Gas-Phase Functionalization of Phytoglycogen Nanoparticles and the Role of Reagent Structure in the Formation of Self-Limiting Hydrophobic Shells.

A suite of acyl chloride structural isomers (C6H11OCl) was used to effect gas-phase esterification of starch-based phytoglycogen nanoparticles (PhG NPs). The surface degree of substitution (DS) was quantified using X-ray photoelectron spectroscopy, while the overall DS was quantified using 1H NMR spectroscopy. Gas-phase modification initiates at the NP surface, with the extent of surface and overall esterification determined by both the reaction time and the steric footprint of the acyl chloride reagent. The less sterically hindered acyl chlorides diffuse fully into the NP interior, while the branched isomers are restricted to the near-surface region and form self-limiting hydrophobic shells, with shell thicknesses decreasing with increasing steric footprint. These differences in substitution were also reflected in the solubility of the NPs, with water solubility systematically decreasing with increasing DS. The ability to separately control both the surface and overall degree of functionalization and thereby form thin hydrophobic shells has significant implications for the development of polysaccharide-based biopolymers as nanocarrier delivery systems.

Electrostatics Control Nanoparticle Interactions with Model and Native Cell Walls of Plants and Algae.

A lack of mechanistic understanding of nanomaterial interactions with plants and algae cell walls limits the advancement of nanotechnology-based tools for sustainable agriculture. We systematically investigated the influence of nanoparticle charge on the interactions with model cell wall surfaces built with cellulose or pectin and performed a comparative analysis with native cell walls of Arabidopsis plants and green algae (Choleochaete). The high affinity of positively charged carbon dots (CDs) (46.0 ± 3.3 mV, 4.3 ± 1.5 nm) to both model and native cell walls was dominated by the strong ionic bonding between the surface amine groups of CDs and the carboxyl groups of pectin. In contrast, these CDs formed weaker hydrogen bonding with the hydroxyl groups of cellulose model surfaces. The CDs of similar size with negative (-46.2 ± 1.1 mV, 6.6 ± 3.8 nm) or neutral (-8.6 ± 1.3 mV, 4.3 ± 1.9 nm) ζ-potentials exhibited negligible interactions with cell walls. Real-time monitoring of CD interactions with model pectin cell walls indicated higher absorption efficiency (3.4 ± 1.3 10-9) and acoustic mass density (313.3 ± 63.3 ng cm-2) for the positively charged CDs than negative and neutral counterparts (p < 0.001 and p < 0.01, respectively). The surface charge density of the positively charged CDs significantly enhanced these electrostatic interactions with cell walls, pointing to approaches to control nanoparticle binding to plant biosurfaces. Ca2+-induced cross-linking of pectin affected the initial absorption efficiency of the positively charged CD on cell wall surfaces (∼3.75 times lower) but not the accumulation of the nanoparticles on cell wall surfaces. This study developed model biosurfaces for elucidating fundamental interactions of nanomaterials with cell walls, a main barrier for nanomaterial translocation in plants and algae in the environment, and for the advancement of nanoenabled agriculture with a reduced environmental impact.

Role of Phosphorus Type and Biodegradable Polymer on Phosphorus Fate and Efficacy in a Plant-Soil System.

Phosphorus (P) is critical for crop production but has a high nutrient use inefficiency. Tomato was grown in soil amended with five P-sources, used as-is, or embedded within a biodegradable polymer, polyhydroxyalkanoate (PHA). Correlation analysis identified treatments that maintain plant growth, improve bioavailable soil P, and reduce P loss. Three performance classes were identified: (i) micro- and nanohydroxyapatite, which did not increase bioavailable P, plant P-uptake, or change P in runoff/leaching compared to controls; (ii) monocalcium phosphate (MCP), dicalcium phosphate (DCP), calcium pyrophosphate nanoparticles (CAP), and PHA-MCP that increased P-uptake and/or bioavailable P but also increased P loss in runoff/leaching; and (iii) PHA-DCP and PHA-CAP, where increased bioavailable P and plant P-uptake were achieved with minimal P loss in runoff/leaching. In addition to identifying treatments that maintain plant growth, increase bioavailable P, and minimize nutrient loss, correlation plots also revealed that (i) bioavailable P was a good indicator of plant P-uptake; (ii) leached P could be predicted from water solubility; and (iii) P loss through runoff versus leaching showed similar trends. This study highlights that biopolymers can promote plant P-uptake and improve bioavailable soil P, with implications for mitigating the negative environmental impacts of P loss from agricultural systems.

