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At least 181 records · Page 10

Protein Extraction, Precipitation, and Recovery from Chlorella sorokiniana Using Mechanochemical Methods

Protein extraction, precipitation, and recovery methods were evaluated by this study using a green alga—Chlorella sorokiniana. A mechanochemical cell disruption process was applied to facilitate protein extraction from microalgal biomass. Optimization of the mechanochemical process resulted in milling conditions that achieved a protein extraction of 52.7 ± 6.45%. The consequent acid precipitation method was optimized to recover 98.7% of proteins from the microalgal slurry. The measured protein content of the protein isolate was 41.4% w/w. These results indicate that the precipitation method is successful at recovering the extracted proteins in the algal slurry; however, the removal of non-protein solids during centrifugation and pH adjustment is not complete. The energy balance analysis elucidated that the energy demand of the protein extraction and recovery operation, at 0.83 MJ/kg dry algal biomass, is much lower than previous studies using high-pressure homogenization and membrane filtration. This study concludes that mechanochemical protein extraction and recovery is an effective, low-energy processing method, which could be used by algal biorefineries to prepare algal proteins for value-added chemical production as well as to make algal carbohydrates and lipids in the residual biomass more accessible for biofuel production.

59 BASIC BIOLOGICAL SCIENCES↗

Synthesis and Evaluation of a Bifunctional Chelator for Thorium-227 Targeted Radiotherapy

Thorium-227 (227Th) is an α-emitting radionuclide currently under investigation for targeted alpha therapy. Available chelators used for this isotope suffer from challenging multistep syntheses. Here, we present the synthesis and preclinical evaluation of a novel bifunctional chelator, p-SCN-Bn-DOTHOPO, which contains an isothiocyanate group that is suitable for conjugation to biological molecules. This bifunctional chelator was prepared with a 26% overall yield in four steps and conjugated to the human epidermal growth factor receptor 2 targeting antibody, trastuzumab. The resulting immunoconjugate was labeled with [227Th]ThIV (pH 5.5, room temperature, 60 min) with ≥95% radiochemical yield and purity. The conjugate was also labeled with zirconium-89 (89Zr), which can be used for positron emission tomography imaging. The radiometal complexes were subsequently investigated for their biological stability. The results described here provide insight into ligand design strategies and optimization of chelators for the development of the next generation of 89Zr and 227Th radiopharmaceuticals.

Thorium↗

Distinctive features of structural evolution and thermodynamic response in wide-bandgap semiconductors driven by intense electronic excitation

Radiation-tolerant material selection requires balancing lattice rigidity, defect dynamics, and electronic stability, as shown by covalent SiC outperforming ionic Ga 2 O 3 and GaN under extreme environments. Responding to intense electronic excitation, irradiation-driven phase segregation (β → δ/κ in Ga 2 O 3 ) and core–shell track (disordered structure in GaN), accompanied by elemental redistribution, contrastingly, exceptional radiation tolerance manifested by comparatively minimal lattice distortion (0.17 % strain variation) was demonstrated in SiC. These differential responses are primarily attributed to two fundamental mechanisms: (i) thermodynamic driving forces governing defect migration and phase separation, and (ii) the synergistic effects of robust covalent bonding composition coupled with efficient defect recombination processes. Here, the stronger electron–phonon (e-ph) coupling in Ga 2 O 3 (4.34 × 1018 W m −3 K −1 ) and GaN (3.55 × 10 18 W m −3 K −1 ) enhances lattice energy deposition, triggering thermal spikes (ΔT ≫ T m ) and structural transition behaviors, whereas weaker e-ph coupling in SiC (3.69 × 10 18 W m −3 K −1 ), relatively high thermodynamic parameters and efficient energy dissipation suppress thermal spikes to maintaining lattice integrity. The photoresponse degradation driven by enhanced radiative recombination is dominant in N-doped SiC, while V-doped systems achieve defect-mediated photoconduction optimization characterized by abrupt current transitions, matching fluorescence yield evolutions, and directly connecting defect engineering to optoelectronic performance.

