Application of thermal ion-molecule reactions in tackling spectroscopic inferences in inductively coupled plasma mass spectrometry

Part I: Ultra-trace determination of vanadium in lake sediments: a performance comparison using O2, N20, and NH3 as reaction gases in ICP-DRC-MS Thermal ion-molecule reactions, targeting removal of specific spectroscopic interference problems, have become a powerful tool for method development in quadrupole based inductively coupled plasma mass spectrometry (ICP-MS) applications. A study was conducted to develop an accurate method for the determination of vanadium in lake sediment samples by ICP-MS, coupled with a dynamic reaction cell (DRC), using two differenvchemical resolution strategies: a) direct removal of interfering C10+ and b) vanadium oxidation to VO+. The performance of three reaction gases that are suitable for handling vanadium interference in the dynamic reaction cell was systematically studied and evaluated: ammonia for C10+ removal and oxygen and nitrous oxide for oxidation. Although it was able to produce comparable results for vanadium to those using oxygen and nitrous oxide, NH3 did not completely eliminate a matrix effect, caused by the presence of chloride, and required large scale dilutions (and a concomitant increase in variance) when the sample and/or the digestion medium contained large amounts of chloride. Among the three candidate reaction gases at their optimized Eonditions, creation of VO+ with oxygen gas delivered the best analyte sensitivity and the lowest detection limit (2.7 ng L-1). Vanadium results obtained from fourteen lake sediment samples and a certified reference material (CRM031-040-1), using two different analytelinterference separation strategies, suggested that the vanadium mono-oxidation offers advantageous performance over the conventional method using NH3 for ultra-trace vanadium determination by ICP-DRC-MS and can be readily employed in relevant environmental chemistry applications that deal with ultra-trace contaminants.Part II: Validation of a modified oxidation approach for the quantification of total arsenic and selenium in complex environmental matrices Spectroscopic interference problems of arsenic and selenium in ICP-MS practices were investigated in detail. Preliminary literature review suggested that oxygen could serve as an effective candidate reaction gas for analysis of the two elements in dynamic reaction cell coupled ICP-MS. An accurate method was developed for the determination of As and Se in complex environmental samples, based on a series of modifications on an oxidation approach for As and Se previously reported. Rhodium was used as internal standard in this study to help minimize non-spectral interferences such as instrumental drift. Using an oxygen gas flow slightly higher than 0.5 mL min-I, arsenic is converted to 75 AS160+ ion in an efficient manner whereas a potentially interfering ion, 91Zr+, is completely removed. Instead of using the most abundant Se isotope, 80Se, selenium was determined by a second most abundant isotope, 78Se, in the form of 78Se160. Upon careful selection of oxygen gas flow rate and optimization ofRPq value, previous isobaric threats caused by Zr and Mo were reduced to background levels whereas another potential atomic isobar, 96Ru+, became completely harmless to the new selenium analyte. The new method underwent a strict validation procedure where the recovery of a suitable certified reference material was examined and the obtained sample data were compared with those produced by a credible external laboratory who analyzed the same set of samples using a standardized HG-ICP-AES method. The validation results were satisfactory. The resultant limits of detection for arsenic and selenium were 5 ng L-1 and 60 ng L-1, respectively.

Arsenic speciation by ion-exchange chromatography with on- line determination by hydride generation: electronic modification of the D.C. plasma by photon counting

