Buckminsterfullerene's (C60) octanol-water partition coefficient (Kow) and aqueous solubility

To assess the risk and fate of fullerene C60 in the environment, its water solubility and partition coefficients in various systems are useful. In this study, the log Kow of C60 was measured to be 6.67, and the toluene-water partition coefficient was measured at log Ktw = 8.44. From these values and the respective solubilities of C60 in water-saturated octanol and water-saturated toluene, C60's aqueous solubility was calculated at 7.96 ng/L(1.11 x 10(-11) M) for the organic solvent-saturated aqueous phase. Additionally, the solubility of C60 was measured in mixtures of ethanol-water and tetrahydrofuran-water and modeled with Wohl's equation to confirm the accuracy of the calculated solubility value. Results of a generator column experiment strongly support the hypothesis that clusters form at aqueous concentrations below or near this calculated solubility. The Kow value is compared to those of other hydrophobic organic compounds, and bioconcentration factors for C60 were estimated on the basis of Kow.     

Solubility of C60 in solvent mixtures

The potential large-scale production of fullerene C60 and its widespread use in consumer products may translate into occupational and public exposure and in long-term environmental exposure. To assess the risk and fate of C60 in the environment, it is important to understand its solvate formation in common industrial solvents as the solvates may affect various properties of C60 including reactivity and toxicity, particularly when solvates occur in C60 clusters. In this study, the solubility measurements in mixed solvent system can provide useful information about solvate formation. The solubility of C60 was measured in pure toluene, tetrahydrofuran, ethanol, and acetonitrile to be 3000, 11, 1.4, and 0.04 mg/L, respectively. Additionally, the solubility of C60 was measured in mixtures of toluene-acetonitrile, toluene-ethanol, toluene-tetrahydrofuran, and acetonitrile-tetrahydrofuran. The solubility data were modeled with some accuracy using Wohl's equation. The estimated crystal energy term for C60 in tetrahydrofuran was different than that in the other solvents, indicating that the C60 solid phase in equilibrium with tetrahydrofuran solution may be a solvated crystal.     

C₆₀ oxide as a key component of aqueous C₆₀ colloidal suspensions

Stable aqueous fullerene colloidal suspensions (nC(60)) are demonstrated to rely on the [6,6]-closed epoxide derivative of the fullerene (C(60)O) for stability. This derivative is present, though often unrecognized, in small quantities in nearly all C(60) starting materials due to a reaction with air. The low-yield formation of nC(60) from organic solvent solutions results from a preferential partitioning and thus enrichment of C(60)O in the colloidal particles. This partitioning is significantly retarded in the nC(60) synthesis method that does not involve organic solvent solutions: long-term stirring in water. Instead, this method relies on trace levels of ozone in the ambient atmosphere to produce sufficient C(60)O at the surfaces of the nC(60) particles to allow stable suspension in water. Controlled-atmosphere syntheses, deliberate C(60)O enrichment, light scattering measurements, and extraction followed by HPLC analysis and UV-visible absorption spectroscopy support the above model of nC(60) formation and stabilization.     

Impact of natural organic matter on the physicochemical properties of aqueous C60 nanoparticles

Existing toxicity data indicate that industrial-scale production of C60 fullerene poses a potential threat to the environment. Evaluating the environmental impact of C60 requires careful characterization of its physicochemical properties in the natural aqueous environment. Our study aims to determine the effects of aquatic natural organic matter (NOM) on the physicochemical properties of aqueous C60 nanoparticles, nC60. Stable nC60 suspensions were formed using three different solvent exchange protocols. They were thoroughly characterized for particle size, morphology, and electrophoretic mobility in the absence or presence of two model NOM components, Suwannee River humic acid and fulvic acid. NOM caused disaggregation of nC60 crystals and aggregates under typical solution conditions of natural water, leading to significant changes in particle size and morphology. Such effect increased with increasing NOM concentration. The changes in nC060 size and morphology strongly depended on the nC60 formation pathway. Results from this study indicate that NOM may play a critical role in the transport and toxicity of C60 in the natural aqueous environment.     

