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).

Calculation of the optical conductivity for the Anderson impurity model using the slave boson technique

The optical conductivity of the Anderson impurity mode l has been calculated by emp l oying the slave boson technique and an expansion in powers of l i N, where N is the d egeneracy o f the f electron level . This method has been used to find the effective mass of the conduction electrons for temperatures above and below the Kondo tempera ture. For low temperatures, the mass enhancement is f ound to be large while a t high t emperatures, the mass enhancement is sma ll. The conductivity i s f ound to be Drude like with frequency dependent effective mass and scattering time for low independent effective mass and temperatures and scattering time f requency for high t emperatures. The behavior of both the effective mass and the conductivity is in qualitative agreement with experimental r esul t s .

Far-infrared optical properties of the heavy fermion superconductor UB[E13]

Temperature dependent resistivity, p, magnetic susceptibility, X, and far-infrared reflectance measurements were made on the low Tc superconductor UBe13. Two variants of UBe13 have been proposed, named 'L'- (for low Tc ) and 'H'-type (for high Tc ). Low temperature resistivity measurements confirmed that our sample was of H-type and that the transition temperature was at 0.9 K. This was further confirmed with the observation of this transition in the AC-susceptibility. Low temperature reflectance measurements showed a decrease in the reflectivity as the temperature is lowered from 300 to 10 K, which is in qualitative agreement with the increasing resistivity in this temperature range as temperature is lowered. No dramatic change in the reflectivity was observed between 10 and 0.75 K. A further decrease of the reflectance was observed for the temperature of 0.5 K. The calculated optical conductivity shows a broad minimum near 80 cm-1 below 45 K. Above 45 K the conductivity is relatively featureless. As the temperature is lowered, the optical conductivity decreases. The frequency dependent scattering rate was found to be flat for temperatures between 300 and 45 K. The development of a peak, at around 70 cm-1 was found for temperatures of 45 K and below. This peak has been associated with the energy at which the transition to a coherent state occurs from single impurity scattering in other heavy fermion systems. The frequency dependent mass enhancement coefficient was found to increase at low frequencies as the frequency decreases. Its' magnitude as frequency approaches zero also increased as the temperature decreased.

Set-up and evaluation of a mid-infrared reflectometer and investigation of the optical properties of doped tin telluride

A system comprised of a Bomem interferometer and a LT3-110 Heli-Tran cryostat was set up to measure the reflectance of materials in the mid-infrared spectral region. Several tests were conducted to ensure the consistency and reliability of the system. Silicon and Chromium, two materials with well known optical properties were measured to test the accuracy of the system, and the results were found to be in good agreement with the literature. Reflectance measurements on pure SnTe and several Pb and Mn-doped alloys were carried out. These materials were chosen because they exhibit a strong plasma edge in the mid infrared region. The optical conductivity and several related optical parameters were calculated from the measured reflectance. Very low temperature measurements were carried out in the far-infrared on Sn9SMn2Te, and the results are indicative of a spin glass phase at 0.8 K. Resistivity measurements were made at room temperature. The resistivity values were found, as expected, to decrease with increasing carrier concentration and to increase with increasing manganese concentration.

The measurement of the optical absorption cross section of photosystem 1 and photosystem 2 from whole live cells of porphyridium cruentum, in light state 1 and light state 2

