The purpose of this study was to prepare concentrated and stable gold colloids for the enhancement of the signal response of the SPR technique for detecting small molecules such as progesterone. The gold colloids developed in this study were prepared by hydrazine hydrate, sodium borohydride, and tri-potassium citrate reduction routes. The study revealed that the sodium borohydride reduced gold colloids were extremely stable and it was able to be utilised in the progesterone immunoassay developed previously by Mitchell et al. The experiment was carried out on BIAcore 3000 using two different sensor surfaces (CM5 and SAM). The results showed that the enhancement species prepared from the borohydride-reduced gold colloids were able to improve the SPR signal response by 13 times higher than SPR signal produced without the enhancement species on the CM5 surface. The signal enhancement on the SAM surface using the same enhancement species was even greater at 29 times higher. The sensitivity of the assay was, however, unable to be determined due to time constraint. The limit of detection (LOD) of the progesterone assay using the CM5 chip was estimated to be ca. 5-20 pg/mL. Whilst for the SAM chip, the LOD of the progesterone assay was estimated to be ca. 5-20 fg/mL. Further work is required to confirm these estimated LOD values.

Flame Atomic Absorption Spectrometry (FAAS) still keeps its importance despite the relatively low sensitivity / because it is a simple and economical technique for determination of metals. In recent years atom traps have been developed to increase the sensitivity of FAAS. Although the detection limit of FAAS is only at the level of mg/L, with the use of atom traps it can reach to ng/mL. Slotted quartz tube (SQT) is one of these atom traps, it is applied for determination of volatile elements / it is economical, commercially available and easy to use. In this study, a sensitive analytical method has been developed for the determination of lead with the help of SQT. Regarding the angle between the two slots of SQT, 120&deg / and 180&deg / configurations were used and the results were compared. There were three modes of SQT used. The first application was for providing longer residence time of analyte atoms in the measurement zone / 3 fold sensitivity enhancement was observed. The second mode was the usage of SQT for preconcentration of lead atoms. In the presence of a lean air-acetylene flame, analyte atoms were trapped in the inner surface of SQT for a few minutes. Then, by the help of a small volume (10-50 &amp / #956 / L) of Methyl isobutyl ketone (MIBK), analyte atoms were revolatilized and a rapid atomization took place. Using this mode, a sensitivity enhancement of 574 was obtained at a rather low (3.9 mL/min) suction rate / 1320 fold improvement was reached at higher sample suction rate (7.4 mL/min) for 5.0 min collection. The last mode involves coating of the inner surface of SQT with several kinds of transition metals. The best sensitivity enhancement, 1650 fold, was obtained by the Ta coated SQT. In addition, effects of some elements and anions on Pb signal in Tacoated-SQT-AT-FAAS were examined. Final step consists of surface analysis / chemical nature of Pb trapped on quartz and Ta surface, and the chemical nature of Ta on quartz surface were investigated by X-ray Photoelectron Spectroscopy (XPS) and Raman Spectroscopy.

ABSTRACT DETERMINATION OF CADMIUM USING SLOTTED QUARTZ TUBE ATOM TRAP ATOMIC ABSORPTION SPECTROMETRY AND METAL COATINGS &Ouml / zcan Gurbetoglu, G. Pelin M.S., Department of Chemistry Supervisor: Prof. Dr. O. Yavuz Ataman July 2010, 76 pages Flame atomic absorption spectroscopy (FAAS) is a common technique for detecting metals and metalloids in environmental, biological and metallurgical samples. Although it is a rather old technique, it is still very reliable, simple to use and inexpensive. The technique can be used to determine the concentration of over 70 different metals in a solution. However, it has detection limits at mg/L levels. Some atom trapping methods have been developed to reach the detection limits of ng/mL levels. Slotted quartz tube (SQT) is one of these atom trapping methods. It is an important technique, since it is easy to use, applicable in all laboratories, commercially available and economical. This thesis consists of development of a sensitive method for cadmium with the help of SQT atom trap. In this study, it was used for two different purposes. One was for keeping the analyte atoms more in the light path / in other words, for increasing the residence times of analyte atoms in the measurement zone. This first application was provided a 2.9 times enhancement with respect to conventional FAAS. Second application was for trapping the analyte on the surface of the SQT, in other words, for performing on-line preconcentration of cadmium in SQT. In the presence of a lean flame, analyte samples were trapped and collected for a few minutes at a low suction rate. After finishing the collection period, analyte atoms were revolatilized with the help of a small volume of (10-50 &micro / L) methyl isobutyl ketone (MIBK) and a rapid atomization occurred. This introduction also altered the flame composition momentarily and analyte atoms were released from the surface of the SQT. Application of this method enhanced the sensitivity 2065 times with respect to conventional FAAS. Another approach to this type of atom trapping has been investigated also in this study, which was coating of SQT with some metals having low volatility. Therefore, some transition metals were coated to the surface of SQT and among them zirconium was selected as the best coating material as having the most sensitivity enhancement factor. That is why, rest of the study was performed with the Zr coated SQT. The enhancement was 3368 as compared with FAAS. Cd determination with this method provides LOD value of 8 pg/mL and Co value of 19 pg/mL. In order to see the effect of some other type of elements or ions on determination of cadmium, interference study was done.