Effect of encapsulating agents on dispersion status and photochemical reactivity of C60 in the aqueous phase

This study demonstrates that the degree of C60 clustering in the aqueous phase is strongly dependent on the type and concentration of encapsulating agents, such as surfactant, polymer, and natural organic matter that interact with C60. The degree of C60 clustering was quantitatively analyzed using ultraviolet-visible spectral characteristics. The dispersion status played a critical role in determining the photochemical reactivity of C60, in particular, its ability to mediate energy transfer and to produce singlet oxygen in the presence of oxygen. Consistent with findings in the organic phase, C60 in the aqueous phase lost its intrinsic photochemical reactivity when they formed aggregates. Experiments performed using a laser flash photolysis suggested that the loss of reactivity resulted from a drastic decrease in lifetime of a key reaction intermediate, that is, triplet-state C60. This study suggests that the photochemical reactivity of C60 in the aqueous phase, which has been linked to oxidative damage in biological systems in earlier studies, is strongly dependent on the media environment surrounding C60.     

Effect of dispersion on adsorption of atrazine by aqueous suspensions of fullerenes

With the widespread application of fullerenes, it is critical to assess their environmental behaviors and their impacts on the transport and bioavailability of organic contaminants. The effects of fullerene particle size, chemistry of the solution, and natural organic matter on the adsorption of atrazine by aqueous dispersions of fullerenes (C(60)) were investigated in this work. The results showed that the Polanyi-Manes model could fit the adsorption isotherms well. Smaller sizes of fullerene particles led to increased available sites and, consequently, enhanced the adsorption of atrazine on C(60). However, intensely dispersed C(60) systems might not possess suitably high adsorptive capacities due to surface chemistry change. Adsorption of atrazine by aqueous dispersions of C(60) increased with a decrease in the pH of the solution. Introduction of humic acid significantly reduced the size of the C(60) particles, and resulted in the increase of the adsorption amount. Fullerene materials, once released into the aquatic environment, are inclined to form aqueous suspensions with different degrees of dispersion, which would greatly affect the transport and fate of organic contaminants.     

C60 colloid formation in aqueous systems: effects of preparation method on size, structure, and surface charge

The discovery that negatively charged aggregates of C60 fullerene are stable in aqueous environments has elicited concerns regarding the potential environmental and health effects of these aggregates. Many previous studies have used aggregates synthesized using intermediate organic solvents. This work primarily employed an aggregate production method that more closely emulates the fate of C60 upon accidental release into the environment: extended mixing in water. The aggregates formed via this method (aqu/nC60) differ from those produced using the more common solvent exchange methods. The aqu/nC60 aggregates are heterogeneous in size (20 nm and larger) and shape (facetted to spherical), negatively charged, and crystalline in structure, exhibiting a face centered cubic (FCC) system. Solution characteristics such as aqu/nC60 aggregate size and concentration were found to be dependent upon preparation variables such as initial C60 concentration, initial particle size, and the presence or absence of natural organic matter. These results indicate that care should be taken when attempting to compare experimental results obtained with aqu/nC60 to nC60 produced by solvent exchange methods.     

Bacteriophage inactivation by UV-A illuminated fullerenes: role of nanoparticle-virus association and biological targets

Inactivation rates of the MS2 bacteriophage and (1)O(2) generation rates by four different photosensitized aqueous fullerene suspensions were in the same order: aqu-nC(60) < C(60)(OH)(6) ≈ C(60)(OH)(24) < C(60)(NH(2))(6). Alterations to capsid protein secondary structures and protein oxidation were inferred by detecting changes in infrared vibrational frequencies and carbonyl groups respectively. MS2 inactivation appears to be the result of loss of capsid structural integrity (localized deformation) and the reduced ability to eject genomic RNA into its bacterial host. Evidence is also presented for possible capsid rupture in MS2 exposed to UV-A illuminated C(60)(NH(2))(6) through TEM imagery and detection of RNA infrared fingerprints in ATR-FTIR spectra. Fullerene-virus mixtures were also directly visualized in the aqueous phase using a novel enhanced darkfield transmission optical microscope fitted with a hyperspectral imaging (HSI) spectrometer. Perturbations in intermolecular extended chains, HSI, and electrostatic interactions suggest that inactivation is a function of the relative proximity between nanoparticles and viruses and (1)O(2) generation rate. MS2 log survival ratios were linearly related to CT (product of (1)O(2) concentration C and exposure time T) demonstrating the applicability of classical Chick-Watson kinetics for all fullerenes employed in this study. Results suggest that antiviral properties of fullerenes can be increased by adjusting the type of surface functionalization and extent of cage derivatization thereby increasing the (1)O(2) generation rate and facilitating closer association with biological targets.     