A method using L-cysteine for the determination of arsenous acid (As(III)), arsenic acid (As(V)), monomethylarsonic acid (MMAA), and dimethylarsinic acid (DMAA) by hydride generation was demonstrated. The instrument used was a d.c. plasma atomic emission spectrometer (OCP-AES). Complete recovery was reported for As(III), As(V), and DMAA while 86% recovery was reported for MMAA. Detection limits were determined, as arsenic for the species listed previously, to be 1.2, 0.8, 1.1, and 1.0 ngemL-l, respectively. Precision values, at 50 ngemL-1 arsenic concentration, were f.80/0, 2.50/0, 2.6% and 2.6% relative standard deviation, respectively. The L-cysteine reagent was compared directly with the conventional hydride generation technique which uses a potassium iodide-hydrochloric acid medium. Recoveries using L-cysteine when compared with the conventional method provided the following results: similar recoveries were obtained for As(III), slightly better recoveries were obtained for As(V) and MMAA, and significantly better recoveries for DMAA. In addition, tall and sharp peak shapes were observed for all four species when using L-cysteine. The arsenic speciation method involved separation by ion exchange .. high perfonnance liquid chromatography (HPLC) with on-line hydride generation using the L.. cysteine reagent and measurement byOCP-AES. Total analysis time per sample was 12 min while the time between the start of subsequent runs was approximately 20 min. A binary . gradient elution program, which incorporated the following two eluents: 0.01 and 0.5 mM tri.. sodium citrate both containing 5% methanol (v/v) and both at a pH of approximately 9, was used during the separation by HPLC. Recoveries of the four species which were measured as peak area, and were normalized against As(III), were 880/0, 290/0, and 40% for DMAA, MMAA and As(V), respectively. Resolution factors between adjacent analyte peaks of As(III) and DMAA was 1.1; DMAA and MMAA was 1.3; and MMAA and As(V) was 8.6. During the arsenic speciation study, signals from the d.c. plasma optical system were measured using a new photon-signal integrating device. The_new photon integrator developed and built in this laboratory was based on a previously published design which was further modified to reflect current available hardware. This photon integrator was interfaced to a personal computer through an AID convertor. The .photon integrator has adjustable threshold settings and an adjustable post-gain device.

Applications of dihydroarenediols to chemoenzymatic synthesis : approaches to total synthesis of morphine alkaloids

The present studies describe, as a primary goal, our recent progess toward the synthesis of morphine alkaloids from aromatic precursors. Model substrates were synthesized which allowed investigation into Diels-Alder, radical cascade, and palladium-catalyzed bond-forming reactions as possible routes to the morphine alkaloid skeleton. As a secondary objective, three separate series of aromatic substrates were subjected to whole-cell oxidation with Escherichia coli JM 109 (pDTG601), a recombinant organism over-expressing the enzyme toluene dioxygenase. Included in this study were bromothioanisoles, dibromobenzenes, and cyclopropylbenzene derivatives. The products of oxidation were characterized by chemical conversion to known intermediates. The synthetic utility of one of these bacterial metabolites, derived from oxidation of o-dibromobenezene, was demonstrated by chemical conversion to (-)conduritol E.

Preoperative education and its influence on perception of recovery for clients awaiting total hip and total knee replacement surgery /

The puqjose of this study was to examine the manner in which an inviting approach to a preoperative teaching and learning educational experience influenced the perception and subsequent recovery of clients who were awaiting total hip and total knee replacement surgery. An in-depth review of the internal and external factors that shape client perceptions was undertaken in this study. In addition, this study also explored whether or not the Prehab Program was preparing clients physically, socially, and psychologically for surgery. Data for this qualitative case study research were collected through preoperative interviews with 4 participants awaiting total hip replacement surgery and 1 participant awaiting total knee replacement surgery. Four postoperative interviews were conducted with the participants who had received total hip replacement surgery. The occupational therapist and physical therapist who were the coleaders of the Prehab Program at the time of this study were also interviewed. The results of this study suggest that while individuals may receive similar educational experiences, their perceptions of the manner in which they benefited from these experiences varied. This is illustrated in the research findings, which concluded that while clients benefited physically from the inviting approach used during the practical teaching session, not all clients perceived the psychological benefits of this practice session, especially clients with preexisting high levels of anxiety. In addition to increasing the understanding of the internal as well as external factors that influence the perceptions of clients, this study has also served as an opportunity for reflection on practice for the Prehab therapists and other healthcare educators.