Flame Atomic Absorption Spectroscopy (FAAS) has lover sensitivity than similar analytical methods, however it has an important place for analysis due to its easy application and economic practicability especially in metal determinations. In order to increase the sensitivity of FAAS from mg/L level to ng/L level, various atom trap systems have been used. One of these atom traps, Slotted Quartz Tube (SQT), which is easy, economical and useful for volatile element determination, is used in this study as a sensitive analytical method for determination of tellurium. In the study, determination of Te by SQT is handled in three different modules. First, only with SQT itself, longer residence time for Te atoms in the measurement zone is provided and consequently 3.2 fold sensitivity enhancement is obtained both for Te (VI) and Te (IV). In the second module, SQT is used for concentration of tellurium species in a lean flame by sending the analyte into SQT for a definite time and trapping them on the inner surface of the SQT. After trapping the analyte, in order to determine the Te concentration, a small volume (10-50 &micro / L) of organic solvent such as methyl ethyl ketone (MEK) is introduced to the flame for revolatilization and a rapid atomization of Te on the surface is provided. In this trapping method, for 5 minutes collection with a 6 mL/min suction rate, 143 fold enhancement for Te (VI) and 142 fold enhancement for Te (IV) were obtained. In the third module, different from the second one, the inner surface of the SQT is coated with different metals for increasing the amount of Te trapped on the surface and the best enhancement for tellurium is obtained with Tantalum-coated SQT with 252 fold enhancement for Te (VI) and 246 fold enhancements for Te (IV). All improvements are calculated according to the signals obtained in FAAS method. Separate calibration plots were used for Te (IV) and Te (VI).

Silver is a precious metal having antibacterial property and widely used in industry mostly for water purification and medicinal products. Therefore, the determination of trace levels of silver is important for industrial applications. Flame atomic absorption spectrometry (FAAS) is a popular technique for the determination of relatively low concentration levels. This mature technique owes its widespread application to its simplicity and low cost. However, for some occasions, FAAS technique suffers from its low sensitivity because of low nebulization efficiency and relatively short residence time of analyte atoms in the measurement zone. In order to overcome this sensitivity problem, atom traps have been developed in recent years. Slotted quartz tube (SQT) is an accessory designed to use as an atom trap in conventional flame atomic absorption burner head. This thesis study involves the development of a sensitive, simple and economical technique with the help of the SQT for the determination silver. Firstly, the technique known as SQT-FAAS was used to increase the residence time of analyte atoms in the measurement zone. In this case, limit of detection (LOD) and characteristic concentration (C0) values were found to be 19 ng/mL and 35 ng/mL, respectively. Enhancement in sensitivity with respect to FAAS was found to be 2.31 fold using SQT-FAAS. Regarding the angle between the two slots of the SQT, 180&deg / configuration was used. Secondly, in order to improve sensitivity further, the SQT was used as an atom trap (AT) where the analyte is accumulated in its inner wall prior to re-atomization. The signal is formed after reatomization of analyte atoms on the trap surface by introduction of organic solvent. For this purpose, uncoated SQT was used as a trap medium. However, there was a memory effect. Therefore, the SQT inner surface was coated with different coating elements and theoptimum conditions were found by using W-coated SQT-AT-FAAS technique. In the presence of a lean air-acetylene flame, analyte atoms were trapped in the inner surface of the SQT for 5.0 min and then revolatilized with the introduction of 25 &mu / L isobutyl methyl ketone (IBMK) / afterwards, a transient signal was obtained. These optimized parameters were used for uncoated SQT, W-coated SQT and Zr-coated SQT atom trap techniques. Sample suction rate was 6.25 mL/min in all techniques. Sensitivity was increased 54 fold using uncoated SQT-AT-FAAS technique with respect to simple FAAS technique. When W-coated SQT-AT-FAAS technique was applied, 135 fold sensitivity enhancement was obtained with respect to FAAS technique. The best sensitivity enhancement, 270 fold, was obtained using Zr-coated SQT-AT-FAAS technique. In addition, the Ag signals were more reproducible (%RSD, 1.21) when Zr was used as a coating element. After the sensitive technique was developed, interference effects of some transition and noble metals and hydride forming elements on Ag signals were investigated. Finally, surface studies were done to determine the chemical state of Ag during trapping period by using X-ray Photoelectron Spectroscopy (XPS). It was observed that the Ag analyte is retained on the SQT surface in its oxide form.