Photochemical production of reactive oxygen species by C60 in the aqueous phase during UV irradiation

The objective of this study was to investigate photochemical production of singlet oxygen (1O2) and superoxide radical anion (02*-) by C60 in water. It was demonstrated that photoexcited C60 in the aqueous phase efficiently mediated transfer of absorbed energy to oxygen and produced singlet oxygen when associated with surfactant (Triton X100 and Brij 78) or polymer (polyvinylpyrrolidone), which is consistent with previously observed behavior in organic solvents. However, when C60 was present as colloidal aggregate suspension, prepared through solvent exchange or sonication, this intrinsic character was lost. Similarly, C60 associated with surfactant mediated electron transfer from electron donor (triethylamine) to oxygen producing superoxide radical, while C60 aggregates and C60 associated with polymer did not. These results suggestthat the ability of C60 to mediate energy and electron transfer may be affected by the degree of C60 aggregation in the aqueous phase as well as characteristics of associated stabilizing molecules. Dependence of photochemical reactivity of C60 on its dispersion status in the aqueous phase is critical in assessing environmental impact and cytotoxicity of this material, as C60 associated with model natural organic matter was found to exist in aggregate form and did not produce reactive oxygen species under UV irradiation.     

Effect of surfactants and dispersed components on the activity and reactivity of sorbic acid

In common with many other carboxylic acids, sorbic acid shows significant solubility in aqueous and non-aqueous solvents. The presence of a non-aqueous phase (e.g. fat) can markedly affect the concentration of the preservative in the aqueous phase. Solute distribution between the two phases is pH- and concentration-dependent. The presence of dissolved surfactants in the aqueous phase will also affect the activity of sorbic acid. This effect is due to the partitioning of the solute into surfactant micelles. The presence of dispersed components and surfactant micelles also has a marked effect on the reactivity of sorbic acid. Whereas thiols react slowly with sorbic acid, the rate of reaction is increased many-fold by the addition of low molecular weight surfactants. The mechanism of this catalysis will be explained. It has been suggested that sorbic acid inhibits enzymes by reacting with sulphydryl groups of the proteins. Kinetic data from model system studies suggest that the sorbic acid-thiol reaction may be too slow for it to be an obvious means of enzyme inhibition. However, this does not take account of possible catalysis of the reaction in the microenvironment of the protein, perhaps in a manner similar to that identified with low molecular weight surfactants.     

Preparation and Properties of Physically Modified Banana Starch Prepared by Alcoholic‐Alkaline Treatment

Granular cold‐water‐soluble (GCWS) starches were prepared from banana starch treating it with 40 and 60% aqueous ethanol at two controlled temperatures (25 and 35 °C). GCWS starches prepared at 25 °C and with 40 and 60% aqueous ethanol had the lowest cold‐water solubility, that prepared with 40% aqueous ethanol at 35 °C and stored at room temperature showed low tendency to retrogradation, as assessed by transmittance. Solubility and swelling profiles were similar for GCWS starches and the freeze‐thaw stability of GCWS starches was increased as compared with native starch. The apparent viscosity of GCWS banana starches was higher than that of its native starch counterpart.     

富勒烯[C60] 作为油脂抗氧化剂的研究

研究富勒烯[C60]对油脂的抗氧化效果。通过烘箱加热法研究富勒烯[C60]与叔丁基对苯二酚(TBHQ)、二丁基羟基甲苯(BHT)、没食子酸丙酯(PG)、V_E对橄榄油、文冠果油、亚麻籽油和猪油的过氧化值和防护因子PF20的影响并进行加热实验。结果表明,在亚麻籽油和文冠果油中的抗氧化效果为:TBHQ富勒烯[C60]PGBHTV_E;在橄榄油中的抗氧化效果为:富勒烯[C60]TBHQPGBHTV_E;在猪油中的抗氧化效果为:TBHQPGBHT富勒烯[C60]V_E。在加热实验中,添加抗氧化剂的油脂均没有析出物且色值不发生变化。表明富勒烯[C60]在油脂中具有很好的抗氧化性能,可作为食品加工、生产与储存中油脂的抗氧化剂。     

Nucleophilic aromatic substitution reactions of chloroazines with bisulfide (HS-) and polysulfides (Sn2-)