Intense electronic excitation↗

Experimental-based mechanistic study and optimization of hydrothermal liquefaction of anaerobic digestates

Valorization of agricultural and food waste digestates is crucial for sustainable waste management to reduce environmental impacts and improve the economics of commercial farms. Hydrothermal liquefaction (HTL) of anaerobic digestates was evaluated to recover resources by converting them into carbon-dense biocrude oil and a nutrient-rich HTL aqueous phase (HTL-AP) coproduct. The effects of HTL temperature (280–360 °C), reaction time (10–50 min), feedstock pH (2.5–8.5), digestate salt content (1–5 wt%), and digestate cellulose-to-lignin ratio (0.2–1.8) on energy and nutrient recovery were systematically investigated in a set of well-designed experiments following a half-fractional central composite protocol. Response surface analysis combined with HTL product characterization and comparative literature study produced a comprehensive reaction pathway for HTL of anaerobic digestates. Moreover, this analysis revealed the importance of acidic feedstocks (pH 3.00–5.53), high reaction temperatures (337–360 °C), and reaction times <45 or 45–50 min for digestates with Cel/Lig >1 or <1, for maximizing the energy recovered in biocrude (high carbon yield and low heteroatom content) and the amounts of P, NH 3 –N, and Mg distributed in the HTL-AP. Acidic conditions catalyzed biocrude production, inhibited the Maillard reaction (lowering the nitrogen content in biocrude), and partitioned nutrients into the HTL-AP. Higher reaction temperatures coupled with longer reaction times activated hydro-denitrogenation and deoxygenation reactions to improve biocrude quality. Finally, this work provides not only validated methods to achieve targeted resource recovery for specific feedstock compositions using HTL, but also a comprehensive mechanistic understanding of the HTL of biomass waste for controlling target product characteristics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Effects of Temperature on the Assembly of Gold Nanoparticle by Interpolymer Complexation

Using synchrotron-based small-angle X-ray scattering techniques, we demonstrate that poly(ethylene glycol)-functionalized gold nanoparticles (PEG-AuNPs) are assembled into close-packed structures that include short-range order with face-centered cubic structure, where crystalline qualities are varied by controlling the electrolyte concentration, pH, and temperature of the suspensions. Here, we show that interpolymer complexation with poly(acrylic acid) (PAA) is induced by lowering the pH level of the PEG-AuNPs suspensions, and furthermore, increasing the temperature of the suspension strengthens interparticle attraction, leading to improved supercrystal structures. Our results indicate that this strategy creates robust nanoparticle superlattices with high thermal stability. The effects of PAA and PEG chain lengths on the assemblies are also investigated, and their optimal conditions for creating improved superlattices are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluations of the Fates of Alkali Metals, Actinides, Mercury, and Iodine During DWPF Recycle Diversion

The fates of alkali metals, actinides, mercury, and iodine in the Defense Waste Processing Facility Recycle Diversion process (as currently conceptualized) have been evaluated through paper studies based on available knowledge of the chemistry, physical properties, solubility, and volatility of the various species involved. The effect of pH in the range from 9 to 13 has been discussed. Recommendations for additional studies to close technology gaps have been provided, many of which are contingent upon the results of pending testing and sample characterization efforts. There is uncertainty in the amounts of soluble actinides passing through the process filter, though the bulk of the actinides should be captured on the filter with the Recycle Collection Tank solids and the total amounts of actinides should be relatively low. The Recycle Collection Tank pH could impact the fraction of actinides reaching the evaporator, but the primary factors determining the actinide fate are expected to be the amount of CO 2 sorption from air sparging or, for certain actinides (such as plutonium), oxidation and/or sorption to MnO 2 solids from permanganate additions to destroy the glycolate anion. Process optimization could minimize the amounts of actinides passing the filter. Depending upon the levels of mercury observed in recycle stream samples and because of the volatility of mercury, the evaporator should be designed with the capability to remove dense mercury phases from the condensate to avoid exceeding ETP WAC limits. The facility design must be adequate to transfer dense mercury phases and testing to confirm mercury transfer is needed. Simulant containing mercury is recommended for both filtration and evaporation testing. OLI Modeling of the various recycle streams is recommended to provide insight on the fate of iodine. Iodine-spiked simulants are recommended for upcoming evaporation tests. The pro) ect should consider the likelihood and impact of NAS scale formation in the evaporators. Process optimization may be needed to minimize the accumulation of NAS scale and possibly the sorption of actinides in the evaporator. Actual waste testing of the Recycle Diversion filtration and evaporation should include the analysis of actinides, mercury, and iodine to determine their partitioning.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Microbial necromass in cropland soils: A global meta-analysis of management effects