Solvent-free bottom-up patterning of zeolitic imidazolate frameworks.

Patterning metal-organic frameworks (MOFs) at submicrometer scale is a crucial yet challenging task for their integration in miniaturized devices. Here we report an electron beam (e-beam) assisted, bottom-up approach for patterning of two MOFs, zeolitic imidazolate frameworks (ZIF), ZIF-8 and ZIF-67. A mild pretreatment of metal oxide precursors with linker vapor leads to the sensitization of the oxide surface to e-beam irradiation, effectively inhibiting subsequent conversion of the oxide to ZIFs in irradiated areas, while ZIF growth in non-irradiated areas is not affected. Well-resolved patterns with features down to the scale of 100 nm can be achieved. This developer-free, all-vapor phase technique will facilitate the incorporation of MOFs in micro- and nanofabrication processes.

Charged Particle-Induced Surface Reactions of Organometallic Complexes as a Guide to Precursor Design for Electron- and Ion-Induced Deposition of Nanostructures.

Focused electron beam-induced deposition (FEBID) and focused ion beam-induced deposition (FIBID) are direct-write fabrication techniques that use focused beams of charged particles (electrons or ions) to create 3D metal-containing nanostructures by decomposing organometallic precursors onto substrates in a low-pressure environment. For many applications, it is important to minimize contamination of these nanostructures by impurities from incomplete ligand dissociation and desorption. This spotlight on applications describes the use of ultra high vacuum surface science studies to obtain mechanistic information on electron- and ion-induced processes in organometallic precursor candidates. The results are used for the mechanism-based design of custom precursors for FEBID and FIBID.

Biodegradation of Functionalized Nanocellulose.

Nanocellulose has attracted widespread interest for applications in materials science and biomedical engineering due to its natural abundance, desirable physicochemical properties, and high intrinsic mineralizability (i.e., complete biodegradability). A common strategy to increase dispersibility in polymer matrices is to modify the hydroxyl groups on nanocellulose through covalent functionalization, but such modification strategies may affect the desirable biodegradation properties exhibited by pristine nanocellulose. In this study, cellulose nanofibrils (CNFs) functionalized with a range of esters, carboxylic acids, or ethers exhibited decreased rates and extents of mineralization by anaerobic and aerobic microbial communities compared to unmodified CNFs, with etherified CNFs exhibiting the highest level of recalcitrance. The decreased biodegradability of functionalized CNFs depended primarily on the degree of substitution at the surface of the material rather than within the bulk. This dependence on surface chemistry was attributed not only to the large surface area-to-volume ratio of nanocellulose but also to the prerequisite surface interaction by microorganisms necessary to achieve biodegradation. Results from this study highlight the need to quantify the type and coverage of surface substituents in order to anticipate their effects on the environmental persistence of functionalized nanocellulose.

Electron beam induced modification of ZIF-8 membrane permeation properties.

Modification of the gas permeation properties of ZIF-8 membranes using electron beam irradiation is reported. 3.8 and 3.2 fold enhancements in ideal selectivity for CO2/N2 and CO2/CH4 can be achieved with less than 1 min exposure time.

Water-processable, biodegradable and coatable aquaplastic from engineered biofilms.

Petrochemical-based plastics have not only contaminated all parts of the globe, but are also causing potentially irreversible damage to our ecosystem because of their non-biodegradability. As bioplastics are limited in number, there is an urgent need to design and develop more biodegradable alternatives to mitigate the plastic menace. In this regard, we report aquaplastic, a new class of microbial biofilm-based biodegradable bioplastic that is water-processable, robust, templatable and coatable. Here, Escherichia coli was genetically engineered to produce protein-based hydrogels, which are cast and dried under ambient conditions to produce aquaplastic, which can withstand strong acid/base and organic solvents. In addition, aquaplastic can be healed and welded to form three-dimensional architectures using water. The combination of straightforward microbial fabrication, water processability and biodegradability makes aquaplastic a unique material worthy of further exploration for packaging and coating applications.

