Open Access Publications - Department of Chemical and Biomolecular Engineering
Permanent URI for this collection
Open access publications by faculty, postdocs, and graduate students in the Department of Chemical and Biomolecular Engineering
Browse
Recent Submissions
Item Small Angle X-Ray Scattering Studies on the Effects of Ultra Shear Technology on Model Animal and Plant-Based Protein Solutions(Journal of Food Process Engineering, 2025-05-19) Janahar, Jerish Joyner; Hu, Hetian; Balasubramaniam, V. M.; Teixeira, Susana C. M.The effects of shear, temperature, and high pressure on model solutions of bovine milk and plant proteins were investigated. Samples of bovine β-lactoglobulin (BLG), pea lectin (PL), and their mixture (MIX) were treated by high-pressure processing (HPP) and ultra-shear technology (UST). BLG and PL are known for their allergenic properties, and processing conditions can potentially be used to decrease allergenicity, as well as engineer beverage properties of interest. Small angle X-ray scattering (SAXS) and confocal laser scanning microscopy were used to measure the impact of processing on the protein solutions from the microscopic to the molecular scale. SAXS data were analyzed by various approaches to assess changes in protein size and shape, oligomerization, and aggregation. The results are consistent with the BLG sensitivity to shear, pressure, and temperature. The pressure holding time was shown to be critical and thermal effects at ambient pressure are distinct from those observed under pressure. Although some changes in shape were detected, PL showed structural and colloidal resistance to the processing conditions applied. The MIX solutions appear to show a convolution of the effects observed on the isolated protein solutions, granting further investigation to clarify potential interactions between the proteins. These findings are valuable for the development of liquid beverages based on animal and plant proteins and their blends, enhancing control over functional properties and expanding their applications in food, nutraceuticals, and biomedical fields.Item Nanostructured iron and nickel oxide aerogels revolutionizing asphaltene removal in hydrocarbon processing(Scientific Reports, 2025-04-13) Babaei, Elahe; Bazyari, Amin; Shojaei, Behzad; Thompson, Levi T.Asphaltenes, complex molecules in crude oil, cause significant challenges in oil production and refining due to their tendency to form agglomerates and precipitate. This study investigates the effectiveness of preparation method of metal oxide-based adsorbents (NiO and Fe2O3) in removing asphaltenes. Nanostructured NiO and Fe2O3 xerogels and aerogels were produced through the Pechini-type and epoxide-derived sol − gel methods and employed for the adsorption of Ap1, a specific asphaltene extracted from Iranian crude oil. The nanomaterials were characterized by XRD, N2 adsorption-desorption, FE-SEM, EDS, and FT-IR. The influence of synthesis parameters, including citric acid to metal precursor molar ratio, type of adsorbent, textural characteristics, adsorption temperature, sol-gel protocols, calcination temperatures, and drying conditions, on the adsorbent performance was systematically studied. The NiO(X-300) xerogel synthesized by the epoxide-derived sol − gel with calcination at 300 °C exhibited the highest asphaltene adsorption capacity (q = 558 mg/g) among all xerogels tested. This capacity was 102% and 87% higher than those achieved on optimized reference NiO(P-600) (q = 276 mg/g) and Fe2O3(P-600) (q = 298 mg/g) adsorbents prepared by the Pechini-type method, respectively. The textural properties of both NiO and Fe2O3 materials were improved upon supercritical CO2 drying of the epoxide-derived gels, leading to the nanostructured NiO(A-300) (q = 699 mg/g) aerogel with significantly higher (~ 135%) asphaltene adsorption capacity than Fe2O3(P-600). For the best aerogels, NiO(A-300) and Fe2O3(A-450), the adsorption isotherms and the kinetic data were best fitted by the Jovanovic and the Elovich models, respectively. Ap1 exhibited rapid adsorption onto NiO(A-300) and NiO(X-300), achieving equilibrium within 20 min. The adsorption process was demonstrably spontaneous and exothermic.Item Gas-Phase Oxidative Dehydrogenation of Ethane via NO/O2 Mixtures(Industrial & Engineering Chemistry Research, 2025-05-13) Houck, Nicholas M.; Lobo, Raul F.A kinetic and thermodynamic tubular reactor model for the oxidative dehydrogenation of ethane using homogeneous NO/O2 mixtures is developed to investigate the factors controlling the ethylene selectivity. Two primary mechanisms for ethane oxidative dehydrogenation are identified from the model: the reaction between NO and NO2 to form OH radicals drives ethane dehydrogenation at large NO volume fractions (≥5%), and H2O2 homolysis drives the reaction at low NO volume fractions (<5%). The reaction conditions were optimized for C2H6 conversion; a near three-fold increase in conversion was achieved with a final 53% ethane conversion and a 90% ethylene selectivity. CO, CO2, H2O, He, and N2 were explored to control the selectivity and reaction kinetics but had little impact. Under optimal conditions, most initial NO radicals were converted into NO2; replacement of NO with NO2 was investigated. NO2/O2 mixtures achieved a maximum of 38% ethane conversion at a 90% ethylene selectivity with a 5% NO2 conversion.Item Catalytic Ethane Dehydrogenation Using a Porcupine Heating Element in a Joule-Heated Reactor(Industrial & Engineering Chemistry Research, 2025-05-03) Burentugs, Enerelt; Lobo, Raul F.A Joule-heated reactor containing a porous catalyst film deposited on a FeCrAl porcupine coil as the heating element was assembled and evaluated. The catalytic ethane dehydrogenation reaction was investigated utilizing a ZSM-5-supported MnOx catalyst. The system achieved an ethylene production rate of 31.3 mmolC2H4 gcat–1 h–1 with an ethylene selectivity exceeding 99% and 98 + % carbon balance and has a larger volumetric catalyst inventory than other Joule-heated reactor configurations reported to date. Despite ample insulation, computational fluid dynamics (CFD) simulations using ANSYS-CFX revealed axial and radial temperature gradients within the reactor, reducing the catalyst utilization effectiveness. The simulations demonstrate that adiabatic operation (perfect insulation and reflecting radiative heat back into the system) could double the ethylene production rate while improving energy efficiency. Mass and heat transfer resistances did not affect rates for catalyst layer thicknesses up to 135 μm. Analysis of the flow pattern revealed that buoyancy effects are significant at low inlet gas velocities (υin = 0.53 cm s–1 or Reinlet = 1.7), leading to reverse flows near the front and back coil terminals. These insights provide a foundation for optimizing Joule-heated reactor geometry, configuration, and performance.Item Influence of Pressure Holding Time on Ovalbumin Solution Behavior via Small-Angle Neutron Scattering and Diffusing Wave Spectroscopy(Journal of Food Process Engineering, 2025-04-14) Paul, Brian; Furst, Eric M.; Lenhoff, Abraham M.; Gilbert, Elliot P.; Wagner, Norman J.; Teixeira, Susana C. M.Protein–protein interactions (PPIs) were characterized as a function of salt concentration and applied hydrostatic pressure for hen egg ovalbumin solutions. In situ data were collected using small-angle neutron scattering (SANS) at various concentrations of ammonium sulfate. The nondestructive nature of SANS allows for extended pressure holding times and the investigation of the reversibility of effects on PPIs. An empirical scaling developed previously is shown to capture the dependence of the reduced osmotic second virial coefficient on an effective pressure, combining osmotic and hydrostatic contributions. A comparison to small-angle X-ray scattering data for ovalbumin indicates enhanced net attraction at all conditions investigated with longer pressure holding times. Pressure effects on PPIs measured by SANS are shown not to be fully reversible in the presence of salt. Pressure-triggered aggregation was detected in the hours after depressurization at moderate salt concentrations, with slow recovery of pressure-induced attraction at high salt concentrations. Consistency is demonstrated between predicted solution viscosities and experimental observations from viscometry and in situ high-pressure diffusing wave spectroscopy. Furthermore, both the strength of ovalbumin PPIs and the relative solution viscosity display Barus-like scaling with effective pressure, exhibiting