Microbial necromass is a large and persistent component of soil organic carbon (SOC), especially under croplands. The effects of cropland management on microbial necromass accumulation and its contribution to SOC have been measured in individual studies but have not yet been summarized on the global scale. For this study, we conducted a meta-analysis of 481-paired measurements from cropland soils to examine the management effects on microbial necromass and identify the optimal conditions for its accumulation. Nitrogen fertilization increased total microbial necromass C by 12%, cover crops by 14%, no or reduced tillage (NT/RT) by 20%, manure by 21%, and straw amendment by 21%. Microbial necromass accumulation was independent of biochar addition. NT/RT and straw amendment increased fungal necromass and its contribution to SOC more than bacterial necromass. Manure increased bacterial necromass higher than fungal, leading to decreased ratio of fungal-to-bacterial necromass. Greater microbial necromass increases after straw amendments were common under semi-arid and in cool climates in soils with pH <8, and were proportional to the amount of straw input. In contrast, NT/RT increased microbial necromass mainly under warm and humid climates. Manure application increased microbial necromass irrespective of soil properties and climate. Management effects were especially strong when applied during medium (3–10 years) to long (10+ years) periods to soils with larger initial SOC contents, but were absent in sandy soils. Close positive links between microbial biomass, necromass and SOC indicate the important role of stabilized microbial products for C accrual. Microbial necromass contribution to SOC increment (accumulation efficiency) under NT/RT, cover crops, manure and straw amendment ranged from 45% to 52%, which was 9%–16% larger than under N fertilization. In summary, long-term cropland management increases SOC by enhancing microbial necromass accumulation, and optimizing microbial necromass accumulation and its contribution to SOC sequestration requires site-specific management.

59 BASIC BIOLOGICAL SCIENCES↗

Progressive Hedging Decomposition for Solutions of Large-Scale Process Family Design Problems

Rapid, wide-scale deployment of green process systems, such as carbon capture or water desalination systems, is essential for combatting climate change. Methods relying on traditional design or modularity fail to capture the benefits of both economies of numbers and economies of scale. We have proposed process family design, which designs a family of processes simultaneously exploiting opportunities for common elements. In previous work, we explored different optimization formulations to solve this problem. In this work, we develop a decomposition approach to tackle larger problems efficiently. We solve a water desalination case study, which is too large to solve within a reasonable timeframe with the discretization formulation. We exploit the block angular structure of the discretization problem to decompose and solve using Progressive Hedging (PH). We use the open-source Python package mpi-sppy to execute PH which allows us to leverage parallelization and a HPC cluster to further improve solution time.

Stinchfield, Georgia↗

Polyamide-Based Ion Exchange Membranes: Cation-Selective Transport through Water Purification Membranes

Ion-selective membranes are necessary components of many electrochemical systems including fuel cells, electrolyzers, redox flow batteries, and electrodialyzers. Perfluorinated sulfonated membranes (PFSMs) dominate these applications due to their excellent combination of fast ion transport, stability, and processability. However, perfluorinated cation exchange membranes (CEMs) are expensive, and their production process involves chemistry that generates toxic perfluorinated chemicals. The development of affordable, nonfluorinated membranes with a competitive combination of high ion selectivity, transport, and stability could help enable the widespread use of the technologies listed above while hastening the development of emerging electrochemical systems, including aqueous alkaline CO 2 sorbent regeneration. To this end, we pursue the use of thin-film composite polyamide (PA-TFCs) membranes–those that typically find application in reverse osmosis and nanofiltration desalination–as cation-selective exchange membranes. Given their negative surface charge under neutral-to-alkaline conditions, PA-TFCs can serve as effective CEMs in these pH regimes. We prepared a series of PA-TFCs from traditional monomers (trimesoyl chloride and piperazine) and compared their thicknesses, charge densities, water transport properties, ion transport properties, and long-term stability in a high pH environment to traditional CEMs (Nafion and FKE) and commercial nanofiltration and reverse osmosis membranes. We find that some of the best-performing PA-TFC membranes have similar resistances and Na + transference numbers compared to Nafion 117 in Na 2 SO 4 and NaHCO 3 -containing solutions. This proof-of-principle study suggests that further optimization of PA-TFCs could enable cost-effective ion exchange membrane alternatives to PFSMs.