Arsenic and germanium determination by hydride generation in the D.C. plasma optical emission spectrometer

Modifications to the commercial hydride generator, manufactured by Spectrametrics, resulted in improved operating procedure and enhancement of the arsenic and germanium signals. Experiments with arsenic(III) and arsenic(V) showed that identical reiults could be produced from both oxidation states. However, since arsenic(V) is reduced more slowly than arsenic(III), peak areas and not peak heights must be measured when the arsine is immediately stripped from the system (approximately 5 seconds reaction). When the reduction is allowed to proceed for 20 seconds before the arsine is stripped, peak heights may be used. For a 200 ng/mL solution, the relative standard deviation is 2.8% for As(III) and 3.8% for As(V). The detection limit for arsenic using the modified system is 0.50 ng/mL. Studies performed on As(V) standards show that the interferences from 1000 mg/L of nickel(II), cobalt(II), iron(III), copper(II), cadmium(II), and zinc(II) can be eliminated with the aid of 5 M Hel and 3% L-cystine. Conditions for the reduction of germanium to the corresponding hydride were investigated. The effect of different concentrations of HCl on the reduction of germanium to the covalent hydride in aqueous media by means of NaBH 4 solutions was assessed. Results show that the best response is accomplished at a pH of 1.7. The use of buffer solutions was similarly characterized. In both cases, results showed that the element is best reduced when the final pH of the solution after reaction is almost neutral. In addition, a more sensitive method, which includes the use of (NH4)2S208' has been developed. A 20% increase in the germanium signal is registered when compared to the signal achieved with Hel alone. Moreover, under these conditions, reduction of germanium could be accomplished, even when the solution's pH is neutral. For a 100 ng/mL germanium standard the rsd is 3%. The detection limit for germanium in 0.05 M Hel medium (pH 1.7) is 0.10 ng/mL and 0.09 ng/mL when ammonium persulphate is used in conjunction with Hel. Interferences from 1000 mg/L of iron(III), copper(II), cobalt(II), nickel(II), cadmium(II), lead(II), mercury(II), aluminum(III), tin(IV), arsenic(III), arsenic(V) and zinc(II) were studied and characterized. In this regard, the use of (NH4)ZS20S and Hel at a pH of 1.7 proved to be a successful mixture in the sbppression of the interferences caused by iron, copper, aluminum, tin, lead, and arsenic. The method was applied to the determination of germanium in cherts and iron ores. In addition, experiments with tin(IV) showed that a 15% increase in the tin signal can be accomplished in the presence of 1 mL of (NH4)2S20S 10% (m/V).

Continuous hydride generation in the presence of L- cysteine for the determination of arsenic, bismuth, antimony and tin in steels by inductively coupled plasma atomic emission spectrometry

Arsenic, bismuth, germanium, antimony and tin were simultaneously determined by continuous hydride generation and inductively coupled plasma-atomic emission spectrometry . I Hydrides were introduced into four different types of gas-liquid separators. Two of the gas-liquid separators were available in-house. A third was developed for this project and a fourth was based on a design used by CET AC. The best signal intensity was achieved by the type II frit-based gas-liquid separator, but the modified Cetac design gave promise for the future, due to low relative standard deviation. A method was developed for the determination of arsenic, bismuth, antimony and tin in low-alloy steels. Four standard reference materials from NIST were dissolved in 10 mL aqua regia without heat. Good agreement was obtained between experimental values and certified values for arsenic, bismuth, antimony and tin. The method was developed to provide the analyst with the opportunity to determine the analytes by using simple aqueous standards to prepare calibration lines. Within the limits of the samples analyzed, the method developed is independent of matrix.

Effectiveness of life skills training on the total behaviour of six individuals in a job preparation program

In the first week of a Job preparation Program all twelve female members of the class were invited to be part of a study to determine the effect of Life Skills training on their behaviour over the twelve-week period of the program. Six females volunteered and each was interviewed four times during the Job preparation Program and once after the program ended. The interviews focused on three areas of skill deficiency addressed in Life Skills lessons: their knowledge about themselves and attitude towards themselves; their interpersonal relationships; and their problem-solving ability. The participants' comments over the sixteen-week period of the interviews were used to decide if the total behaviour of the participants, (i.e., what they did, thought, and felt) changed so that each became more effective in satisfying her needs. The study suggested that the total behaviour of three of the six women changed so that they became more effective in satisfying their needs. The fourth female's total behaviour changed in only two of the three areas focused on in the interviews, and the total behaviour of the fifth and sixth females showed no change.

