Simple Synthetic Method Toward Solid Supported C₆₀ Visible Light-Activated Photocatalysts

Solid supported fullerene materials are prepared in aims of creating a fullerene-based photocatalyst that is capable of producing ¹O₂ in the aqueous phase. Past studies of using fullerene as a photocatalyst in water have exclusively focused on using water soluble fullerene derivatives and employed sophisticated chemistry to create immobilized fullerene materials. The method presented herein is much less synthetically complex and utilizes pristine fullerene, providing a drastically simpler route to supported fullerene materials and furthering their potential for use in environmental applications. Covalent immobilization was achieved through the nucleophilic addition of a terminal amine (located on a solid support) across a [6,6] fullerene double bond, resulting in attachment directly to C₆₀’s cage. Immobilization allowed supported fullerene moieties to produce ¹O₂ in water under various illumination conditions and inactivate MS2 bacteriophages. In a water with natural organic matter, supported fullerene materials produced ¹O₂ under visible light irradiation without exhibiting significant loss of photocatalytic activity after successive cycling

Sorbic Acid as a Triplet Probe: Triplet Energy and Reactivity with Triplet-State Dissolved Organic Matter via 1O2 Phosphorescence

Sorbic acid (2,4-hexadienoic acid; HDA) is commonly used as a probe and quencher for triplet-excited chromophoric dissolved organic matter (3CDOM*), an important transient species in natural waters, yet much remains unknown about its reactivity with 3CDOM* and its triplet energy. To better understand the quenching behavior of HDA, we measured HDA quenching rate constants for various humic substance isolates and whole waters with singlet oxygen (1O2) phosphorescence and determined the triplet energy of HDA. Low-temperature phosphorescence measurements determined the triplet energy of HDA to be 217 kJ mol–1, whereas a complementary method based on triplet quenching kinetics found a triplet energy of 184 ± 7 kJ mol–1. Time-resolved 1O2 phosphorescence measurements yielded different HDA quenching rate constants depending on the fitting method. Using an approach that considered the reactivity of the entire triplet pool produced values of (∼1–10) × 108 M–1 s–1, while an approach that considered only the reactivity of the high-energy triplets output higher rate constants ((∼7–30) × 108 M–1 s–1). In addition, the model based on high-energy triplet reactivity found that ∼30–60% of 3CDOM* is not quenched by HDA. Findings from this study provide a more comprehensive view on the use of HDA as a probe for 3CDOM*.ISSN:0013-936XISSN:1520-585

Sorbic Acid as a Triplet Probe: Reactivity of Oxidizing Triplets in Dissolved Organic Matter by Direct Observation of Aromatic Amine Oxidation

Sorbic acid (2,4-hexadienoic acid; HDA) isomerization is frequently used to probe triplet-state dissolved organic matter (3CDOM*) reactivity, but there remain open questions about the reaction kinetics of 3CDOM* with HDA due to the difficulties of directly measuring 3CDOM* quenching rate constants. Using our recently developed approach based on observing the radical cation of N,N,N′,N′-tetramethyl-p-phenylenediamine (TMPD) formed through oxidation of TMPD by 3CDOM*, we studied 3CDOM* quenching kinetics with HDA monitored via transient absorption spectroscopy. A competition kinetics-based approach utilizing formation yields of TMPD•+ was developed, validated with model sensitizers, and used to determine bimolecular rate constants between 3CDOM* oxidants and HDA for diverse DOM isolates and natural waters samples, yielding values in the range of (2.4–7.7) × 108 M–1 s–1. The unquenchable fraction of TMPD-oxidizing triplets showed that, on average, 41% of 3CDOM* oxidants cannot be quenched by HDA. Conversely, cycloheptatriene quenched nearly all TMPD•+-forming triplets in CDOM, suggesting that most 3CDOM* oxidants possess energies greater than 150 kJ mol–1. Comparing results with our companion study, we found slight, but noticeable differences in the 3CDOM* quenching rate constants by HDA and unquenchable triplet fractions determined by oxidation of TMPD and energy transfer to O2 (1O2 formation) methods.ISSN:0013-936XISSN:1520-585

Differential Photoactivity of Aqueous [C₆₀] and [C₇₀] Fullerene Aggregates

Many past studies have focused on the aqueous photochemical properties of colloidal suspensions of C₆₀ and various [C₆₀] fullerene derivatives, yet few have investigated the photochemistry of other larger cage fullerene species (e.g., C₇₀, C₇₄, C₈₄, etc.) in water. This is a critical knowledge gap because these larger fullerenes may exhibit different properties compared to C₆₀, including increased visible light absorption, altered energy level structures, and variable cage geometries, which may greatly affect aggregate properties and resulting aqueous photoactivity. Herein, we take the first steps toward a detailed investigation of the aqueous photochemistry of larger cage fullerene species, by focusing on [C₇₀] fullerene. We find that aqueous suspensions of C₆₀ and C₇₀, nC₆₀ and nC₇₀, respectively, exhibit many similar physicochemical properties, yet nC₇₀ appears to be significantly more photoactive than nC₆₀. Studies are conducted to elucidate the mechanism behind nC₇₀’s superior ¹O₂ generation, including the measurement of ¹O₂ production as a function of incident excitation wavelength, analysis of X-ray diffraction data to determine crystal packing arrangements, and the excited state dynamics of aggregate fullerene species via transient absorption spectroscopy

Dual-Functionality Fullerene and Silver Nanoparticle Antimicrobial Composites via Block Copolymer Templates