36 MATERIALS SCIENCE↗

Hydrogen production in microbial electrolysis cells with biocathodes

Electroautotrophic microbes at biocathodes in microbial electrolysis cells (MECs) can catalyze the hydrogen evolution reaction with low energy demand, facilitating long-term stable performance through specific and renewable biocatalysts. However, MECs have not yet reached commercialization due to a lack of understanding of the optimal microbial strains and reactor configurations for achieving high performance. Here, we critically analyze the criteria for the inocula selection, with a focus on the effect of hydrogenase activity and microbe–electrode interactions. We also evaluate the impact of the reactor design and key parameters, such as membrane type, composition, and electrode surface area on internal resistance, mass transport, and pH imbalances within MECs. Furthermore, this analysis paves the way for advancements that could propel biocathode-assisted MECs toward scalable hydrogen gas production.

Biotechnology & Applied Microbiology↗

Major element composition controls rare earth element solubility during leaching of coal fly ash and coal by-products

Coal combustion ash and pre-combustion coal refuse are currently under consideration as potential sources of rare earth elements. One of the early steps in recovering REEs from coal by-products is often acid leaching, which can result in low pH leachates with complex aqueous chemistry. The aim of this work was to understand the connection between REE solubility, pH, and major elemental components of leachates for coal by-products. To accomplish this, we investigated the effects of solids concentration (i.e., pulp density) and pH adjustment on REE solubility in acid leachates of coal fly ashes from the Powder River Basin (PRB) and Appalachian Basin in the United States, and a coal processing refuse from the Southwestern U.S. For PRB ashes, the concentrations of soluble REEs generally increased with increasing pulp density; however, at pulp density values above 80–100 g/L, the soluble REE concentrations in the leachates were markedly lower. Similarly, the soluble concentrations of other major solutes (Fe, Al, Si) that leached from PRB fly ashes were also non-linear with pulp density. These major elements tended to reach maximum concentration values at 60–70 g/L pulp density. In contrast, for the Appalachian fly ashes and the coal by-product, soluble concentrations of REE and major elements in leachates increased linearly with pulp density. Chemical equilibria calculations of mineral saturation indices indicated that trends in soluble REE concentrations could be explained by saturation conditions for Fe and Al-(hydr)oxides and possibly sulfate minerals, but not lanthanide hydroxides. Furthermore, pH adjustment of the acid leachates showed that REEs and many major solutes were removed from solution at pH values above 4.5, also consistent with Fe- and Al-(hydr)oxide precipitation. These results highlight the importance of understanding the chemical composition of leachates when designing REE recovery processes for low-grade geologic feedstocks and that precipitation of hydr(oxide) or sulfate minerals of major elements rather than discreet formation of REE mineral phases could be used for process optimization.

01 COAL, LIGNITE, AND PEAT↗

Assessing the Accuracy of Property Model Predictions for Cost Optimization of Desalination Technologies

Accurate modeling of seawater thermophysical and thermodynamic properties is critical for optimizing desalination processes. This study compares three seawater property models, a Reaktoro multicomponent model, the thermophysical seawater properties library from the Massachusetts Institute of Technology, and a simplified sodium chloride model, in the context of levelized cost of water (LCOW) minimization for reverse osmosis (RO) and mechanical vapor compression systems. Process simulations and cost optimizations reveal that although all three models yield comparable LCOW and specific energy consumption (SEC) estimates under baseline conditions, deviations among their predictions increase with salinity. Relative differences in LCOW and SEC reach up to 6% and 8%, respectively. RO results show greater variability due to differences in osmotic pressure predictions, which affect pressure constraints at high recoveries. Computational performance varies substantially; specifically, Reaktoro simulations are up to 28 times slower than empirical models due to their detailed equilibrium calculations. These results suggest that empirical models offer acceptable accuracy for routine desalination process design, while Reaktoro provides advantages in scenarios requiring detailed speciation, such as scaling or pH adjustment studies. These findings underscore the importance of selecting appropriate property models based on the modeling objective of desalination applications and motivate future work integrating thermodynamic rigor with empirical efficiency.

Physical and chemical properties↗

Autonomous Nanoparticle Synthesis Guided by In Situ Multiscale Structural Characterization