Reactions of bisulfide and polysulfides with chloroazines (important constituents of agrochemicals and textile dyes) were examined in aqueous solution at 25 degrees C. For atrazine, rates are first-order in polysulfide concentration, and polysulfide dianions are the principal reactive nucleophiles; no measurable reaction occurs with HS-. Second-order rate constants for reactions of an array of chloroazines with polysulfides are several orders of magnitude greater than for reactions with HS-. Transformation products indicate the substitution of halogen(s) by sulfur. Ring aza nitrogens substantially enhance reactivity through a combination of inductive and mesomeric effects, and electron-withdrawing or electron-donating substituents markedly enhance or diminish reactivity, respectively. The overall second-order nature of the reaction, the products observed, and reactivity trends are all consistent with a nucleophilic aromatic substitution (S(N)Ar) mechanism. Rate constants for reactions with HS- and Sn2- (n = 2-5) correlate only weakly with lowest unoccupied molecular orbital energies, suggesting that the electrophilicity of a chloroazine is not the sole determinant of its reactivity. When second-order rate constants are extrapolated to HS- and Sn2- concentrations reported in salt marsh pore waters, half-lives of minutes to years are obtained. Polysulfides in particular could play an important role in effecting abiotic transformations of chloroazines in hypoxic marine waters.     

Recovery and Purification of 10-oxo-trans-8-decenoic Acid Enzymatically Produced Using a Crude Homogenate of Agaricus bisporus

A two‐step method was developed to recover 10‐oxo‐trans‐8‐decenoic acid (ODA) at 85% purity using GRAS solvents that may be used either at laboratory or industrial scale. ODA was recovered from an aqueous reaction broth via extraction with ethyl acetate followed by evaporation. The residue was dissolved in hot hexane and subsequently crystallized at 5 °C. Optimal recovery of ODA from the reaction broth was optimized by determining the partition coefficient between phosphate buffer (range pH 2.0 to 7.5) and ethyl acetate. The intrinsic partition coefficients were 75.38 and 1.43 for the undissociated and dissociated forms, respectively. To obtain a good recovery, the optimal pH was determined to be 3.0. Purification was optimized by determining the solubility curve of ODA in hexane as a function of temperature. The solubility of ODA in hexane decreased from 0.7 mg/mL at 50 °C to 0.05 mg/ mL at 10 °C. The solubility at intermediate temperatures followed a linear van't Hoff model, indicating an approximately constant enthalpy of solution. Even when the solubility of ODA in hexane is relatively low, the temperature‐solubility profile was adequate to recrystallize ODA.     

Photochemistry of aqueous C₆₀ clusters: wavelength dependency and product characterization

To construct accurate risk assessment models for engineered nanomaterials, there is urgent need for information on the reactivity (or conversely, persistence) and transformation pathways of these materials in the natural environment. As an important step toward addressing this issue, we have characterized the products formed when aqueous C(60) clusters (nC(60)) are exposed to natural sunlight and also have assessed the wavelengths primarily responsible for phototransformation. Long-wavelength light (λ ≥ 400 nm) isolated from sunlight, was shown to be important in both the phototransformation of nC(60) and in the production of (1)O(2). The significance of visible light in mediating the phototransformation of nC(60) was supported by additional experiments with monochromatic light in which the apparent quantum yield at 436 nm (Φ(436 nm) = (2.08 ± 0.08) × 10(-5)) was comparable to that at 366 nm (Φ(366 nm) = (2.02 ± 0.07) × 10(-5)). LDI-TOF mass spectrometry indicated that most of the photoproducts formed after 947 h of irradiation in natural sunlight retain a 60 atom carbon structure. A combination of (13)C NMR analysis of (13)C-enriched nC(60), X-ray photoelectron spectroscopy and FTIR indicated that photoproducts have olefinic carbon atoms as well as a variety of oxygen-containing functional groups, including vinyl ether and carbonyl or carboxyl groups, whose presence destroys the native π-electron system of C(60). Thus, the photoreactivity of nC(60) in sunlight leads to the formation of water-soluble C(60) derivatives.     

Impact of fullerene (C60) on a soil microbial community

The nascent state of the nanoproduct industry calls for important early assessment of environmental impacts before significant releases have occurred. Clearly, the impact of manufactured nanomaterials on key soil processes must be addressed so that an unbiased discussion concerning the environmental consequences of nanotechnology can take place. In this study, soils were treated with either 1 microg C60 g(-1) soil in aqueous suspension (nC60) or 1000 microg C60 g(-1) soil in granularform, a control containing equivalent tetrahydrofuran residues as generated during nC60 formation process or water and incubated for up to 180 days. Treatment effects on soil respiration, both basal and glucose-induced, were evaluated. The effects on the soil microbial community size was evaluated using total phospholipid derived phosphate. The impact on community structure was evaluated using both fatty acid profiles and following extraction of total genomic DNA, by DGGE after PCR amplification of total genomic DNA using bacterial variable V3 region targeted primers. In addition, treatment affects on soil enzymatic activities for beta-glucosidase, acid-phosphatase, dehydrogenase, and urease were followed. Our observations show that the introduction of fullerene, as either C60 or nC60, has little impact on the structure and function of the soil microbial community and microbial processes.     