Investigation into the determination of arsenic by direct current plasma atomic emission spectrometer

Improvements have been made on the currently available hydride generator system manufactured by SpectraMetrics Incorporated, because the system was found to be unsatisfactory with respect to the following: 1. the drying agent, anhydrous calcium chloride, 2. the special sample tube, 3. the direction of argon flow through the Buchner funnel when it came to dealing with real sample, that is, with reference only to aqueous extracts of soil samples. Changes that were made on the system included the replacement of anhydrous calcium chloride with anhydrous calcium sulphate and the replacement of the special sample tube with a modified one made from silica. Re-directing the flow of argon through the top of the Buchner funnel appeared to make the system compatible with aqueous extracts of soil samples. The interferences from 1000 ~g/mL of nickel(II) , cobalt(II), iron(III), copper(II) have been eliminated with the aid of 1.4 M hydrochloric acid and 1% (weight/volume) L-cystine. Greater than 90% recovery of 0.3 ~g/mL arsenic signal was achieved in each case. Furthermore, 103% of arsenic signal was accomplished in the presence of 1000 ~g/mL cadmium with 5 M Hel. tVhen each of the interferents was present in solution at 1000 ppm, a recovery of 85% was achieved by using 5 M hydrochloric acid and 3% (weight/volume) L-cystine. Without L-cystine and when 1.4 M hydrochloric acid was used, the recoveries were 0% (Ni), 0% (Co), 88% (Fe), 15% (Cu), 18% (Cd). Similarly, a solution containing 1000 ppm of each interferent gave a zero percent recovery of arsenic. The reduction of trivalent and pentavalent arsenic at a pH less than one has also been investigated and shown to be quantitative if peak areas are measured. The reproducibility determination of a 0.3 Vg/mL standard arsenic solution by hydride generation shows a relative standard deviation of 3.4%. The detection limits with and without Porapak Q have been found to be 0.6 ng/mL and 1.0 ng/mL, respectively.

Organizational change: implications of culture and leadership in the transformation to a total quality management paradigm

The study was undertaken to investigate organizational readiness for change to a total quality management (TQM) paradigm as the corporate-wide strategy within a long-term care facility. The focus of the study was on leadership values and organizational cultural characteristics that could either accelerate or impede the change process at The Public Hospital. structurally, the ~tudy included 'three distinct components. The first component examined the management philosophy outlined by Deming (1986) and his contemporary Juran (1989) in order to determine what leadership values best support the new Total Quality Management paradigm. Secondly, this information was compared to present leadership values at The Public Hospital with the purpose of identifying opportunities for improvement within the organization's current culture as the hospital moves toward the desired TQM culture. The final component, a roadmap, was developed to reflect the most appropriate direction for organizational change at The Public Hospital.

Total synthesis of (S)-4-hydroxy-[a]-Lapachone

(S)-4-Hydroxy-a-lapachone has been prepared for the first time. The commercially available compound 2-acetyl-1-naphthol was used as the starting material. The synthesis involved methylation, followed by Baeyer-Villiger oxidation, and hydrolysis of the acetate to give 1-methoxy-2-naphthol. After protecting of the hydroxyl group, t-BuLi was used to form 3-(3',3'-dimethyl-acryloyl)-1- meth oxy-2- (meth oxymethoxy)-naphthalen e. eycl izationand oxidation then gave 4-keto-a-lapachone. Finally enzymic biotransformation by Mortierella isabellina ATCC 42613 was used to yield the target compound. The enantiomeric excess of the product was determined to be ~98% by using 1H NMR chiral shift analysis. The overall yield is 80/0. The biological activity of (S)-4-hydroxy-alapachone and its acetate are under investigation.