Autonomous synthesis platforms promise rapid exploration of vast parameter spaces; yet, integrating in situ structural characterization in closed-loop synthesis optimization remains challenging. We demonstrate a realization of such a closed-loop platform coupled with a droplet-flow microreactor, in situ X-ray scattering methods (SAXS/WAXS), and Gaussian process optimization to synthesize citrate-reduced Au nanoparticles with targeted characteristics. The system efficiently explored ∼19,000 synthesis recipes through 365 experiments, achieving precise control over size (4–60 nm) and polydispersity (σ < 0.11) across large citrate/gold ratios, exceeding traditional synthesis boundaries (1–10). Beyond confirming classical Turkevich–Frens trends, partial-dependence analysis revealed strong nonlinear coupling among precursor, citrate, and pH effects. Combining quantitative SAXS/WAXS analysis with electron microscopy characterization, we uncovered that crystallite size (d c ) and particle size (d) follow d c = 0.18d + β, where synthesis chemistry controls the intercept β while maintaining a universal slope. This parallel-band structure enables independent tuning of crystallite domain size at fixed particle diameter through a combination of chloride, gold precursor, citrate, and pH contributions (cross-validated Spearman ρ = 0.7 ± 0.1). High-resolution electron microscopy shows multiple lattice-fringe orientations within single particles, directly confirming polycrystalline domains and the ability to tune d c at the fixed d. The platform’s validation includes indistinguishable static versus flowing measurements, stable droplet transport at 100 °C, and <5% run-to-run variation, establishing a robust framework for mapping and controlling multiscale nanoparticle structure across expansive chemical spaces. In conclusion, the developed closed-loop platform can be applied to a borad range of nanosyntheis processes.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

The Model System Saccharomyces cerevisiae Versus Emerging Non-Model Yeasts for the Production of Biofuels

Microorganisms are effective platforms for the production of a variety of chemicals including biofuels, commodity chemicals, polymers and other natural products. However, deep cellular understanding is required for improvement of current biofuel cell factories to truly transform the Bioeconomy. Modifications in microbial metabolic pathways and increased resistance to various types of stress caused by the production of these chemicals are crucial in the generation of robust and efficient production hosts. Recent advances in systems and synthetic biology provide new tools for metabolic engineering to design strategies and construct optimal biocatalysts for the sustainable production of desired chemicals, especially in the case of ethanol and fatty acid production. Yeast is an efficient producer of bioethanol and most of the available synthetic biology tools have been developed for the industrial yeast Saccharomyces cerevisiae. Non-conventional yeast systems have several advantageous characteristics that are not easily engineered such as ethanol tolerance, low pH tolerance, thermotolerance, inhibitor tolerance, genetic diversity and so forth. Currently, synthetic biology is still in its initial steps for studies in non-conventional yeasts such as Yarrowia lipolytica, Kluyveromyces marxianus, Issatchenkia orientalis and Pichia pastoris. Therefore, the development and application of advanced synthetic engineering tools must also focus on these underexploited, non-conventional yeast species. Herein, we review the basic synthetic biology tools that can be applied to the standard S. cerevisiae model strain, as well as those that have been developed for non-conventional yeasts. In addition, we will discuss the recent advances employed to develop non-conventional yeast strains that are efficient for the production of a variety of chemicals through the use of metabolic engineering and synthetic biology.

09 BIOMASS FUELS↗

Graphene-polyelectrolyte multilayer membranes with tunable structure and internal charge

One great advantage of graphene-polyelectrolyte multilayer (GPM) membranes is their tunable structure and internal charge for improved separation performance. In this study, we synthesized GO-dominant GPM membrane with internal negatively-charged domains, polyethyleneimine (PEI)-dominant GPM membrane with internal positively-charged domains and charge-balanced dense/loose GPM membranes by simply adjusting the ionic strength and pH of the GO and PEI solutions used in layer-by-layer membrane synthesis. A combined system of quartz crystal microbalance with dissipation (QCM-D) and ellipsometry was used to analyze the mass deposition, film thickness, and layer density of the GPM membranes. The performance of the GPM membranes were compared in terms of both permeability and selectivity to determine the optimal membrane structure and synthesis strategy. One effective strategy to improve the GPM membrane permeability-selectivity tradeoff is to assemble charge-balanced dense membranes under weak electrostatic interactions. This balanced membrane exhibits the highest MgCl 2 selectivity (~86%). Another effective strategy for improved cation removal is to create PEI-dominant membranes that provide internal positively-charged barrier to enhance cation selectivity without sacrificing water permeability. Finally, these findings shine lights on the development of a systematic approach to push the boundary of permeability-selectivity tradeoff for GPM membranes.