No description available.

Sensor interfaces are needed to communicate the measured real-world analog values to the base¬band digital processor. They are dominated by the presence of high accuracy, high resolution analog to digital converters (ADC) in the backend. On most occasions, sensing is limited to small range measurements and low-modulation sensors where the complete dynamic range of ADC is not utilized. Designing a subsystem that integrates the sensor and the interface circuit and that works with a low resolution ADC requiring a small die-area is a challenge. In this work, we present a CMOS based area efficient, integrated sensor interface for applications like capacitance, temperature and dielectric-constant measurement. In addition, potential applica-tions for this work are in Cognitive Radios, Software Defined Radios, Capacitance Sensors, and location monitoring. The key contributions in the thesis are: 1 High Sensitivity Frequency-domain CMOS Capacitance Interface: A frequency domain capacitance interface system is proposed for a femto-farad capacitance measurement. In this technique, a ring oscillator circuit is used to generate a change in time period, due to a change in the sensor capacitance. The time-period difference of two such oscillators is compared and is read-out using a phase frequency detector and a charge pump. The output voltage of the system, is proportional to the change in the input sensor capacitance. It exhibits a maximum sensitivity of 8.1 mV/fF across a 300 fF capacitance range. 2 Sensitivity Enhancement for capacitance sensor: The sensitivity of an oscillator-based differential capacitance sensor has been improved by proposing a novel frequency domain capacitance-to-voltage (FDC) measurement technique. The capacitance sensor interface system is fabricated in a 130-nm CMOS technology with an active area of 0.17mm2 . It exhibits a maximum sensitivity of 244.8 mV/fF and a measurement resolution of 13 aF in a 10-100 fF measurement range, with a 10 pF nominal sensor capacitance and an 8-bit ADC. 3 Frequency to Digital Converter for Time/Distance measurement: A new architecture for a Vernier-based frequency-to-digital converter (VFDC) for location monitoring is pre¬sented, in which, a time interval measurement is performed with a frequency domain approach. Location monitoring is a common problem for many mobile robotic applica¬tions covering various domains, such as industrial automation, manipulation in difficult areas, rescue operations, environment exploration and monitoring, smart environments and buildings, robotic home appliances, space exploration and probing. The proposed architecture employs a new injection-locked ring oscillator (ILR) as the clock source. The proposed ILR oscillator does not need complex calibration procedures, usually required by Phase Locked Loop (PLL) based oscillators in Vernier-based time-to-digital convert¬ers. It consumes 14.4 µW and 1.15 mW from 0.4 V and 1.2 V supplies, respectively. The proposed VFDC thus achieves a large detectable range, fine time resolution, small die size and low power consumption simultaneously. The measured time-difference error is less than 50 ps at 1.2 V, enabling a resolution of 3 mm/kHz frequency shift. 4 A bio-sensor array for dielectric constant measurement: A CMOS on-chip sensor is presented to measure the dielectric constant of organic chemicals. The dielectric constant of these chemicals is measured using the oscillation frequency shift of a current controlled os¬cillator (CCO) upon the change of the sensor capacitance when exposed to the liquid. The CCO is embedded in an open-loop frequency synthesizer to convert the frequency change into voltage, which can be digitized using an off-chip analog-to-digital converter. The dielectric constant is then estimated using a detection procedure including the calibration of the sensor. 5 Integrated Temperature Sensor for thermal management: An integrated analog temper¬ature sensor which operates with simple, low-cost one-point calibration is proposed. A frequency domain technique to measure the on-chip silicon surface temperature, was used to measure the effects of temperature on the stability of a frequency synthesizer. The temperature to voltage conversion is achieved in two steps i.e. temperature to frequency, followed by frequency to voltage conversion. The output voltage can be used to com¬pensate the temperature dependent errors in the high frequency circuits, thereby reduc¬ing the performance degradation due to thermal gradient. Furthermore, a temperature measurement-based on-chip self test technique to measure the 3 dB bandwidth and the central frequency of common radio frequency circuits, was developed. This technique shows promise in performing online monitoring and temperature compensation of RF circuits.