Ultrafast Spectroscopies of Nitrophenols and Nitrophenolates in Solution: From Electronic Dynamics and Vibrational Structures to Photochemical and Environmental Implications.

Nitrophenols are a group of small organic molecules with significant environmental implications from the atmosphere to waterways. In this work, we investigate a series of nitrophenols and nitrophenolates, with the contrasting ortho-, meta-, and para-substituted nitro group to the phenolic hydroxy or phenolate oxygen site (2/3/4NP or NP-), implementing a suite of steady-state and time-resolved spectroscopic techniques that include UV/Visible spectroscopy, femtosecond transient absorption (fs-TA) spectroscopy with probe-dependent and global analysis, and femtosecond stimulated Raman spectroscopy (FSRS), aided by quantum calculations. The excitation-dependent (400 and 267 nm) electronic dynamics in water and methanol, for six protonated or deprotonated nitrophenol molecules (three regioisomers in each set), enable a systematic investigation of the excited-state dynamics of these functional "nanomachines" that can undergo nitro-group twisting (as a rotor), excited-state intramolecular or intermolecular proton transfer (donor-acceptor, ESIPT, or ESPT), solvation, and cooling (chromophore) events on molecular timescales. In particular, the meta-substituted compound 3NP or 3NP- exhibits the strongest charge-transfer character with FSRS signatures (e.g., C-N peak frequency), and thus, does not favor nitroaromatic twist in the excited state, while the ortho-substituted compound 2NP can undergo ESIPT in water and likely generate nitrous acid (HONO) after 267 nm excitation. The delineated mechanistic insights into the nitro-substituent-location-, protonation-, solvent-, and excitation-wavelength-dependent effects on nitrophenols, in conjunction with the ultraviolet-light-induced degradation of 2NP in water, substantiates an appealing discovery loop to characterize and engineer functional molecules for environmental applications.

Molecularly imprinted spin column extraction coupled with high-performance liquid chromatography for the selective and simple determination of trace nitrophenols in water samples.

In this study, we developed a simple and selective spin column extraction technology utilizing hydrophilic molecularly imprinted polymers as the sorbents for extracting nitrophenol pollutants in water samples (the East Lake, the Yangtze River, and wastewater). The whole procedure was achieved by centrifugation of the spin column, and multiple samples were simultaneously processed with a low volume of solvent and without evaporation. Under the optimized condition, recoveries of nitrophenol compounds on the spin column packed with hydrophilic molecularly imprinted polymers ranged from 87.3 to 92.9% and an excellent purification effect was obtained. Compared with activated carbon, multi-walled carbon nanotubes, LC-C18 sorbents, hydrophilic molecularly imprinted polymers exhibited a highly selective recognition ability for nitrophenol compounds and satisfactory sample extraction efficiency. Subsequently, the spin column extraction coupled with high-performance liquid chromatography was established, which was found to be linear in the range of 2-1000 ng/mL for 2,4-dinitropehnol and 2-nitrophenol, and 6-1000 ng/mL for 4-nitrophenol with correlation coefficients greater than 0.998. The detection limits ranged from 0.3-0.5 ng/mL. It is shown that the proposed method can be used for the determination of trace nitrophenol pollutants in complex samples, which is not only beneficial for water quality analysis but also for environmental risk assessment.

PLA/CS-ZnO bionanocomposite for rapid catalytic reduction of nitrophenol compounds as a heterogeneous nanocatalyst.

In this research, a high efficiency and environmentally friendly method to reduce nitrophenol compounds such as 4-nitrophenol (4-NP), 2,4,6-trinitrophenol (2,4,6-TNP) and 2,4-dinitrophenol (2,4-DNP) was used in the presence of poly(lactic acid)/chitosan-ZnO ( PLA/CS-ZnO) bionanocomposite. Using FT-IR, SEM, XRD and UV-Vis techniques, PLA/CS-ZnO bionanocomposite was identified after synthesis. Also, the mechanical properties of the bionanocomposite were investigated using the stress-strain curve. The mentioned bionanocomposite showed a very good efficiency in reducing nitrophenol compounds to aminophenolic compounds, so that under optimal conditions, 100% conversion and selectivity in the reduction of 4-NP, 2,4,6-TNP and 2,4-DNP to 4-aminophenol (4-AP), 2,4,6-triaminophenol (2,4,6-TAP) and 2,4-diaminophenol (2,4-DAP) were observed. UV-Vis absorption spectrum at different times were used to evaluate the progress of the reaction. Furthermore, after the reaction, PLA/CS-ZnO was recovered and used for the next cycle. The results showed that the bionanocomposite can perform ten consecutive cycles without a significant decrease in efficiency. The comparison of catalytic activity with other catalysts showed that the bionanocomposite synthesized in the present research has a higher efficiency in reduction of nitrophenol compounds.

Formation of halonitromethanes from different nitrophenol compounds during UV/post-chlorination: Impact factors, DFT calculation, reaction mechanisms, and toxicity.

As ubiquitous chemical substances in water bodies, nitrophenol compounds (NCs) can form chlorinated halonitromethanes (Cl-HNMs) in the chlorination process. This work chose six typical NCs to explore Cl-HNMs produced during the UV/post-chlorination process, and Cl-HNMs yields from these NCs followed the increasing order of 4-, 2-, 2-amino-3-, 2-methyl-3-, 3-, and 2-chloro-3-nitrophenol. The Cl-HNMs yields increased continually or increased firstly and declined with post-chlorination time. Increasing chlorine dosage favored Cl-HNMs formation, while excessive chlorine dosage decreased Cl-HNMs produced from 2- and 4-nitrophenol. Besides, appropriate UV radiation, acidic pH, and higher precursor concentrations facilitated Cl-HNMs formation. Then, the reaction mechanisms of Cl-HNMs generated from these different NCs were explored according to density functional theory calculation and identified transformation products (TPs), and the main reactions included chlorine substitution, benzoquinone compound formation, ring opening, and bond cleavage. Moreover, the Cl-HNMs generated from 2-chloro-3-nitrophenol were of the highest toxicity, and the six NCs and their TPs also presented ecotoxicity. Finally, two kinds of real waters were used to explore Cl-HNMs formation and toxicity, and they were significantly distinguishable compared to the phenomena observed in simulated waters. This work will give new insights into Cl-HNMs formation from different NCs in water disinfection processes and help better apply the UV/post-chlorination process to water treatments.