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Novel Synthesis and Applications of Gold Nanoclusters : (1) Sensing of GSH, (2) Sensing of Mercury(II), and (3) Cluster-Assisted LDI MSChen, Tzu-Heng 11 July 2012 (has links)
This paper, contain three parts, focus on develop synthesis method for novel functional nanocluster, base on its special optical and reactive property. In the first part, lysozyme VI was mixed with HAuCl4 under acidic condition(pH~3) and yield blue fluorescent Au8 nanocluster. When this Au8 cluster was incubate under alkaline condition (pH~12) a size evolution from Au8 to Au25 took place and monitored with fluorescence spectrum, MALDI MS, DLS. On the other hand, on the role of structural characteristic, fluorescence of Au8 cluster can be quenched by GSH as GSH induced core-etching reaction took place. Take advantage of this reaction, GSH in RBC can be quantitatively analysis by Au8 cluster. Compare with standard medical analysis method, this assay got comparable quantitative result and advantage in environmental friendly, low cost and low sample demand. Follow the first part, it was knowing that Hg2+quench fluorescence of Au25 but Au8 cluster. The second part of research development a ratiometric fluorescence assay for Hg2+ in drinking water sample, by control size evolution of nanocluster mentioned in first part by adding Ag+ into protein direct synthesis nanocluter process. Under optimize condition of bimetallic nanocluster synthesis, two separately fluorescence peak locate under 613 nm and 471 nm represent bigger size and smaller nanoclusters. Using fluorescence intensity ratio of two wavelength, concentration of Hg2+ in water sample can be determined by standard addition method with high reproducibility. Limit of detection was determined to be 0.1 and 0.4 nM, both lower than EPA permitted level in drinking water. On the third part, SA and HAuCl4 was mixed under water contained acetonitrile solution and SA caped nanocluster was form. This nanocluster after self essemble possess special crystalline and surface phenomenon and fit matrix for high reproducible laser desorption/ionization mass spectrometry. Compare with traditional matrix SA, the cluster matrix show 6.6% in RSD with 33%. And the desorption/ionization efficiency of nanocluster matrix is also much higher. Insulin, myoglobin and HSA sample can be quantitative with this matrix with mean RSD lower than 10%.
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Development of Thermal Desorption Electrospray Ionization Mass Spectrometry and its Applications in Food SafetyLiu, Te-Lin 28 July 2012 (has links)
Ambient ionization mass spectrometry, which has witnessed a flurry of recent developments, is a set of useful techniques for the analysis of samples under open-air conditions. It allows direct, rapid, real-time, high-throughput analysis with little or no sample pretreatment for the chemicals in solids or liquids. In this study, thermal desorption electrospray ionization mass spectrometry ( TD-ESI/MS ) involving direct insertion probe ( DIP ), thermal desorption ( TD ) and electrospray ionization ( ESI ) was used for the rapid screening of various types of samples. The source mainly consists of the sampling probe device, thermal desorption heating device, electrospray ionization device, ion source and temperature controller. A novel strategy involved in TD-ESI/MS processes where sampling, desorption, and ionization are separated as three independent events. The sampling probe is first used for the sampling of analytes and then inserted into a heat unit for thermal desorption. The desorbed analytes are finally carried into a reaction region with a stream of nitrogen gas, where charged methanol droplets were generated continuously by electrospray for post-ionization. Total analysis time is less than 10 seconds.
Traditionally, three standard methods are used for the analysis for pesticide residues, biochemical, immunoassay and instrument. And, the instrument analysis is the most widely used because it provides lots of advantages in particularly accurate quantitative approach. However, its complicated steps take a long period of time for preparation. Here, we used TD-ESI/MS to rapidly screen the pesticide residues on the surface of fruits and vegetables. The MS/MS analysis was also performed to confirm those detected compounds. The experimental results of the standard deviation for reproducibility is 13.2% (n = 10), and the detection limit is approximately 10 ppb. Furthermore, several fruits and vegetables purchased from local market were used as test samples and pesticide residues on the surface of samples can be successfully detected via TD-ESI/MS. In addition, the TD-ESI/MS technique was also applied to the analysis of illegal additives or phthalates in food. In this study, the TD-ESI/MS technique emerges lots of advantages such as direct, rapid, real-time analysis of sample surface and sample pretreatment is not necessary, and shows highly potential for rapid screening of chemicals in food safety.