Some ecological factors affecting the input and population level of total and faecal coliforms and salmonella in Twelve Mile Creek, Lake Ontario and sewage waters near St. Catharines, Ontario

Some Ecological Factors Affecting the Input and Population Levels of Total and Faecal Coliforms and Salmonella in Twelve Mile Creek, Lake Ontario and Sewage Waters Near St. Catharines, Ontario. Supervisor: Dr. M. Helder. The present study was undertaken to investigate the role of some ecological factors on sewage-Dorne bacteria in waters near St. Catharines, Ontario. Total and faecal coliform levels and the presence of Salmonella were monitored for a period of a year along with determination of temperature, pH, dissolved oxygen, total dissolved solids, nitrate N, total phosphate P and ammonium N. Bacteriological tests for coliform analysis were done according to APHA Standard Methods by the membrane filtration technique. The grab sampling technique was employed for all sampling. Four sample sites were chosen in the Port Dalhousie beach area to determine what bacteriological or physical relationship the sites had to each other. The sample sites chosen were the sewage inflow to and the effluent from the St. Catharines (Port Dalhousie) Pollution Control Plant, Twelve Mile Creek below the sewage outfall and Lake Ontario at the Lakeside Park beach. The sewage outfall was located in Twelve Mile Creek, approximately 80 meters from the creek junction with the beach and piers on Lake Ontario. Twelve Mile Creek normally carried a large volume of water from the WeIland Canal which was diverted through the DeCew Generating Station located on the Niagara Escarpment. An additional sample site, which was thought to be free of industrial wastes, was chosen at Twenty Mile Creek, also in the Niagara Region of Ontarioo 3 There were marked variations in bacterial numbers at each site and between each site, but trends to lower_numbers were noted from the sewage inflow to Lake Ontario. Better correlations were noted between total and faecal coliform population levels and total phosphate P and ammonium N in Twenty Mile Creek. Other correlations were observed for other sample stations, however, these results also appeared to be random in nature. Salmonella isolations occurred more frequently during the winter and spring months when water temperatures were minimal at all sample stations except the sewage inflow. The frequency of Salmonella isolations appeared to be related to increased levels of total and faecal coli forms in the sewage effluent. However, no clear relationships were established in the other sample stations. Due to the presence of Salmonella and high levels of total and faecal coliform indicator organisms, the sanitary quality of Lake Ontario and Twelve Mile Creek at the sample sites seemed to be impaired over the major portion of the study period.

Chemoenzymatic synthesis of amaryllidaceae alkaloids and their C-1 analogues : symmetry based approach to total synthesis of thebaine

Described herein is the chemoenzymatic total synthesis of several Amaryllidaceae constituents and their unnatural C-I analogues. A new approach to pancratistatin and related compounds will be discussed along with the completed total synthesis of 7 -deoxypancratistatin and trans-dihydrolycoricidine. Evaluation of all new C-l analogues as cancer cell growth inhibitory agents is described. The enzymatic oxidation of dibromobenzenes by Escherichia coli 1M 109 (pDTG60 1) is presented along with conversion of their metabolites to (-)-conduritol E. Investigation into the steric and functional factors governing the enzymatic dihydroxylation of various benzoates by the same organism is also discussed. The synthetic utility of these metabolites is demonstrated through their conversion to pseudo-sugars, aminocyclitols, and complex bicyclic ring systems. The current work on the total synthesis of some morphine alkaloids is also presented. Highlighted will be the synthesis of several model systems related to the efficient total synthesis of thebaine.

Development of thermally stable versions of the Burgess Reagent : approaches to the chemoenzymatic total synthesis of morphine

The present studies describe our recent work on expanding the use of the Burgess reagent and its reaction with oxiranes. Several new variants of the Burgess reagent and its chiral auxiliary version were evaluated for their thermal stability by NMR spectroscopy. Three new versions of the reagent were synthesized and their stability was determined. The reactivity of all five Burgess reagents was compared in a dehydration reaction and reactions with epoxides and diols. Progress toward a chemoenzymatic synthesis of morphine is also included in this report. The synthesis began with the whole cell oxidation of bromobenzene by Escherichia coli JMI09(pDTG601). The preparation of several precursors for a key step involving the lohnson-Claisen rearrangement and progress toward the total synthesis are described.

