Photochemical Sciences Ph.D. Dissertations

Design, synthesis, and application of cross-reactive fluorescent macrocyclic supramolecular sensors for detection and quantitation of phosphates and their mixtures

Date of Award

2022

Document Type

Dissertation

Degree Name

Doctor of Philosophy (Ph.D.)

Department

Photochemical Sciences

First Advisor

Pavel Anzenbacher Jr. (Advisor)

Second Advisor

Malcolm Forbes (Committee Member)

Third Advisor

Jayaraman Sivaguru (Committee Member)

Fourth Advisor

Hrishikesh Joshi (Committee Member)

Abstract

Given that the world's population is growing quickly and is predicted to reach 9 billion by 2050, food production and sustainability are among humanity's top priorities. Since phosphorus is one of the three fundamental nutrients commonly integrated in commercial fertilizers, phosphorus (phosphate) plays a crucial role in the food production processes. Additionally, global demand for phosphorus increases roughly 3% every year, and yet, most phosphorus ends up in the waste! Most of the wasted phosphorus enters our water systems (rivers, lakes, seas, oceans) resulting in the eutrophication phenomena. The excessive amount of phosphorus and phosphates from various anthropogenic and natural resources create eutrophication, a dangerous form of water body pollution. Inorganic phosphates have enormous application in industry as both raw materials and fertilizers, often over-used in the agricultural settings. Organophosphates are a type of phosphorus-based compounds that are found to be harmful to the environment. For instance, abuse of chemical warfare agents since their invention in the 1930s has had a harmful effect on the society. Overuse of the commercially available herbicide Glyphosate (Roundup) has been linked to the cancerogenic effects to humans. To overcome these social, ecological, and economical burdens, new scientific and technological progresses have been developed. Chemistry has been one of the most important scientific branches that has played a substantial role in tackling environmental issues, thus dramatically improving the quality of life. A qualitative and quantitative determination of inorganic and organic phosphates demands development of chemosensors capable of operating in the various media, preferably in water. The present work describes the design and synthesis of macrocyclic fluorescent based chemosensors and their utilization in the state-of-the-art sensing methods employing pattern recognition protocols for identification and quantification of various phosphates and organophosphates. Aim and contribution of this work are to demonstrate practical utility of a single selective, yet cross-reactive sensing probe for discrimination of phosphates and their mixtures, thereby simplifying pattern recognition protocols while maintaining the high overall reliability of the sensing process.

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