The optical cross section of PS I in whole cells of Porphyridium cruentum (UTEX 161), held in either state 1 or state 2, was determined by measuring the change in absorbance at 820nm, an indication of P700+; the X-section of PS2 was determined by measuring the variable fluorescence, (Fv-Fo)/Fo, from PS2. Both cross-sections were 7 determined by fitting Poisson distribution equations to the light saturation curves obtained with single turnover laser flashes which varied in intensity from zero to a level where maximum yield occurred. Flash wavelengths of 574nm, 626nm, and 668nm were used, energy absorbed by PBS, by PBS and chla, and by chla respectively. There were two populations of both PSi and PS2. A fraction of PSi is associated with PBS, and a fraction of PS2 is free from PBS. On the transition S1->S2, only with PBS-absorbed energy (574nm) did the average X-section of PSi increase (27%), and that of PS2 decrease (40%). The fraction of PSi associated with PBS decreased, from 0.65 to 0.35, and the Xsection of this associated PS 1 increased, from 135±65 A2 to 400±300A2. The cross section of PS2 associated with PBS decreased from 150±50 A2 to 85±45 A2, but the fraction of PS2 associated with PBS, approximately 0.75, did not change significantly. The increase in PSi cross section could not be completely accounted for by postulating that several PSi are associated with a single PBS and that in the transition to state2, fewer PSi share the same number of PBS, resulting in a larger X-section. It is postulated that small changes occur in the attachment of PS2 to PBS causing energy to be diverted to the attached PSi. These experiments support neither the mobile-PBS model of state transitions nor that of spillover. From cross section changes there was no evidence of energy transfer from PS2 to PSi with 668nm light. The decrease in PS2 fluorescence which occurred at this wavelength cannot be explained by energy transfer; another explanation must be sought. No explanation was found for an observed decrease in PSi yield at high flash intensities.

Transmission measurements using a new far-infrared set-up

A system comprised of a Martin-Puplett type polarizing interferometer and a Helium-3 cryostat was developed to study the transmission of materials in the very-far-infrared region of the spectrum. This region is of significant interest due to the low-energy excitations which many materials exhibit. The experimental transmission spectrum contains information concerning the optical properties of the material. The set-up of this system is described in detail along with the adaptations and improvements which have been made to the system to ensure the best results. Transmission experiments carried out with this new set-up for two different varieties of materials: superconducting thin films of lead and biological proteins, are discussed. Several thin films of lead deposited on fused silica quartz substrates were studied. From the ratio of the transmission in the superconducting state to that in the normal state the superconducting energy gap was determined to be approximately 25 cm-1 which corresponds to 2~/kBTc rv 5 in agreement with literature data. Furthermore, in agreement with theoretical predictions, the maximum in the transmission ratio was observed to increase as the film thickness was increased. These results provide verification of the system's ability to accurately measure the optical properties of thin low-Tc superconducting films. Transmission measurements were carried out on double deionized water, and a variety of different concentrations by weight of the globular protein, Bovine Serum Albumin, in the sol, gel and crystalline forms. The results of the water study agree well with literature values and thus further illustrate the reproducibility of the system. The results of the protein experiments, although preliminary, indicate that as the concentration increases the samples become more transparent. Some weak structure in the frequency dependent absorption coefficient, which is more prominent in crystalline samples, may be due to low frequency vibrations of the protein molecules.

A naturalistic observation of the play behaviour of children with autism spectrum disorders /

Cognitive and social levels of play engaged in by four-to-eight-year-old children with autism spectrum disorders were examined in naturalistic classroom settings. In addition, play at home was compared with play at school via parent and educator interviews. Seventeen school-age children, their educators and caregivers participated in the study. The most frequently observed play behaviours included parallel-functional play, adult interactions and solitary-functional play. The play of the children in the current study was consistent with that of typically-developing preschoolers. Mothers and educators did not differ significantly in their perspectives of the participants' play behaviours. In general, educators' and caregivers' reports were positively related to researcher observations of participants' play behaviours. Methodological considerations and practical implications for the findings are discussed.

Exploring an emotion intervention for preschoolers with autism spectrum disorder /

The purpose of this multiple case study was 1) to explore the effectiveness of an emotions recognition program for preschoolers with Autism Spectrum Disorders (ASD), and 2) to investigate one parent's perception of the emotions program. To address these objectives, the emotion unit scores of 7 preschoolers with ASD aged 3 to 5 years old (1 female, 6 males) were graphed and analyzed using visual inspection. In addition, the mother of 1 participant was interviewed to explore her perceptions of the emotions program and emotional learning. Overall, results revealed that participants' emotion recognition scores increased over the course of the emotions unit. The parent reported improvements in her son's expression and understanding of emotion, but noted that he continued to have difficulty with regulation of emotion. Implications for theory, education, and future research are discussed.