Evaluating performance, degradation, and release behavior of a nanoform pigmented coating after natural and accelerated weathering.

Pigments with nanoscale dimensions are added to exterior coatings to achieve desirable color and gloss properties. The present study compared the performance, degradation, and release behavior of an acrylic coating that was pigmented by a nanoform of Cu-phthalocyanine after both natural (i.e., outdoor) and accelerated weathering. Samples were weathered outdoors in three geographically distinct locations across the United States (Arizona, Colorado, Maryland) continuously for 15 months. Identically prepared samples were also artificially weathered under accelerated conditions (increased ultraviolet (UV) light intensity and elevated temperatures) for three months, in one-month increments. After exposure, both sets of samples were characterized with color, gloss, and infrared spectroscopy measurements, and selectively with surface roughness measurements. Results indicated that UV-driven coating oxidation was the principal degradation pathway for both natural and accelerated weathering samples, with accelerated weathering leading to an increased rate of oxidation without altering the fundamental degradation pathway. The inclusion of the nanoform pigment reduced the rate of coating oxidation, via UV absorption by the pigment, leading to improved coating integrity compared to non-pigmented samples. Release measurements collected during natural weathering studies indicated there was never a period of weathering, in any location, that led to copper material release above background copper measurements. Lab-based release experiments performed on samples weathered naturally and under accelerated conditions found that the release of degraded coating material after each type of exposure was diminished by the inclusion of the nanoform pigment. Release measurements also indicated that the nanoform pigment remained embedded within the coating and did not release after weathering.

Unveiling the Synergistic Role of Oxygen Functional Groups in the Graphene-Mediated Oxidation of Glutathione.

This is the first report of an atomic-scale direct oxidation mechanism of the thiol group in glutathione (GSH) by epoxides on graphene oxide (GO) at room temperature. The proposed reaction mechanism is determined using a coupled experimental and computational approach; active sites for the reaction are determined through examination of GO surface chemistry changes before and after exposure to GSH, and density functional theory (DFT) calculations determine the reaction barriers for the possible GO-GSH reaction schemes. The findings build on the previously established catalytic mechanism of GSH oxidation by graphenic nanocarbon surfaces and importantly identify the direct reaction mechanism which becomes important in low-oxygen environments. Experimental results suggest epoxides as the active sites for the reaction with GSH, which we confirm using DFT calculations of reaction barriers and further identify a synergism between the adjacent epoxide and hydroxyl groups on the GO surface. The direct oxidation mechanism at specific oxygen sites offers insight into controlling GO chemical reactivity through surface chemistry manipulations. This insight is critical for furthering our understanding of GO oxidative stress pathways in cytotoxicity as well as for providing rational material design for GO applications that can leverage this reaction.

Influence of Oxygen-Containing Functional Groups on the Environmental Properties, Transformations, and Toxicity of Carbon Nanotubes.

Carbon nanotubes (CNTs) have unique physical and chemical properties that drive their use in a variety of commercial and industrial applications. CNTs are commonly oxidized prior to their use to enhance dispersion in polar solvents by deliberately grafting oxygen-containing functional groups onto CNT surfaces. In addition, CNT surface oxides can be unintentionally formed or modified after CNTs are released into the environment through exposure to reactive oxygen species and/or ultraviolet irradiation. Consequently, it is important to understand the impact of CNT surface oxidation on the environmental fate, transport, and toxicity of CNTs. In this review, we describe the specific role of oxygen-containing functional groups on the important environmental behaviors of CNTs in aqueous media (e.g., colloidal stability, adsorption, and photochemistry) as well as their biological impact. We place special emphasis on the value of systematically varying and quantifying surface oxides as a route to identifying quantitative structure-property relationships. The role of oxygen-containing functional groups in regulating the efficacy of CNT-enabled water treatment technologies and the influence of surface oxides on other carbon-based nanomaterials are also evaluated and discussed.

UV-Vis quantification of hydroxyl radical concentration and dose using principal component analysis.

