Proefschrift--Leyden. / "Samenyatting" in Dutch. "Literature": p. 119-122.

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This thesis discusses diverse electrochemical strategies for the determination of the concentration of the gases hydrogen sulfide, ammonia and halothane. The chemical tagging of sulfide by a variety of structurally diverse substituted benzoquinone species was studied over a wide range of pH (2<pH<10). Each derivative was found to respond to increasing concentration of sulfide (typically over a range 10-200 μM). The electrochemically initiated reaction of N,N-diethyl-pphenylenediamine (DEPD) with sulfide in N,N-dimethylformamide (DMF) was next examined with quantitative detection of sulfide (linear range= 28-3290 μM, LoD= 22 μM) achieved by analysis of the increase in the second oxidation wave. This is consistent with the sulfide attacking the doubly oxidised species in a 1,4-Michael addition. The direct oxidation of sulfide at a nickel hydroxide film on a nickel electrode in alkaline solution has provided the basis for the design of a simple and inexpensive sensor for monitoring H₂S in the range 20-200 μM. More sensitive (LoD= 1 (μM) amperometric detection of sulfide was obtained at modified nickel electrodes in acidic media in which sulfide was stripped from the nickel oxide layer. This approach was exploited further by using nickel modified screen printed carbon (Ni-SPC) electrodes as economical and disposable sensors for sulfide. Next, two different strategies for determining gaseous ammonia in the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluromethylsulfonyl)imide, [EMIM][N(Tf)₂], and in DMF are described. The first approach exploits the effect of ammonia as a proton acceptor species on the anodic oxidation of hydroquinone, resulting in a linear detection range from 10 to 95 ppm ammonia (LoD= 4.2 ppm). The second approach is based on the direct oxidation of ammonia in either DMF or [EMIM][N(Tf)₂]. The possibility of photochemically induced electrocatalytic processes within microdroplets containing p-chloranil (2,3,5,6-tetrachloro-1,4-benzoquinone, TCBQ) was examined as a means of detecting the anaesthetic gas halothane.</p> Finally, two of the more promising routes for sulfide detection were studied at elevated temperatures (up to 70 °C) with a view to developing H₂S sensors capable of meeting the demands of oilfield applications.

Hydrogen Sulfide (H2S) is an important biologically produced gasotransmitter along with carbon monoxide (CO) and nitric oxide (NO). Unlike CO and NO, the bioinorganic chemistry of H2S reactivity with biologically relevant metal centers remains underinvestigated. To address this gap, several model bio(in)organic complexes were used to understand the ligation and reaction chemistry of H2S, including phthalocyanine, protoporphyrin IX, tetraphenyl porphyrin, and a pyridine diimine zinc complex. In addition to being a reactive gasotransmitter, the hydrosulfide anion (HS–) has been found to be an important biological anion. Studies with readily available cobalt and zinc phthalocyanines in organic solution illustrated the importance of protonation state in the ligation and redox chemistry of H2S and highlighted the need for an organic-soluble source of HS–. To address this need, we developed a simple method to prepare tetrabutylammonium hydrosulfide (NBu4SH). Using NBu4SH, we expanded the knowledge of H2S reaction chemistry to encompass a significantly larger set of biologically relevant metals beyond iron using the protoporphyrin IX scaffold, revealing three principle reaction pathways: binding, no response, or reduction and binding. Iron in biology is of particular importance given its role in oxygen transport in hemoglobin. The swamp-dwelling bivalve L. Pectinata hemoglobin 1 (Hb1) transports H2S, via ligation to heme, to symbiotic bacteria. The stabilization of H2S in Hb1 is believed to be from one of the following: a protected pocket, hydrogen bonding with a proximal glutamate residue, or a complex combination of these or other factors. By using Collman's "Picket-Fence" porphyrin to isolate the protected pocket model, we determined that a protected pocket alone as insufficient to account for H2S stabilization on Hb1. This realization led to an examination of hydrogen bonding in the secondary coordination sphere of a zinc complex. Finally, we explored the role of HS– as a biologically relevant anion using a bis(ethynylaniline) supramolecular receptor. We determined that rather than covalently modifying the receptor molecule, HS– was bound in the pocket, similar to bacterial anion transport channel. This dissertation includes previously published co-authored material.