A comparison of functional behaviour assessment rating scales in a sample of children and youth with autism spectrum disorders

This study sought to compare the results of the Motivation Assessment Scale (MAS; Durand & Crimmins, 1988), Questions About Behavior Function Scale (QABF; Matson & Vollmer, 1996) and Functional Analysis Screening Tool (FAST; Iwata & Deleon, 1996), when completed by parent informants in a sample of children and youth with autism spectrum disorders (ASD) who display challenging behaviour. Results indicated that there was low agreement between the functional hypotheses derived from each of three measures. In addition, correlations between functionally analogous scales were substantially lower than expected, while correlations between non-analogous subscales were stronger than anticipated. As indicated by this study, clinicians choosing to use FBA questionnaires to assess behavioural function, may not obtain accurate functional hypotheses, potentially resulting in ineffective intervention plans. The current study underscores the caution that must be taken when asking parents to complete these questionnaires to determine the function(s) of challenging behaviour for children/youth with ASD.

Creativity and the schizophrenia spectrum unveiled : the similarities and the differences

This study examined the commonalities and the differences between creativity and the schizophrenia spectrum. The variables measured as potential commonalities and differences were creativity, schizotypy, cognitive inhibition, spatial ability, balancing skills, positive and negative presence, absorption, mystical experiences, childhood abuse, and neuroticism. Three community groups were recruited, consisting of 31 artists, 10 people with schizophrenia, and 31 comparisons matched for gender and age with the artists. A larger student group consisting of 102 students was also recruited in order to examine the correlations among the same variables within a larger, more normative, group. The largest commonality between the artist and the schizophrenic groups, who represented the extreme end of the schizophrenia spectrum, was the propensity to mystical experiences. The greatest differences between the artist and the schizophrenic groups were that the artists were higher in creativity, performed better on spatial abilities, had better balance, had more positive states of presence, and were lower in neuroticism than the schizophrenic group. In the student group, creativity was correlated with spatial ability, positive presence, absorption, and mystical experiences. In addition, creativity was significantly related to two facets of schizotypy, unusual experiences and impulsive nonconformity. In other words, students high in certain facets of schizotypy, who may share certain characteristics with those who have schizophrenia, are higher in creativity, but people who are on the extreme end of the schizophrenia spectrum, who have been diagnosed with schizophrenia, are not. The differences between the artist and schizophrenic groups on spatial ability, balance, sense of presence, and neuroticism may help to determine whether mystical experiences help to integrate creative work or destabilize and disorganize the sense of self. It may be that mystical experiences can be used more positively by the creative individuals than people with schizophrenia, in that artists and people high in creativity were higher in positive traits such as positive presence and lower on negative variables such as neuroticism, and introvertive anhedonia.

Functional analysis and treatment of OCD-related behaviour in a child with Autism Spectrum Disorder

Research indicates that Obsessive-Compulsive Disorder (OCD; DSM-IV-TR, American Psychiatric Association, 2000) is the second most frequent disorder to coincide with Autism Spectrum Disorder (ASD; Leyfer et aI., 2006). Excessive collecting and hoarding are also frequently reported in children with ASD (Berjerot, 2007). Although functional analysis (Iwata, Dorsey, Slifer, Bauman, & Richman, 1982/1994) has successfully identified maintaining variables for repetitive behaviours such as of bizarre vocalizations (e.g., Wilder, Masuda, O'Connor, & Baham, 2001), tics (e.g., Scotti, Schulman, & Hojnacki, 1994), and habit disorders (e.g., Woods & Miltenberger, 1996), extant literature ofOCD and functional analysis methodology is scarce (May et aI., 2008). The current studies utilized functional analysis methodology to identify the types of operant functions associated with the OCD-related hoarding behaviour of a child with ASD and examined the efficacy of function-based intervention. Results supported hypotheses of automatic and socially mediated positive reinforcement. A corresponding function-based treatment plan incorporated antecedent strategies and differential reinforcement (Deitz, 1977; Lindberg, Iwata, Kahng, and DeLeon, 1999; Reynolds, 1961). Reductions in problem behaviour were evidenced through use of a multiple baseline across behaviours design and maintained during two-month follow-up. Decreases in symptom severity were also discerned through subjective measures of treatment effectiveness.