42 ENGINEERING↗

Electrolyte Engineering for Efficient Electrochemical Nitrate Reduction to Ammonia on a Titanium Electrode

Nitrates from agricultural runoff and industrial waste streams are a notorious waste product and hazardous pollutant. Traditional electrochemical water remediation approaches aim to solve this problem by converting nitrates to environmentally benign N 2 while minimizing the production of environmentally hazardous side products such as ammonia and nitrous oxide in a process known as “denitrification”. We modify this concept and outline an opportunity to optimize the conversion of nitrates into ammonia, which is also a key commodity product used as a fertilizer, potential fuel, and chemical precursor. The electrochemical conversion of nitrates to ammonia recycles the fixed nitrogen and offers an appealing and supplementary alternative to the energy- and resource-intensive Haber-Bosch process. In this study, we investigated the effect of varying electrochemical conditions (pH, nitrate concentration, and applied potential) on the selective reduction of nitrate to ammonia at a titanium cathode. We observed that high concentrations of both protons and nitrate ions are needed to achieve high selectivity, reaching a peak of 82% Faradaic efficiency to ammonia at an applied potential of -1 V versus RHE and a partial current density to NH 3 of -22 mA/cm 2 , using 0.4 M [NO 3 – ] at pH ~0.77. The Ti electrode, as a poor hydrogen evolution catalyst with notable corrosion resistance, provides a large window of operating conditions to achieve high selectivity in the reduction of nitrate anions. Stability of the system was evaluated, and we found a high Faradaic efficiency throughout the course of an 8 h experiment. After electrochemical testing, titanium hydride was observed at the cathode surface. We also show a preliminary technoeconomic study, indicating that it may be feasible to employ an electrochemical strategy for the production of ammonium nitrate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Soft matter approach for creating novel protein hydrogels using fractal whey protein assemblies as building blocks

In this study, mesoscopic sized fractal assembly (FA) particles were prepared using whey protein isolate; the coldset gelation properties of FA particles were investigated in-depth. Two types of FA particles (FA -62 and FA -90) with different mean sizes were synthesized through controlled thermal treatment of whey protein solutions at two concentrations (62 g/L and 90 g/L). Particle characteristics e.g. hydrodynamic radius, ζ-potential and surface hydrophobicity were dependent on pH and structure of FA. Transmission electron microscopy (TEM) observation confirmed the fractal morphology and small-angle X-ray scattering (SAXS) analysis suggested an internal fractal structure for the obtained FA particles. Eight cold-set FA protein gels (2 % w/v) were manufactured by controlling two gelling factors at two levels: pH (5.8 and 7.0) and Ca 2+ content (5 mM and 10 mM). Rheological characteristics in the large amplitude oscillatory shear regime revealed that pH 7.0 gels were softer and elastic while pH 5.8 gels were harder and brittle. Rheology Pipkin diagrams demonstrated that the strain softening/stiffening and the shear-thinning/thickening behaviors may be fine-tuned by manipulating the key gelation factors: e.g. FA structure, pH, and Ca 2+ . The entrainment speed-dependent friction coefficient curves showed that at an intermediate velocity regime (6-250 mm s -1 ), FA -90 particles induced hydrogels had superior lubrication effect compared to FA -62 gels. Further, this work demonstrated a food structure design approach regarding tuning texture and lubrication properties of protein gels without changing protein content and protein composition. The optimized protein hydrogels may be used as texturizer for "cleaner label" food formulas and/or as delivery system for carrying micronutrients.

60 APPLIED LIFE SCIENCES↗

Electrochemical Behavior of Copper Ion Complexed with Nanoparticle Organic Hybrid Materials

Nanoscale Organic Hybrid Materials (NOHMs) have unique properties that show potential for their use as novel electrolytes that can interact with redox active species. In this work, we probe the effects of adding poly(ethyleneimine)-based NOHMs (NOHM-I-PEI) on copper ion electrochemical reactions. As NOHM-I-PEI is added to a solution containing Cu(II), the voltammetric peak current decreases. This is likely caused by strong complex formation between the PEI nitrogen and the copper, similar to complexation observed in solutions of the polymer with copper. Upon copper addition to a NOHM-I-PEI solution, the pH decreases from 10.1, plateauing at pH = 5.3 at ~3:1 N:Cu ratio indicating that Cu(II) displaces protons. The UV–visible spectra exhibit a Cu-PEI peak, the intensity of which levels off at ~2.8 N:Cu. Acid titration of the N-moieties of the PEI reveals three inflections corresponding to N-environments in the PEI. Upon controlling the pH of the solution by buffering, the "sequestration" of Cu(II) is found to occur when there are unprotonated nitrogens present in the NOHM-I-PEI system; this phenomenon is also supported by UV-vis results. Furthermore, this work highlights the potential of and the design of NOHMs to carry charged electroactive species in solutions along with key factors to control for optimal function.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