Typescript. / Digitized by Kansas Correctional Industries

Hydrogen sulfide (H2S) is a gas commonly produced in manure pits. When the manure is disturbed through manure handling activities such as pressure washing, agitating, and pumping out manure, H2S is released. During these activities H2S concentrations increase quickly and reach hazardous concentrations. Many fatalities from high H2S concentrations during manure handling activities have been reported internationally as well as in the Midwest. Occupations in general industry that have identified the potential for high H2S concentrations use monitors to warn worker of high H2S concentrations. However, in agriculture the adoption of H2S monitors is low. To encourage farmers to adopt H2S monitors, interactive training materials were created. Displays were deployed to locations that farmers frequent such as agricultural stores, extension offices, and cooperatives. Agricultural stores are defined here as locations that sell agricultural supplies wholesale, or retail, and services. These displays contained educational materials, two H2S monitors, and two types of bump testing gas for farmers to use. Along with the display passive trainings, six in-person trainings were completed where participants filled out surveys. The survey asked questions about the farmers knowledge and use of H2S monitors, likelihood of purchasing a H2S monitor in the future, easiest bump testing gas to use and the one preferred for future bump testing, and the location that farmers would prefer to go to for bump testing and monitor education. Survey participants were placed into two groups: livestock producers and commercial manure applicators. A total of 43 surveys were completed by these groups. The majority of both livestock producers and commercial manure applicators knew what H2S monitors were, but less than half of the participants actually used H2S monitors. Outreach focusing on H2S monitor use and maintenance should be continued. Hydrogen sulfide monitor use and maintenance training had the more attendance when added to an already existing training or meeting such as the manure applicator trainings or livestock producer meetings. In the survey, livestock producers and commercial manure applicators were asked the easiest type of bump testing gas where both groups chose that the calibration gas is easiest to use. When prices were included in the survey question for both bump testing gas systems, many more of livestock producers and commercial manure applicators responded that they could see themselves using neither in the future. Price of bump testing systems ($130-$220) can be a potential barrier for some farmers to not bump test their monitors, it would be beneficial for multiple farmers to share one bump testing system. Putting a bump testing system in at agricultural stores, cooperatives and extension offices would allow many farmers to use it. Commercial manure applicators reported that they had no preference in future locations for bump testing and monitor advice between the agricultural store, cooperatives, and extension offices. Livestock producers preferred agricultural stores a little more than cooperatives and extension offices, but all three locations should be used for continuing H2S monitor education. In our study agricultural stores had the most bump tests recorded, bump testing gas used, they purchased a bump testing system for their customers.

Hydrogen sulfide (H2S) is the newest member of the gasotransmitter family and is becoming well known for its cardioprotective effects in preclinical trials. Many recent studies have shown the benefits of exogenous H2S in the setting of acute myocardial infarction (AMI) and pressure overload-induced heart failure, but current formulations are derived from inorganic salts which have shortcomings in the precision and control of release of H2S. The main objective of this thesis was to determine if the novel, orally active, slow-releasing compound, SG1002, can attenuate the severity of damage and adverse remodeling caused by ischemia/reperfusion injury through an induction of angiogenesis. A traditional sodium salt, Na2S, which has been previously shown to be cardioprotective, was used as a positive control. SG1002 improved overall left ventricular function as measured by increased ejection fraction from echocardiography and decreased QRS interval from electrocardiography compared to untreated animals following MI. SG1002 therapy was also associated with an induction of angiogenesis, which was determined through qRT-PCR, western blot, and histological methods. SG1002 increased VEGF protein levels, which was paralleled with an increase in capillary density in the infarct region. SG1002 also upregulated microRNA-126, which is thought to repress the inhibitor of VEGF, Spred-1. It is possible that this “angiomiR” plays a key role in the angiogenesis-related cardioprotection of H2S. The combination of increased pro-angiogenic factors along with greater vascular density resulting from SG1002 therapy indicates the therapeutic potential for this drug in the prevention and/or treatment of ischemic heart failure.