Using the Reliable Change Index Statistic to Analyze Developmental Changes in Infants at Risk for Autism Spectrum Disorder

Longitudinal studies of the development of autism spectrum disorders (ASD) provide an understanding of which variables may be important predictors of an ASD. The objective of the current study is to apply the reliable change index (RCI) statistic to examine whether the Parent Observation of Early Markers Scale (POEMS) is sensitive to developmental change, and whether these changes can be quantified along a child’s developmental trajectory. Ninety-six children with older siblings with autism were followed from 1-36 months of age. Group-based RCI analysis confirms that the POEMS is capable of detecting significant changes within pre-defined diagnostic groups. Within-subject analysis suggests that ongoing monitoring of a child at-risk for an ASD requires interpretation of both significant intervals identified by the RCI statistic, as well as the presence of repeated high (i.e., >70) scores. This study provides preliminary evidence for a reasonably sensitive and specific means by which individual change can be clinically monitored via parent report.

Comparison of the Behavioural Development of Infants at Low and High-Risk for Autism Spectrum Disorders

By identifying early signs of Autism Spectrum Disorder, early intervention or parent training could be implemented and assist in increasing the developmental trajectory for these infants. This cross sectional study used the Parent Observation of Early Markers Scale (POEMS) to identify early signs of ASD in 69 high-risk (older sibling diagnosed with ASD) and 69 matched low-risk infants' families (no family history of ASD) between 6 and 36 months of age. The preliminary results showed the high-risk children had significantly more elevated POEMS items than the low-risk children at 12, 18,24,30 and 36 months of age. The results suggest that at-risk infants may show signs of ASD as early as 12 months of age, and that the POEMS could be used to guide early intervention or parent training for children 12 months or older.

Optical Properties of Sb2Te3, and Dilute Magnetic Semiconductors Sb1.97 VO.03 Te3 and Sb1.94 CrO.06 Te3

This thesis reports on the optical properties of the dilute magnetic semiconductors, Sb1.97 V 0.03 Te3 and Sb1.94Cr0.06Te3, along with the parent compound Sb2Te3' These materials develop a ferromagnetic state at low temperature with Curie temperatures of 22 K and 16 K respectively. All three samples were oriented such that the electric field vector of the light was perpendicular to the c-axis. The reflectance profile of these samples in the mid-infrared (500 to 3000 cm-1) shows a pronounced plasma edge which retracts with decreasing temperature. The far-infrared region of these samples exhibits a phonon at ~ 60 cm-1 which softens as temperature decreases. Kramers-Kronig analysis and a Drude-Lorentz model were employed to determine the optical constants of the bulk samples. The real part of the optical conductivity is shown to consist of intraband contributions at frequencies below the energy gap (~0.26 eV) and interband contributions at frequencies above the energy gap. The temperature dependence of the scattering rate show that a mix of phonon and impurity scattering are present, while the signature of traditional spin disorder (magnetic) scattering was difficult to confirm.

Infrared Spectroscopy of Gadolinium

Measurements of the optical reflectivity of the normal incident light along c-axis [0001] have been made on a Gadolinium single crystal, for temperatures between 50 K and room temperature just above the Curie temperature of Gd, which is 293 K. And covering the spectrum range between 100 -11000 cm-I . This work is the first study of Gd in the far infrared range. In fact it fills the gap below 0.2 eV which has never been measured before. Extreme attention was paid to the fact that Gadolinium is a very reactive metal with air. Thus, the sample was mechanically polished and carefully handled during the measurement. However, temperature dependent optical measurements have been made in the same frequency range for a sample of Gd2O3. For comparison, both samples of Gd and Gd2O3 were examined by X-Ray diffraction. XRD analysis showed that the sample was pure gadolinium and the oxide layer either does not exist, or is very thin. Furthermore, this fact was supported by the absence of any of Gd2O3 features in the Gd sample reflectivity. Kramers Kronig analysis was applied to extract the optical functions from the reflectance data. The optical conductivity shows a strong temperature dependence feature in the mid-infrared. This feature disappears completely at room temperature which supports a magnetic origin.