Frontal Lobe Function and Performance Monitoring following Total Sleep Deprivation

Imaging studies have shown reduced frontal lobe resources following total sleep deprivation (TSD). The anterior cingulate cortex (ACC) in the frontal region plays a role in performance monitoring and cognitive control; both error detection and response inhibition are impaired following sleep loss. Event-related potentials (ERPs) are an electrophysiological tool used to index the brain's response to stimuli and information processing. In the Flanker task, the error-related negativity (ERN) and error positivity (Pe) ERPs are elicited after erroneous button presses. In a Go/NoGo task, NoGo-N2 and NoGo-P3 ERPs are elicited during high conflict stimulus processing. Research investigating the impact of sleep loss on ERPs during performance monitoring is equivocal, possibly due to task differences, sample size differences and varying degrees of sleep loss. Based on the effects of sleep loss on frontal function and prior research, it was expected that the sleep deprivation group would have lower accuracy, slower reaction time and impaired remediation on performance monitoring tasks, along with attenuated and delayed stimulus- and response-locked ERPs. In the current study, 49 young adults (24 male) were screened to be healthy good sleepers and then randomly assigned to a sleep deprived (n = 24) or rested control (n = 25) group. Participants slept in the laboratory on a baseline night, followed by a second night of sleep or wake. Flanker and Go/NoGo tasks were administered in a battery at 1O:30am (i.e., 27 hours awake for the sleep deprivation group) to measure performance monitoring. On the Flanker task, the sleep deprivation group was significantly slower than controls (p's <.05), but groups did not differ on accuracy. No group differences were observed in post-error slowing, but a trend was observed for less remedial accuracy in the sleep deprived group compared to controls (p = .09), suggesting impairment in the ability to take remedial action following TSD. Delayed P300s were observed in the sleep deprived group on congruent and incongruent Flanker trials combined (p = .001). On the Go/NoGo task, the hit rate (i.e., Go accuracy) was significantly lower in the sleep deprived group compared to controls (p <.001), but no differences were found on false alarm rates (i.e., NoGo Accuracy). For the sleep deprived group, the Go-P3 was significantly smaller (p = .045) and there was a trend for a smaller NoGo-N2 compared to controls (p = .08). The ERN amplitude was reduced in the TSD group compared to controls in both the Flanker and Go/NoGo tasks. Error rate was significantly correlated with the amplitude of response-locked ERNs in control (r = -.55, p=.005) and sleep deprived groups (r = -.46, p = .021); error rate was also correlated with Pe amplitude in controls (r = .46, p=.022) and a trend was found in the sleep deprived participants (r = .39, p =. 052). An exploratory analysis showed significantly larger Pe mean amplitudes (p = .025) in the sleep deprived group compared to controls for participants who made more than 40+ errors on the Flanker task. Altered stimulus processing as indexed by delayed P3 latency during the Flanker task and smaller amplitude Go-P3s during the Go/NoGo task indicate impairment in stimulus evaluation and / or context updating during frontal lobe tasks. ERN and NoGoN2 reductions in the sleep deprived group confirm impairments in the monitoring system. These data add to a body of evidence showing that the frontal brain region is particularly vulnerable to sleep loss. Understanding the neural basis of these deficits in performance monitoring abilities is particularly important for our increasingly sleep deprived society and for safety and productivity in situations like driving and sustained operations.

Model studies toward the total synthesis of thebaine by an intramolecular cycloaddition strategy

The present studies describe recent progress toward the synthesis of the thebaine. Model substrates were synthesized using pyridazine derivatives as a starting material, which allowed to assess the key Diels-Alder reaction as a route to construct the thebaine core.