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Adsorption/Desorption Studies of Volatile Organic Compounds Generated from the Optoelectronics Industry by ZeolitesHsu, Ching-shan 12 February 2006 (has links)
Adsorption/desorption behaviors of three volatile organic compounds (VOCs) emitted from the optoelectronics industry by Y-type and ZSM-5 zeolites were studied in this work. Target VOCs include acetone, isopropyl alcohol (IPA), and propylene glycol monomethyl ether acetate (PGMEA). Adsorption/desorption experiments were conducted in a fixed-bed column using various operating conditions to mimic the commercial ones. Also studied include the adsorption kinetics for single-component, two-component, and three-component cases. Experimental results of the single-adsorbate case by both model zeolites have shown that the amount of VOC adsorbed follows the order of PGMEA > IPA > Acetone. This is ascribed to the greatest molecular weight of PGMEA among three VOCs tested. The adsorption capacity of each zeolite for each target VOC was found to increase with its increasing initial concentration. Freundlich isotherm and Langmuir isotherm were found to be suitable for describing the adsorption behaviors for the single-adsorbate case. Results of the desorption experiments also showed that most of the target VOCs could be desorbed at 180¢J in 100 minutes. The adsorption capacities of the regenerated model zeolites were found to be decreasing as the regeneration times increased. As compared with the fresh ones, the regenerated zeolites had reduced specific surface areas, but increased pore sizes. In addition, the Yoon and Nelson equation was employed to study the kinetic behaviors of adsorbing the target VOCs by the model zeolites. A good agreement of the experimental results and predictions by the Yoon & Nelson model was obtained for the single-adsorbate case. However, the Yoon and Nelson model was found to be incompetent to simulate and predict all the multi-adsorbate cases including two-component adsorption and three-component adsorption in this work. Again, it is speculated that the displacement of lower-molecular-weight adsorbates (i.e., acetone and IPA) by PGMEA (an adsorbate of a much greater molecular weight) would be responsible for this finding. For the two-adsorbate case, nevertheless, the Yoon and Nelson equation was found to be capable of describing the adsorption behavior under the circumstance of C/C0 < 1.
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New Approach of High Performance Nano-Ink: Development, Preparation and CharacterizationWu, Heng-hsi 28 June 2006 (has links)
A series of novel metallic nanoparticle and suspension were developed and synthesized for ink-jet printing and spin coating applications. Organic components, such as alkanethiols and amines, were used as new capping agent design. The suspension was characterized by NMR, ESCA, TEM, SEM, EDS, TGA, DTG, DSC, TA-MS for chemical composition and three-dimension SAMs desorption.
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Thickness Effects In Hydrogen Sorption Of Magnesium/palladium Thin FilmsGharemeshg Gharavi, Ayshe 01 February 2012 (has links) (PDF)
Magnesium (Mg) thin films with various thicknesses ranging from 50 to 1000 nm capped with nominally 20 nm Palladium (Pd) were prepared by a thermal evaporation unit. A total of 25 glass substrates were used in each experiment. The unit had a rotatable macro shutter, rectangular in shape, rotation axes opposite to the Mg source, which allowed controlled exposure of the substrates. Thin films of 50, 100, 150, 200, 300, 400, 500, 600, 800 nm and 1000 nm were produced in a single experiment. Hydrogenation and dehydrogenation of the films were examined using a gas loading chamber which allowed in-situ resistance measurement. Samples were hydrogenated isochronally up to 453 K with a heating rate of 1.5 K/min. Samples cooled to room temperature were subjected to dehydrogenation test. The chamber was taken under vacuum (~10-2 mbar) and the sample was heated up to 453 K at a rate of 1.5 K/min. The results showed that the hydrogenation and dehydrogenation temperatures correlate with the film thickness, thinner films reacting with hydrogen at low temperatures. While 200 nm thin film hydrogenated at 420 K and desorbed it at 423 K, 50 nm thin film hydrogenated at room temperature and desorbed it at 405 K. Thicker films needed higher temperatures to react with hydrogen. It is concluded that films thinner than 200 nm react fully with hydrogen / while a considerable portion of the thicker films remain unreacted. Significance of this is discussed with reference to the design of hydrogen storage systems based on thin films or nanoparticles.
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Methyl arsenic adsorption and desorption behavior on iron oxidesLafferty, Brandon James 29 August 2005 (has links)
Arsenic is a toxic element that is widely distributed throughout the earth??s crust as a result of both natural geologic processes and anthropogenic activities. In virtually all environments, methylated forms of arsenic can be found. Because of the widespread distribution and toxicity of arsenic and methyl-arsenic, their adsorption behavior on soil minerals is of great interest. Although considerable attention has been given to the behavior of inorganic arsenic on mineral surfaces, little research has been conducted regarding interactions of the methyl-arsenic forms. The objective of this study was to compare the adsorption and desorption behavior of methylarsonate (MMAsV), methylarsonous acid (MMAsIII), dimethylarsinate (DMAsV), dimethylarsinous acid (DMAsIII), arsenate (iAsV), and arsenite (iAsIII) on iron oxide minerals (goethite and ferrihydrite) by means of adsorption isotherms and adsorption envelopes. Additionally, desorption envelopes were obtained using sulfate and phosphate as competitive ligands. Arsenic was measured by FI-HG-AAS. MMAsV and iAsV were adsorbed in higher amounts than DMAsV on goethite and ferrihydrite at all pH values studied. Although MMAsV and iAsV were adsorbed quantitatively at lower concentrations on goethite and ferrihydrite, as arsenic concentration was increased MMAsV was adsorbed in slightly lower quantities than iAsV. DMAsV was not quantitatively adsorbed at any concentration on goethite or ferrihydrite. MMAsV and iAsV exhibited high adsorption affinities on both goethite and ferrihydrite at pH values below 9 and showed decreasing adsorption above this point (more rapidly for MMAsV). DMAsV was adsorbed only at pH values below 8 on ferrihydrite and below 7 on goethite. MMAsV, iAsV, and DMAsV each exhibited adsorption characteristics suggesting specific adsorption on both goethite and ferrihydrite. Increased methyl substitution resulted in increased ease of arsenic release from the iron oxide surface. MMAsIII and DMAsIII exhibited no evidence for any type of specific adsorption under the conditions studied. Phosphate was a more effective desorbing ion than sulfate, but neither desorbed all arsenic species quantitatively.