New lipophilic catechin derivatives by oxa-Pictet-Spengler reaction

Synthesis of lipophilic catechin derivatives was carried out to improve their solubility in lipidic substances that must be protected against oxidation. For this purpose, an oxa-Pictet-Spengler coupling reaction, which is not only conservative for antioxidative activity, but also simple, mild and inexpensive, was applied. This method permitted grafting of alkyl chains, from various methyl ketones, between the C and B rings of catechin. The derivatives were isolated, on the one hand, by silica gel column chromatography and, on the other, by simple aqueous washing of the crude product. Both treatments produced almost the same purity; products of the second one had best antioxidative activities given by inhibition of the induced oxidation of methyl linoleate and by reactivity with the free radical 2,2-diphenyl-picrylhydrazyl. All derivatives acquired a lipophilic character as proven by measurement of the partition coefficient between octanol and water.     

Intra-aggregate mass transport-limited bioavailability of polycyclic aromatic hydrocarbons to Mycobacterium strain PC01

Biodegradation kinetics for three- and four-ring PAHs by Mycobacterium sp. strain PC01 were measured in whole and density-fractionated estuarine sediments and in a system without intra-aggregate mass transport limitations. The biokinetic data in the systems with and without intra-aggregate mass transport limitations were compared with abiotic PAH desorption kinetics. The results indicate that intra-aggregate mass transport limitations, and not the intrinsic bacterial PAH utilization capacity, were most important in controlling the rate of biodegradation of sediment-sorbed PAHs. Achievable extent of biodegradation could be predicted by the independently measured traction of desorbable PAHs in the fast-diffusion regime of a two-domain intra-aggregate mass transport model. A closed-form mathematical model was developed to describe sediment-pore water partitioning and rapid aqueous-phase diffusion of PAHs through the macropore and mesopore network of sediment aggregates, followed by first-order biodegradation of desorbed PAHs in the bulk aqueous domain. The model effectively predicted independent biodegradation kinetics of PAHs field-aged in two estuarine sediments. Despite low aqueous solubility of PAHs, macropore and mesopore diffusion may be an important mechanism controlling intra-aggregate mass transport and bioavailability of the most readily and extensively desorbed PAHs in sediments.     

Material and energy intensity of fullerene production

Fullerenes are increasingly being used in medical, environmental, and electronic applications due to their unique structural and electronic properties. However, the energy and environmental impacts associated with their commercial-scale production have not yet been fully investigated. In this work, the life cycle embodied energy of C(60) and C(70) fullerenes has been quantified from cradle-to-gate, including the relative contributions from synthesis, separation, purification, and functionalization processes, representing a more comprehensive scope than used in previous fullerene life cycle studies. Comparison of two prevalent production methods (plasma and pyrolysis) has shown that pyrolysis of 1,4-tetrahydronaphthalene emerges as the method with the lowest embodied energy (12.7 GJ/kg of C(60)). In comparison, plasma methods require a large amount of electricity, resulting in a factor of 7-10× higher embodied energy in the fullerene product. In many practical applications, fullerenes are required at a purity >98% by weight, which necessitates multiple purification steps and increases embodied energy by at least a factor of 5, depending on the desired purity. For applications such as organic solar cells, the purified fullerenes need to be chemically modified to [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM), thus increasing the embodied energy to 64.7 GJ/kg C(60)-PCBM for the specified pyrolysis, purification, and functionalization conditions. Such synthesis and processing effects are even more significant for the embodied energy of larger fullerenes, such as C(70), which are produced in smaller quantities and are more difficult to purify. Overall, the inventory analysis shows that the embodied energy of all fullerenes are an order of magnitude higher than most bulk chemicals, and, therefore, traditional cutoff rules by weight during life cycle assessment of fullerene-based products should be avoided.     

Fullerol-sensitized production of reactive oxygen species in aqueous solution

The relative production rate of reactive oxygen in aqueous solution sensitized by fullerol (a polyhydroxylated, water-soluble form of the fullerene C60) was measured and compared to known reactive oxygen sensitizers using an oxygen consumption method. The solutions were irradiated by polychromatic visible and ultraviolet light. Reactive oxygen species were generated under both visible and ultraviolet light sources. The greatest rates of oxygen consumption were observed at acidic pH. We show for the first time evidence of both singlet oxygen and superoxide production by fullerol under both UV and polychromatic light sources.