distinct pressure-viscosity coefficients from those of water.Item Rheological, electrochemical, and microstructural properties of graphene oxides as flowable electrodes for energy storage applications(RSC Advances, 2025-03-25) Pincot, André; Chin, Jeffrey; Murphy, Ryan; Burpo, F. John; Yi, Caspar; Chen, Edward; Bahaghighat, H. Daniel; Thompson, Benjamin; Yuk, Simuck F.; McKinley, Gareth H.; Nagelli, Enoch A.; Armstrong, MatthewInterest in novel energy storage and conversion methods has prompted a broad interest in potential applications of conductive, complex materials such as graphene oxide slurries. Investigating the complex rheological, material, and chemical properties of chemically exfoliated graphene oxide suspensions is a potential means to address that interest. The morphological size and clustering, rheology, and electronic conductivity are determined to characterize the properties of graphene oxide (GO) suspensions from variable centrifugation speeds. The evolution of viscosity is then analyzed under oscillatory shear, steady shear, and transient shear characteristics. The resulting microstructure is then analyzed via neutron scattering analysis and imaged with scanning electron microscopy. Small-Angle Neutron Scattering (SANS) of a 500g centrifuged GO suspension determined that particle structure is locally flat sheet-like at lengths below 100 nm, crumpled aggregates of GO sheets with surface roughness at length scales from 200 nm to 2 μm, and a dense mass fractal of overlapping GO sheets extending up to length scales of 20 μm. Increased centrifugation force of the 1000g GO suspension corresponded with lower zero-shear viscosity, yield stress, and less pronounced thixotropic behavior. Rheo-dielectric measurements were conducted on 1000g and 500g GO suspensions to determine the ohmic resistance, electronic conductivity, and specific capacitance. The more fluid-like microstructure of 1000g with smaller monodispered thinning GO sheets in suspension had lower ohmic resistance and higher electronic conductivity compared to the 500g GO suspension with more polydispersed larger aggregates. The 1000g GO suspension had the highest specific capacitance of 4.63 mF cm−2 at the highest shear rate of 700 s−1 due to the higher frequency of particle–particle collisions during shear within the network of smaller and more intrinsically conductive GO sheets to store charge. Therefore, the results of this study have implications for future studies in flowable carbon nanomaterials in flow battery and flow capacitor technologies.Item Life Cycle Assessment of Thermoelectrics: Ecological Viability in Intermittent Waste Heat Scenarios(ACS Omega, 2025-04-01) Iyer, Rakesh Krishnamoorthy; Sabet, Morteza; Pilla, SrikanthThis study evaluates the ecological impacts of thermoelectrics (TEs) in stationary applications that periodically generate waste heat using life cycle assessment (LCA) methodology, a first of its kind. Six TE modules are analyzed for a periodic heat-emitting application: a natural gas-based power plant that meets only peak electricity demand. The analysis uses detailed inventories from an earlier study regarding the production and end-of-life stages of the TEs. The results show that while TEs are effective in conserving fossil fuels and lowering greenhouse gas emissions, they do not exhibit significant positive effects on other environmental impacts. These findings persist even when accounting for variations in TE conversion efficiency and lifetime and the implementation of a circular economy approach for recycling and repurposing TE modules. This suggests that the environmental suitability of TEs is predominantly influenced by the type of fossil energy source they replace, making current TEs unsuitable for stationary applications that periodically generate waste heat. The study also highlights the need for further research on the development of new, practical TEs that utilize nontoxic, abundant elements and are produced through less energy-intensive techniques.Item Biophysical modelling of intrinsic cardiac nervous system neuronal electrophysiology based on single-cell transcriptomics(The Journal of Physiology, 2025-03-12) Gupta, Suranjana; Gee, Michelle M.; Newton, Adam J. H.; Kuttippurathu, Lakshmi; Moss, Alison; Tompkins, John D.; Schwaber, James