Hydroxyl radicals (∙OH) are powerful oxidizing species formed naturally in the environment or artificially produced to destroy contaminants in water treatment facilities. Their short lifetime and high reactivity, however, present a significant challenge to quantifying their concentration in solution. Herein, we developed a novel method to accurately measure the steady-state ∙OH concentration and total ∙OH dose produced during the UV photolysis of hydrogen peroxide (H2O2) by monitoring the loss of salicylic acid (SA). This information can be acquired using only benchtop UV-Vis spectroscopy, thus expanding measurement capabilities of resource-limited laboratories by eliminating the need for sophisticated instrumentation. To improve the precision with which the rate of SA loss was measured compared to previous methods, we applied principal component analysis (PCA) to fit the UV-Vis spectra collected during SA exposure to ∙OH. For our experimental conditions consisting of 12 mL solutions composed of ≤ 100 mM H2O2 and 0.07 mM SA, the steady-state ∙OH concentration throughout the complete photolysis of H2O2 was 1.33 × 10-11 M ± 1.14 × 10-12 M. This represents more than a ten-fold improvement in reducing the uncertainty of the measurement, with respect to narrowing the 95 % confidence interval, compared to a previous method that employed matrix analysis to process the spectra. Furthermore, the variance of the measured ∙OH concentrations was reduced by a factor of 100 compared to previous methods. Using PCA, the limit-of-detection and limit-of-quantitation for ∙OH are 5.33 × 10-13 M and 1.23 × 10-12 M, respectively. By developing quantitative relationships among ∙OH concentration, H2O2 concentration, and UV exposure time, we also show how to calculate the equivalent exposure to ∙OH generated in natural aquatic environments by indirect photolysis. Finally, we use this methodology to demonstrate that the presence of suspended carbonaceous nanoparticles at concentrations as high as 300 ppm does not affect ∙OH concentration.

Surface Curvature and Aminated Side-Chain Partitioning Affect Structure of Poly(oxonorbornenes) Attached to Planar Surfaces and Nanoparticles of Gold.

Cationic amphiphilic polymers are often used to coat nanoparticles as they increase chemical stability in solution and exhibit membrane disruption activities. Among these, poly(oxonorbornenes) (PONs) are tunable membrane disruptors. They can be constructed with either one amine-terminated side chain and one hydrophobic alkyl side chain (PON-50) or two amine-terminated side chains (PON-100) on each repeat unit and can then be conjugated to gold nanoparticles using O-(2-carboxyethyl)-O'-(2-mercaptoethyl) heptaethylene glycol (HEG) spacers. While the amine content and membrane disruption activity of PONs can be controlled, the detailed structural properties of PONs conjugated to gold nanoparticles remain less understood. To address this, we performed molecular dynamics simulations of PON-50 and PON-100 to determine the nonbonded energies of PON structures as a function of amine composition. We found increasing energetic stabilization with decreasing amine composition. These results were consistent with experimental observations obtained with X-ray photoelectron spectroscopy (XPS) in which PON-100 was found to have the lowest conjugation efficiency to gold surfaces out of a range of PON amination ratios. Computationally obtained energetics suggest that replacing the aliphatic amine groups with aromatic amine groups can reverse this behavior and lead to more stable PON structures with increasing amine content. We also found that the curvature of the gold nanoparticle surface affects interactions between the surface and the amine groups of PON-50. Increasing curvature decreased these interactions, resulting in a smaller effective footprint of the HEG-PON-50 structure.

Influence of polymer type and carbon nanotube properties on carbon nanotube/polymer nanocomposite biodegradation.

