-Univalent Electrolytes by Equations Containing No Adjustable Parameters in Aqueous Solutions at 298.15 K

Normally either the Güntelberg or Davies equation is used to predict activity coefficients of electrolytes in dilute solutions when no better equation is available. The validity of these equations and, additionally, of the parameter-free equations used in the Bates-Guggenheim convention and in the Pitzerformalism for activity coefficients were tested with experimentally determined activity coefficients of HCl, HBr, HI, LiCl, NaCl, KCl, RbCl, CsCl, NH4Cl, LiBr,NaBr and KBr in aqueous solutions at 298.15 K. The experimental activity coefficients of these electrolytes can be usually reproduced within experimental errorby means of a two-parameter equation of the Hückel type. The best Hückel equations were also determined for all electrolytes considered. The data used in the calculations of this study cover almost all reliable galvanic cell results available in the literature for the electrolytes considered. The results of the calculations reveal that the parameter-free activity coefficient equations can only beused for very dilute electrolyte solutions in thermodynamic studies.

Synthesis, characterization and evaluation of phosphorylated resins in the removal of Pb(2+) from aqueous solutions

Phosphinic-derivative poly(styrene-co-divinylbenzene)-based on PS-DVB copolymers with different porosity degrees have been prepared by aromatic electrophilic substitution reaction using PCl(3)/AlCl(3) followed by base-promoted hydrolysis. The phosphorylation reaction was analyzed by infra-red spectroscopy (FTIR), scanning electron microscopy (SEM), and thermogravimetry (TG/DTG). In addition, the phosphorous content of the phosphorylated copolymers was determined by spectrophotometry using the method based on sodium molybdate reactant so that the extension of that modification could be assessed. The performance of the phosphorylated resins in the extraction of Pb(2+) from aqueous solutions in a batch system was also evaluated. The Pb(2+) content was determined by atomic absorption spectrometry (AAS). These materials presented excellent extraction capacity under the contact time of 30 min and pH 6.