S.; Vadigepalli, Rajanikanth; Lytton, William W.The intrinsic cardiac nervous system (ICNS), termed as the heart's ‘little brain’, is the final point of neural regulation of cardiac function. Studying the dynamic behaviour of these ICNS neurons via multiscale neuronal computer models has been limited by the sparsity of electrophysiological data. We developed and analysed a computational library of neuronal electrophysiological models based on single neuron transcriptomic data obtained from ICNS neurons. Each neuronal genotype was characterized by a unique combination of ion channels identified from the transcriptomic data, using a cycle threshold cutoff that ensured the electrical excitability of the neuronal models. The parameters of the ion channel models were grounded based on passive properties (resting membrane potential, input impedance and rheobase) to avoid biasing the dynamic behaviour of the model. Consistent with experimental observations, the emergent model dynamics showed phasic activity in response to the current clamp stimulus in a majority of neuronal genotypes (61%). Additionally, 24% of the ICNS neurons showed a tonic response, 11% were phasic-to-tonic with increasing current stimulation and 3% showed tonic-to-phasic behaviour. The computational approach and the library of models bridge the gap between widely available molecular-level gene expression and sparse cellular-level electrophysiology for studying the functional role of the ICNS in cardiac regulation and pathology.Item Zeolite-Encapsulated Ni Catalyst for the Direct Conversion of Mono- and Polysaccharides to Ethylene Glycol(ACS Sustainable Chemistry and Engineering, 2025-04-25) Surendhran, Roshaan; Orazov, Marat; Lobo, Raul F.We have developed a simple, scalable, postsynthetic treatment for the encapsulation of Ni nanoparticles inside MFI zeolites as size-selective hydrogenation catalysts. We show that size-selective sieving of glucose from glycolaldehyde by the Ni-MFI-type zeolites enables an improvement in ethylene glycol yield by minimizing sorbitol and mannitol formation. This property is applied for the direct conversion of glucose to ethylene glycol, which can achieve 63% yield with less than 2% sugar alcohols in batch operation at lower reaction temperatures than previously reported (170 °C vs 230 °C). This improvement in size selectivity and yield can be extended to polysaccharides. The impacts of catalyst loadings, temperature, pH, and substrate concentration were studied, and optimal conditions for high selectivity were identified for both glucose and starch.Item Reversible CO2 Hydrogenation, Neutron Crystallography, and Hydride Reactivity of a Triiridium Heptahydride Complex(Angewandte Chemie International Edition, 2025-04-01) Cherepakhin, Valeriy; Do, Van K.; Chavez, Anthony J.; Kelber, Jacob; Klein, Ryan A.; Novak, Eric; Cheng, Yongqiang; Wang, Xiaoping; Brown, Craig M.; Williams, Travis J.The authors report the structure, reactivity, and catalytic utility of a triiridium complex, [Ir3H6(μ3-H)(PN)3]2+ (2-H, PN = (2-pyridyl)CH2PBut2). Despite its unusual stability to unsaturated organics, electrophiles, and even CF3SO3D, they find that complex 2-H catalyzes hydrogenation of CO2 to formate (TONIr = 9600) and reverse formic acid dehydrogenation (TONIr = 54 400). The hydrogenation operates via a reactive intermediate [Ir3H4(μ-H)4(PN)3]+ (5). Neutron crystallography and DFT-supported neutron vibrational spectroscopy of 2-H reveal Ir─H bond lengths and elucidate the vibration modes within the Ir3H7 core. Stoichiometric oxidation of 2-H produces four classes of iridium complexes of varied nuclearity and hydride structure: tetra- and pentanuclear clusters [Ir3H6(μ3-AuPPh3)(PN)3]2+ (2-Au) and [Ag{Ir2H4(μ-OAc)(PN)2}2]3+ (6) are generated using AuPPh3+ and AgOAc, respectively. Further oxidation to class [Ir2H3(μ-X)2(PN)2]+ is possible with AgOAc, Hg(OAc)2, or I2. Finally, a TEMPO/HCl system completely oxidizes the hydrides and gives [Ir2Cl4(μ-Cl)2(PN)2] (11). Graphical Abstract available at: https://doi.org/10.1002/anie.202501943 A novel triiridium heptahydride cluster catalyzes reversible CO2 hydrogenation. Foundational structural and reactivity studies that combine neutron crystallography and spectroscopy, electrochemistry, synthetic studies, and kinetics uncover previously elusive metal–metal cooperative reactivity that enables a unique approach to functionalizing CO2.Item Sensitivity of electronic structure to crystal distortions in infinite-layered LaNiO2(Physical Review B, 2025-01-23) Rathnayaka, S.; Yano, S.; Morée, J.