The interaction of anaerobic microorganisms with carbon nanotube/polymer nanocomposites (CNT/PNC) will play a major role in determining their persistence and environmental fate at the end of consumer use when these nano-enabled materials enter landfills and encounter wastewater. Motivated by the need to understand how different parameters (i.e., polymer type, microbial phenotype, CNT characteristics) influence CNT/PNC biodegradation rates, we have used volumetric biogas measurements and kinetic modeling to study biodegradation as a function of polymer type and CNT properties. In one set of experiments, oxidized multiwall carbon nanotubes (O-MWCNTs) with a range of CNT loadings 0-5% w/w were incorporated into poly-ε-caprolactone (PCL) and polyhydroxyalkanoates (PHA) matrices and subjected to biodegradation by an anaerobic microbial community. For each CNT/PNC, complete polymer biodegradation was ultimately observed, although the rate of biodegradation was inhibited above certain critical CNT loadings dependent upon the polymer type. Higher loadings of pristine MWCNTs were needed to decrease the rate of polymer biodegradation compared to O-MWCNTs, an effect ascribed principally to differences in CNT dispersion within the polymer matrices. Above certain CNT loadings, a CNT mat of similar shape to the initial PNC was formed after polymer biodegradation, while below this threshold, CNT aggregates fragmented in the media. In situations where biodegradation was rapid, methanogen growth was disproportionately inhibited compared to the overall microbial community. Analysis of the results obtained from this study indicates that the inhibitory effect of CNTs on polymer biodegradation rate is greatest under conditions (i.e., polymer type, microbial phenotype, CNT dispersion) where biodegradation of the neat polymer is slowest. This new insight provides a means to predict the environmental fate, persistence, and transformations of CNT-enabled polymer materials.

Photochemical Transformations of Carbon Dots in Aqueous Environments.

The unique physicochemical and luminescent properties of carbon dots (CDs) have motivated research efforts toward their incorporation into commercial products. Increased use of CDs will inevitably lead to their release into the environment where their fate and persistence will be influenced by photochemical transformations, the nature of which is poorly understood. This knowledge gap motivated the present investigation of the effects of direct and indirect photolysis on citric and malic acid-based CDs. Our results indicate that natural sunlight will rapidly and non-destructively photobleach CDs into optically inactive carbon nanoparticles. We demonstrate that after photobleaching, •OH exposure degrades CDs in a two-step process that will span several decades in natural waters. The first step, occurring over several years of •OH exposure, involves depolymerization of the CD structure, characterized by volatilization of over 60% of nascent carbon atoms and the oxidation of nitrogen atoms into nitro groups. This is followed by a slower oxidation of residual carbon atoms first into carboxylic acids and then volatile carbon species, while nitrogen atoms are oxidized into nitrate ions. Considered alongside related CD studies, our findings suggest that the environmental behavior of CDs will be strongly influenced by the molecular precursors used in their synthesis.

Identifying and Rationalizing the Differing Surface Reactions of Low-Energy Electrons and Ions with an Organometallic Precursor.

Surface reactions of electrons and ions with physisorbed organometallic precursors are fundamental processes in focused electron and ion beam-induced deposition (FEBID and FIBID, respectively) of metal-containing nanostructures. Markedly different surface reactions occur upon exposure of nanometer-scale films of (η5-Cp)Fe(CO)2Re(CO)5 to low-energy electrons (500 eV) compared to argon ions (860 eV). Electron-induced surface reactions are initiated by electronic excitation and fragmentation of (η5-Cp)Fe(CO)2Re(CO)5, causing half of the CO ligands to desorb. Residual CO ligands decompose under further electron irradiation. In contrast, Ar+-induced surface reactions proceed by an ion-molecule momentum/energy transfer process, causing the desorption of all CO ligands without significant ion-induced precursor desorption. This initial decomposition step is followed by ion-induced sputtering of the deposited atoms. The fundamental insights derived from this study can be used not only to rationalize the composition of deposits made by FEBID and FIBID but also to inform the choice of a charged particle deposition strategy and the design of new precursors for these emerging nanofabrication tools.

Design, Synthesis, and Evaluation of CF3AuCNR Precursors for Focused Electron Beam-Induced Deposition of Gold.

The Au(I) complexes CF3AuCNMe (1a) and CF3AuCN tBu (1b) were investigated as Au(I) precursors for focused electron beam-induced deposition (FEBID) of metallic gold. Both 1a and 1b are sufficiently volatile for sublimation at 125 ± 1 mTorr in the temperature range of roughly 40-50 °C. Electron impact mass spectra of 1a-b show gold-containing ions resulting from fragmenting the CF3 group and the CNR ligand, whereas in negative chemical ionization of 1a-b, the major fragment results from dealkylation of the CNR ligand. Steady-state depositions from 1a in an Auger spectrometer produce deposits with a similar gold content to the commercial precursor Me2Au(acac) (3) deposited under the same conditions, while the gold content from 1b is less. These results enable us to suggest the likely fate of the CF3 and CNR ligands during FEBID.