We present the facile prepartion of C₇₀ and Ag nanoparticle (NP) loaded block copolymer (BCP) thin films, with C₇₀ and Ag NPs working in tandem to provide virucidal and bactericidal activities, respectively. Polystyrene-<i>block</i>-poly-4-vinylpyridine (PS-P4VP) was used as a template, allowing C₇₀ integration into PS domains and in situ formation of Ag NPs in P4VP domains, while providing control of the nanoscale spatial distribution of functionality as a function of BCP molecular weight (MW). C₇₀ loaded PS-P4VP films were found to generate significant amounts of ¹O₂ under visible light illumination with no apparent dependence on BCP MW. An analogous C₇₀ loaded PS homopolymer film produced notably less ¹O₂, highlighting a possible critical role of morphology on C₇₀ photoactivity. The antimicrobial activity of Ag NP and C₇₀ loaded composites against the model PR772 bacteriophage and Escherichia coli was assessed, finding synergistic inactivation afforded by the dual functionality. BCPs were demonstrated as versatile platforms for the preparation of multifunctional antimicrobial coatings toward combating diverse microbial communities

Dissolved Organic Matter Singlet Oxygen Quantum Yields: Evaluation Using Time-Resolved Singlet Oxygen Phosphorescence

Singlet oxygen (1O2) generation quantum yields from chromophoric dissolved organic matter (CDOM) have been reported for many samples over the past 4 decades. Yet even for standardized isolates such as those from the International Humic Substance Society (IHSS), wide-ranging values exist in the literature. In this manuscript, time-resolved 1O2 phosphorescence was used to determine the 1O2 quantum yields (ΦΔ) of a variety of dissolved organic matter (DOM) isolates and natural waters. In general, the 1O2 quantum yield values in this study are in the middle, although below the median of the range of past reported values (e.g., for Suwannee River Natural Organic Matter IHSS isolate: 1.8% vs 0.23–2.89%). Notably, hydrophobic neutral fractions of DOM isolates were found to possess the highest 1O2 quantum yields, an interesting result given that these fractions are not retained in typical humic and fulvic acid isolation procedures that use XAD resins. The excitation wavelength dependence of 1O2 generation from CDOM was also examined, and an approximate linear decrease with longer excitation wavelength was observed. This work advances the understanding of CDOM photoprocesses, especially in relation to wavelength-dependent 1O2 production, which is valuable for assessing real-world environmental behavior.ISSN:0013-936XISSN:1520-585

Singlet Oxygen Phosphorescence as a Probe for Triplet-State Dissolved Organic Matter Reactivity

Triplet-state chromophoric dissolved organic matter (3CDOM*) plays an important role in aquatic photochemistry, yet much remains unknown about the reactivity of these intermediates. To better understand the kinetic behavior and reactivity of 3CDOM*, we have developed an indirect observation method based on monitoring time-resolved singlet oxygen (1O2) phosphorescence kinetics. The underpinning principle of our approach relies on the fact that O2 quenches almost all triplets with near diffusion limited rate constants, resulting in the formation of 1O2, which is kinetically linked to the precursors. A kinetic model relating 1O2 phosphorescence kinetics to triplet excited states produced from isolated humic substances and in whole natural-water samples (hereafter referred to as 3CDOM*) was developed and used to determine rate constants governing 3CDOM* natural lifetimes and quenching by oxygen and 2,4,6-trimethylphenol (TMP), a common triplet probe molecule. 3CDOM* was found to exhibit smaller O2 and TMP quenching rate constants, ∼9 × 108 and ∼8 × 108 M–1 s–1, respectively, compared with model sensitizers, such as aromatic ketones. Findings from this report shed light on the fundamental photochemical properties of CDOM in organic matter isolates and whole waters and will help refine photochemical models to more accurately predict pollutant fate in the environment.ISSN:0013-936XISSN:1520-585

Improving the Visible Light Photoactivity of Supported Fullerene Photocatalysts through the Use of [C₇₀] Fullerene

We herein present the first instance of employing [C₇₀] fullerene for photocatalytic ¹O₂ production in water, through covalent immobilization onto a mesoporous silica support via nucelophilic amine addition directly to fullerene’s cage. This attachment approach prevents the aggregation of individual fullerene molecules in water, thus allowing fullerene to retain its photoactivity, yet is much less complex than other techniques commonly pursued to create such supported-fullerene materials, which typically rely on water-soluble fullerene derivatives and elaborate immobilization methods. The solid-supported C₇₀ material exhibits significantly improved aqueous visible-light photoactivity compared to previous C₆₀- and C₆₀-derivative-based supported fullerene materials. Further, this material rapidly inactivates MS2 bacteriophage under sunlight illumination, oxidizes various organic contaminants, and does not appear to be significantly fouled by natural organic matter (NOM), highlighting the potential of these materials in real-world applications. Collectively, the ease of preparation and significantly enhanced visible-light photoactivity of these materials advance fullerene-based technologies for water treatment

Functionalized Fullerenes in Water: A Closer Look

The excellent photophysical properties of C₆₀ fullerenes have spurred much research on their application to aqueous systems for biological and environmental applications. Spontaneous aggregation of C₆₀ in water and the consequent diminution of photoactivity present a significant challenge to aqueous applications. The mechanisms driving the reduction of photoactivity in fullerene aggregates and the effects of functionalization on these processes, however, are not well understood. Here, we take a closer look at the molecular phenomena of functionalized fullerene interactions in water utilizing simulation and experimental tools. Molecular dynamic simulations were performed to investigate time-evolved molecular interactions in systems containing fullerenes with water, oxygen, and/or neighboring fullerene molecules, complimented by physical and chemical characterizations of the fullerenes pre- and postaggregation. Aggregates with widely different photoactivities exhibit similar fullerene–water interactions as well as surface and aggregation characteristics. Photoactive fullerene aggregates had weaker fullerene–fullerene and fullerene–O₂ interactions, suggesting the importance of molecular interactions in the sensitization route