Endogenously generated H2S has been found not just a toxic substance but may play positive roles, such as the neuromodulator and vasorelaxant in the physiological system since 1990s. Then the precise control of the amount of Hydrogen Sulfide in the animal body raises great interests recently. However, the traditional methods for the Hydrogen Sulfide measurement need a large amount of tissue samples and take a complex procedure; it is impossible to develop any in-vivo real-time approach to measure H2S along the avenue of these methods. There is a great significance to develop new methods toward the measurement of Hydrogen Sulfide in in-vivo, real time, non- or less invasive manner with high resolution. One general idea to make the measurement less invasive is to take blood as sample i.e., to measure Hydrogen Sulfide in blood. <p>The study presented in this thesis aimed to conceive of new measurement methods for Hydrogen Sulfide in an aqueous solution along with their experimental verification. Though the blood sample will eventually be taken, the present study focused on an aqueous solution, which is a first step towards the final goal to measure Hydrogen Sulfide in blood. The study conducted a thorough literature review, resulting in the proposal of five methods, including: (i) the Hydrogen Sulfide measurement by Atomic Force Microscopy, (ii) the H2S measurement by Raman spectroscopy directly, (iii) the Hydrogen Sulfide measurement by Gas Chromatography/Mass Spectroscopy directly (with the static headspace technique), (iv) the Hydrogen Sulfide measurement by Mass Spectroscopy with Carbon Nanotubes, and (v) the Hydrogen Sulfide measurement by Raman spectroscopy with Carbon Nanotubes. The experiments for each of these methods were carried out, and the results were analyzed. Consequently, this study shows that method (v) is very promising to measure low concentration Hydrogen Sulfide in an aqueous solution, especially with the concentration level down to 10 μM and the presence of a linear relationship between the Hydrogen Sulfide concentration and its luminescent intensity.

Traditionally, hydrogen sulfide (H2S) has been regarded as toxic. It can affect the various human systems and even cause death. However, research in the 1990s has shown that H2S can be endogenously generated by many cells and tissues in mammalian bodies, and that H2S also may play physiological roles such as those of neuromodulator and vasorelaxant in the biological system. As such, the precise measurement of the amount of H2S in a mammalian body has generated researchers strong interest. The ultimate goal of such a measurement should be conducted in-vivo and in real time.<p>The existing methods for H2S measurement require both a large quantity of tissue samples and a complex procedure, so they are not highly practicable for the purpose of achieving the aforementioned goal. In this dissertation, a new method that uses carbon nanotube as an absorbent or transducer and laser-based microscopy techniques (Raman and confocal laser scanning microscopy) as signal excitation and acquisition is proposed and developed. Experimental studies are described of using this new method for analysis of both distilled water samples and serum samples in which a group of proteins are present. <p>The study concludes that the new method (1) can measure H2S in water solutions down to a low level of concentration of 10 µM, (2) can measure H2S in sera down to a low concentration of approximately 20 µM), and (3) has a high feasibility for being used in the clinical context. Regarding (3), this is confirmed by presenting a control system that allows the laser microscopy to track carbon nanotube in a solution that has Brownian motion.<p>While not having reached the ultimate goal as mentioned above, this work advances the state-of-the-art of the measurement of low concentration and nano-quantity of H2S in water and serum samples, in particular providing a promise toward a real-time and in-vivo H2S measurement.

The study presented in this thesis was aimed to gain the fundamental knowledge regarding the mechanism of H2S measurement in sera by using carbon nanotubes (CNT) and fluorescence response. Characterization techniques such as Raman spectroscopy, X-ray absorption spectroscopy (XAS) and confocal laser scanning microscopy (CLSM) were employed to achieve this goal. The model system used for this study was composed of H2S, distilled water, two major serum proteins (albumin and globulin), serum, hemoglobin, and CNT. The results of this study showed that: (1) Two major serum proteins (albumin and globulin) are physically adsorbed on the sidewall of the CNTs; while H2S is adsorbed on the defect site of the CNTs. (2) Presence of the proteins on the CNTs did not affect the CNTs adsorption of H2S. (3) Using CLSM with the incident wavelength of 514 nm and the emission wavelength of 530 to 580 nm to acquire the fluorescence response of the H2S adsorbed on the CNTs is a reliable approach to measure H2S in sera. (4) Single-wall carbon nanotubes (SWNTs) outperform multi-wall carbon nanotubes (MWNTs) in measurement sensitivity. (5) Presence of hemoglobin in a H2S solution did not affect the measurement of H2S with CNTs and CLMS. The study described in this thesis has provided new knowledge of the interaction behaviors of CNTs with H2S and major proteins in sera along with the mechanism which governs these behaviors. Such knowledge is very useful to further advance the CNT approach to sensing H2S in sera and water solution and to further extend the approach to sensing H2S in other mammalian tissues such as blood.