Copper release and transformation following natural weathering of nano-enabled pressure-treated lumber.

Commercially available lumber, pressure-treated with micronized copper azole (MCA), has largely replaced other inorganic biocides for residential wood treatment in the USA, yet little is known about how different outdoor environmental conditions impact the release of ionic, nano-scale, or larger (micron-scale) copper from this product. Therefore, we weathered pressure treated lumber for 18 months in five different climates across the continental United States. Copper release was quantified every month and local weather conditions were recorded continuously to determine the extent to which local climate regulated the release of copper from this nano-enabled product during its use phase. Two distinct release trends were observed: In cooler, wetter climates release occurred primarily during the first few months of weathering, as the result of copper leaching from surface/near-surface areas. In warmer, drier climates, less copper was initially released due to limited precipitation. However, as the wood dried and cracked, the exposed copper-bearing surface area increased, leading to increased copper release later in the product lifetime. Single-particle-ICP-MS results from laboratory prepared MCA-wood leachate solutions indicated that a) the predominant form of released copper passed through a filter smaller than 0.45 micrometers and b) released particles were largely resistant to dissolution over the course of 6 wks. Toxicity Characteristic Leaching Procedure (TCLP) testing was conducted on nonweathered and weathered MCA-wood samples to simulate landfill conditions during their end-of-life (EoL) phase and revealed that MCA wood released <10% of initially embedded copper. Findings from this study provide data necessary to complete a more comprehensive evaluation of the environmental and human health impacts introduced through release of copper from pressure treated lumber utilizing life cycle assessment (LCA).

Next-Generation Complex Metal Oxide Nanomaterials Negatively Impact Growth and Development in the Benthic Invertebrate Chironomus riparius upon Settling.

Most studies of nanomaterial environmental impacts have focused on relatively simple first-generation nanomaterials, including metals or metal oxides (e.g., Ag, ZnO) for which dissolution largely accounts for toxicity. Few studies have considered nanomaterials with more complex compositions, such as complex metal oxides, which represent an emerging class of next-generation nanomaterials used in commercial products at large scales. Importantly, many nanomaterials are not colloidally stable in aqueous environments and will aggregate and settle, yet most studies use pelagic rather than benthic-dwelling organisms. Here we show that exposure of the model benthic species Chironomus riparius to lithium cobalt oxide (Li xCo1- xO2, LCO) and lithium nickel manganese cobalt oxide (Li xNi yMn zCo1- y- zO2, NMC) at 10 and 100 mg·L-1 caused 30-60% declines in larval growth and a delay of 7-25 d in adult emergence. A correlated 41-48% decline in larval hemoglobin concentration and related gene expression changes suggest a potential adverse outcome pathway. Metal ions released from nanoparticles do not cause equivalent impacts, indicating a nanospecific effect. Nanomaterials settled within 2 days and indicate higher cumulative exposures to sediment organisms than those in the water column, making this a potentially realistic environmental exposure. Differences in toxicity between NMC and LCO indicate compositional tuning may reduce material impact.

The role of the dihedral angle and excited cation states in ionization and dissociation of mono-halogenated biphenyls; a combined experimental and theoretical coupled cluster study.

We present a combined theoretical and experimental study on the ionization and primary fragmentation channels of the mono-halogenated biphenyls; 2-chlorobiphenyl, 2-bromobiphenyl and 2-iodobiphenyl. The ionization energies (IEs) of the 2-halobiphenyls and the appearance energies (AEs) of the principal fragments are determined through electron impact ionization, while quantum mechanical calculations at the coupled cluster level of theory are used to elucidate the observed processes and the associated dynamics. The primary fragmentation channels are the direct loss of the halogen upon ionization, the loss of the respective hydrogen halides (HX) as well as loss of the hydrogen halide and an additional hydrogen. We find that the dihedral angle strongly influences the relative potential energy of the neutral and the cation on their respective ground state surfaces, an effect caused by the strong influence of the nuclear motion on the conjugation between the phenyl rings. For the principal dissociative ionization channels from the mono-halogenated biphenyls we reason that these can not be described as statistical decay from the ground state cation, but must rather be understood as direct, state-selective processes from specific excited cationic states characterized through local ionization of either the halogenated or the non-substituted phenyl ring.