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Detection of oxidation in human serum lipoproteinsMyers, Christine Lee 12 April 2006 (has links)
A method for the oxidation of lipoproteins in vitro was developed using the free radical initiator, 2,2?-azobis-(2-amidinopropane) dihydrochloride (AAPH). Following in vitro oxidation, the susceptibility to oxidation of the serum samples was studied using density gradient ultracentifugation and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS).
Shifts in mean buoyant density of the lipoprotein particles, specifically low density lipoprotein (LDL) and high density lipoprotein (HDL), were observed in the density profile following centrifugation. The degree of shift in the density proved to be proportional to the extent of oxidation. Changes in apolipoproteins were studied with MALDI-TOF-MS. Observed variations in the mass spectra include m/z shifts due to chemical modifications and change in isoform distributions.
The oxidation procedure and analysis techniques were applied to a clinical application to study the effects of table grape consumption on lipoprotein susceptibility to oxidation. The main objective of the research, to show feasibility that these methods could be used in a clinical setting, was achieved.
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Development and Applications of Laser-Induced Acoustic Desorption/Electrospray Ionization Mass SpectrometryCheng, Sy-Chyi 27 January 2010 (has links)
none
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Advancements in high throughput protein profiling using surface enhanced laser desorption/ionization time of flight mass spectrometryEmanuele, Vincent A., II 15 November 2010 (has links)
Surface-enhanced laser desorption/ionization time-of-flight mass spectrometry (SELDI)is one of several proteomics technologies that can be used in biomarker discovery studies. Such studies often have the goal of finding protein markers that predict early onset of cancers such as cervical cancer. The reproducibility of SELDI has been shown to be an issue in the literature. There are numerous sources of error in a SELDI experiment starting with sample collection from patients to the signal processing steps used to estimate the protein mass and abundance values present in a sample.
This dissertation is concerned with all aspects of signal processing related to SELDI's use in biomarker discovery projects. In chapter 2, we perform a comprehensive study of the most popular preprocessing algorithms available. Next, in chapter 3, we study the basic statistics of SELDI data acquisition. From here, we propose a quadratic variance measurement model for buffer+matrix only spectra. This model leads us to develop a modified Antoniadis-Sapatinas wavelet denoising algorithm that demonstrates superior performance when compared to MassSpecWavelet, one of the leading techniques for preprocessing SELDI data. In chapter 4, we show that the quadratic variance model 1) extends to real pooled cervical mucus QC data from a clinical study, 2) predicts behavior and reproducibility of peak heights, and 3) finds four times as many reproducible peaks as the vendor-supplied preprocessing programs.
The quadratic variance measurement model for SELDI data is fundamental and promises
to lead to improved techniques for analyzing the data from clinical studies using this instrument.
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Supramolekulare Sensoren und Anreicherung von biogenen Geruchsstoffen für die elektronische OlfaktometrieNieß, Johannes 13 July 2009 (has links) (PDF)
Gegenstand der Arbeit sind Grundlagenuntersuchungen zu einem technischen Messsystem für Gerüche. Das System besteht aus Quarzmikrowaagen als Sensoren und einer Anreicherungseinheit zur Erhöhung der Sensitivität der Sensoren. Als neuartige chemisch sensitive Schichten der Quarzmikrowaage wurden 2 Typen von polymeren Komplexverbindungen untersucht und Erklärungen des Verhaltens vorgeschlagen. Feste Phasen aus der Gaschromatografie besitzen jedoch für den Sensor-Einsatz günstigere Eigenschaften. Die wichtigsten Betriebs-Parameter der Anreicherungseinheit werden unter praxisnahen Bedingungen mit einer rein empirischen Methode untersucht. Damit kann die Empfindlichkeit des Messsystems bei Reinstoffen die menschliche Nase übertreffen.
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