-B.; Kawashima, K.; Akimitsu, J.; Brown, C. M.; Neuefeind, J.; Louca, D.Recent observations of unconventional superconductivity (SC) in thin films of LaNiO2 (critical temperature 𝑇c≃ 10 K) and in bulk single crystals of La3Ni2O7 under pressure 𝑇c≃80K have cemented a long sought-after class of SC nickelates. In La1−𝑥Sr𝑥NiO2, SC appears only in films for reasons not understood. We perform a combination of experiments to probe the crystal structure and magnetic order in bulk LaNiO2 together with ab initio calculations of the electronic structure. We find that the infinite layers are naturally buckled out-of-plane. The electronic bands are largely unaffected by the buckling, but uniaxial compression along the 𝑐 axis may lead to a Lifshitz transition.Item Intensification of Renewable 4,4′-Dimethylbiphenyl Synthesis for Recyclable Diesters(ACS Sustainable Chemistry and Engineering, 2025-02-03) Fields, Charles C., IV; Jain, Preeti; Subramaniam, Bala; Allgeier, Alan M.; Vlachos, Dionisios G.; Lobo, Raul F.Reducing the global dependence on petroleum-derived chemical products requires renewable alternatives to replace established materials. Recent investigations demonstrated a biobased pathway to prepare the platform chemical 4,4′-dimethylbiphenyl (4,4′-DMBP). The synthesis of 4,4′-DMBP follows a two-step process: (1) 2-methylfuran (2-MF) oxidative coupling to 5,5′-dimethyl-2,2′-bifuran (5,5′-DMBF) and (2) 5,5′-DMBF tandem Diels–Alder-dehydration with ethylene to afford 4,4′-DMBP. Here, we report the intensification of reaction conditions in step (1), improving 5,5′-DMBF space-time yield up to 1.10 mol L–1h–1, an 86% increase from the baseline. Scale-up of step (1) was hindered by oxygen-deprivation-induced palladium black formation and reaction exotherms decreasing yields at larger scales. Oxygen sparging, mechanical mixing, and internal cooling implemented simultaneously enabled a 108× increase in 5,5′-DMBF production to an average of 13 g/batch. In step (2), the use of a homogeneous La(OTf)3 catalyst in the Diels–Alder-dehydration reaction─instead of heterogeneous γ-Al2O3─led to a 54% increase in 4,4′-DMBP yield with a 70 °C temperature reduction to 180 °C. Scale-up of the Diels–Alder-dehydration to 3 g/batch maintained para-selectivity for 4,4′-DMBP with full conversion to the product within 20 h. Renewable 4,4′-DMBP is achieved from the improved pathway and isolated in 96.7% purity for further utilization downstream.Item Conversion of Compositionally Diverse Plastic Waste over Earth-Abundant Sulfides(Journal of the American Chemical Society, 2025-04-02) Selvam, Esun; Schyns, Zoé O. G.; Sun, Jessie A.; Kots, Pavel A.; Kwak, Yeonsu; Korley, LaShanda T. J.; Lobo, Raul F.; Vlachos, Dionisios G.Chemical deconstruction of polyolefin plastic wastes via hydroconversion is promising for mitigating plastic accumulation in landfills and the environment. However, hydroconversion catalysts cannot handle complex feedstocks containing multiple polymers, additives, and heteroatom impurities. Here, we report a single-step strategy using earth-abundant metal sulfide catalysts to deconstruct these wastes. We show that NiMoSx/HY catalysts deconstruct polyolefin feedstocks, achieving ∼81–94% selectivity to liquid products. Postsynthetic zeolite modification enhances the catalyst’s activity by >2.5 times, achieving over 95% selectivity to liquid fuels with controllable product distribution in the naphtha, jet fuel, and diesel range. The catalyst is resilient to increasingly complex feedstocks, such as additive-containing polymers and mixed plastics composed of polyolefins and heteroatom-containing polymers, including poly(vinyl chloride). We extend the strategy to single-use polyolefin wastes that can generate toxic byproducts, such as HCl and NH3, and eliminate their emissions by integrating reaction and sorption in a one-step process.Item Toward Sustainable Materials: From Lignocellulosic Biomass to High-Performance Polymers(Accounts of Materials Research, 2025-02-21) Mahajan, Jignesh