Aggregation-induced Emission Guest Functionalized Infinite Coordination Ploymers And Their Application For The Field Analysis Of Water Pollution

Water pollution is a global environmental problem.Among many water environmental problems,antibiotic residues and eutrophication of water bodies have attracted great attention.It will not only destroy water quality,affect the balance of aquatic ecosystems,but also pose a threat to human health and the sustainable development of society in the future.Therefore,the development of convenient,fast,and reliable analytical platforms to realize environmental on-site analysis and monitoring of newly emerging antibiotics contaminants and eutrophication indexes is of great significance.As a new type of multifunctional nanomaterials,infinite coordination polymer nanoparticles(ICPs)with the diversity and designability of central metal ions and ligands,the adaptive encapsulation ability of hosts,and the fast response to external stimuli,have already shown a good developing prospect in the field of environmental analysis and monitoring.However,most of the current research regarding functionalized ICPs is focused on the guest-functionalized lanthanide metal infinite coordination polymer(Ln-ICP),the guest of which exhibited the aggregation-caused quenching effect(ACQ).Taking the practical requirements of environment field application into consideration,the improvement of optical properties from both the host and guest and the expansion of the applicated field is highly desired.The novel presented molecules with aggregation-induced emission effect(AIE)are good candidates for guests to functionalize ICPs,due to their low background,high signal-to-noise ratio,and photobleaching resistance on the solid substrate.To this end,in this paper,by carefully screening the appropriate AIE guest molecules,rationally designing the lanthanide/lanthanide-free metal ICP host,and systematically studying the host-guest interactions and/or the interaction between different guests,AIE guest functionalized infinite coordination polymer nanomaterials with multiple fluorescence response properties were prepared.(1)Regulating by metal coordination interaction,an optical sensor array and its fingerprinting test paper were developed.With the assistance of smart-phones,pattern recognition and systematic analysis of multiple antibiotic residues were realized with the on-site feature.(2)Regulating by metal coordination destruction,a ratiometric fluorescent method was established,which enabled real-time monitoring of the important eutrophication indicator,alkaline phosphatase(ALP).(3)With the surging ALP as an indicator,a colorimetric-fluorescent dual-channel digital algal bloom monitoring and warning platform was constructed with the help of smart-phones.The full text is divided into the following four chapters:Chapter 1.IntroductionThis chapter firstly summarizes the current status of water pollution and the significance of research on antibiotic pollution and water eutrophication.Based on the structure and optical properties of infinite coordination polymer nanomaterials,the applications of infinite coordination polymers and guest-functionalized infinite coordination polymers in the field of environmental analysis are further discussed.Finally,the application of smart-phones in on-site analysis and monitoring is listed,which is of great significance for the subsequent research.Chapter 2.Pattern Recognition and Systematic Analysis of Antibiotics in Water by the AIE Emission Guest Functionalized Dual Ln-ICPs Sensor ArrayThe antibiotic residues have activated wide concern.Face up with the fact that multiple antibiotics were present in the real aquatic environment simultaneously,in this work,according to the chemical structure and physicochemical properties of antibiotics,tetra(4-sulfophenyl)ethene(TPE-TS)with AIE effect was selected as the guest,Ln-ICPs(Eu-AMP ICPs and Tb-AMP ICPs)were chosen as the host.By regulating the antenna effect and photo-induced electron transfer effect between host,guest,and antibiotics,a sensor array based on AIE guest functionalized dual lanthanide ICPs was constructed.In addition,benefiting from the excellent fluorescence analytical properties of TPE-TS and the two ICP hosts,the obvious fluorescence color changes on the test paper could be translated to the three-primary colors alteration.With the smart-phone recognized simultaneous changes of RGB as the sensing elements,the identification ability and analytical performance of as-developed test paper sensor array were further improved,which enabled the field pattern recognition and systematic analysis of different kinds of coexisting antibiotics(flumequine,oxytetracycline,and sulfadiazine)in water environment and has broad the application prospects in the environmental field.Chapter 3.A Ratiometric Fluorescent Method for Real-Time Monitoring Alkaline Phosphatase Activity Based on AIE and ACQ Dual-Guests Functionalized Lanthanide-Free ICPsAlkaline phosphatase(ALP)is one kind of enzyme widely existing in freshwaters,which is closely related to eutrophication and can provide effective information for algal blooms.In this study,according to the catalytical ability of alkaline phosphatase for the hydrolysis of phosphate ester,the lanthanide-free infinite coordination polymer host,Cu-GMP was prepared and served as the substrate for the enzyme,meanwhile,two guests,1,1,2,2-tetra(4-carboxyphenyl)ethylene(H₄TCPE)with aggregation-induced emission effect and sulforhodamine 101(SR101)with aggregation-caused quenching effect were selected and simultaneously been encapsulated into the Cu-GMP ICP host under the modulation of complex host-guest interaction and guest-guest interaction,then H₄TCPE/SR101/Cu-GMP ICPs with dual-responsive optical properties were constructed.Catalyzed by the alkaline phosphatase,the network structure of the ICP host was destroyed through the regulation of metal coordination destruction interaction.Two guests were correspondingly released and displayed the opposite optical response,which constituted the first example of a real-time method for ALP activity monitoring with ratiometric fluorescence by simultaneously regulated AIE and ACQ phenomenon.In addition,the above work is of great significance to break through the fetter of Ln-ICPs on functional ICPs and further expand the practical application of AIE guest functionalized ICPs in the environment field.Chapter 4.Application of AIE and ACQ Dual-Guest Functionalized Lanthanide-Free ICPs in Colorimetric-fluorescence Dual-channel Digital Algal Bloom Monitoring and WarningOn the basis of the complex host-guest interaction and dual-guest interactions,H₄TCPE/SR101/Cu-GMP ICPs were endowed with obvious color changes in both the fluorescent channel(blue-purple to red)and colorimetric channel(blue to pink),which can be easily recognized by the color scanning software installed on the smart-phone,and directly converted to the digital signals readout in the form of RGB value for the establishment of digital platform.Taking advantage of the highly sensitive fluorescence channels,on-site monitoring of ALP activity in both time and space dimensions is realized.The monitoring results also showed that ALP was closely related to water quality,and the surging ALP activity prior to the algae exponential growth phase could be used as an important indicator for eutrophication.Using this digital analytical platform,the colorimetric-fluorescent dual-channel monitoring of ALP was realized,which offers great potential for digital algal bloom monitoring and warning with surging ALP as an effective indicator in the future.