S.; Gottlieb, Eric R.; Kim, Jung Min; Epps, Thomas H., IIIConspectus Lignocellulosic biomass is an ideal feedstock for the next generation of sustainable, high-performance, polymeric materials. Although lignin is a highly available and low-cost source of natural aromatics, it is commonly burned for heat or disposed of as waste. The use of lignin for new materials introduces both challenges and opportunities with respect to incumbent petrochemical-based compounds. These considerations are derived from two fundamental aspects of lignin: its recalcitrant/heterogeneous nature and aromatic methoxy substituents. This Account highlights four key efforts from the Epps group and collaborators that established innovative methods/processes to synthesize polymers from lignin deconstruction products to unlock application potential, with a particular focus on the polymerization of biobased monomer mixtures, development of structure–property–processing relationships for diverse feedstocks, functional benefits of methoxy substituents, and scalability of lignin deconstruction. First, lignin-derivable polymethacrylate systems were probed to investigate the polymerization behavior of methacrylate monomers and predict thermomechanical properties of polymers from monomer mixtures. Notably, the glass transition temperatures (Tgs) of lignin-derivable polymethacrylates (∼100–200 °C) were comparable to, or significantly above, those of petroleum-based analogues, such as polystyrene (∼100 °C), and the Tgs of the complex, biobased copolymers could be predicted by the Fox equation prior to biomass deconstruction. Second, an understanding of structure–property relationships in polymethacrylates was applied to create performance-advantaged pressure-sensitive adhesives (PSAs) using phenolic-rich bio-oil obtained from the reductive catalytic fractionation of poplar wood. The use of actual lignin-derived monomers as the starting material was an important step because it underscored that nanostructure-forming, multiblock polymers could be readily made despite the complexity of real lignin deconstruction products. This work also highlighted that lignin-based phenolics could be used to make colorless/odorless PSAs, without complex separations/purifications, and still perform as well as commercial adhesives. Third, an intensified reductive catalytic deconstruction (RCD) process was developed to deconstruct lignin at ambient conditions, and the deconstructed products were successfully employed in 3D printing. The reactive distillation-RCD process operated at ambient pressure using a low-volatility and biobased solvent (glycerin) as a hydrogen donor, which reduced capital/operating costs, energy use, and safety hazards associated with conventional RCD. Technoeconomic analysis showed that such optimization could lead to a 60% reduction in cost to make the PSAs described above. Fourth, lignin-derivable bisguaiacols/bissyringols were explored as potential alternatives to petroleum-derived bisphenol A (BPA) in diamine-cured epoxy resins. A distinguishing feature of the lignin monomers (vs. BPA/bisphenol F [BPF]) was the presence of methoxy groups on the aromatic rings, and these methoxy moieties enabled tuning of application-specific properties, such as Tg, degradation temperature (Td), and glassy storage modulus (E′), to achieve improved processing and performance. The lignin-derivable thermosets exhibited Tgs above 100 °C, Tds above 300 °C, and E′s above 2 GPa, all values that were comparable to those of BPA-/BPF-based analogues. Moreover, the methoxy groups on these lignin-derivable compounds sterically hindered hormone receptor binding and could mitigate many of the toxicity concerns associated with BPA/BPF. This Account concludes with suggestions on future research needed to advance lignin-derived materials as sustainable and performance-advantaged alternatives by leveraging recycling/upcycling strategies and scaling-up/commercializing biomass waste.Item Coarse-grained molecular dynamics simulations of mixtures of polysulfamides(RSC Applied Polymers, 2025-02-20) Shah, Jay; Jayaraman, ArthiPolysulfamides are a new class of polymers that exhibit favorable chemical and physical properties, making them a sustainable alternative to commodity polymers like polyurea. To advance the fundamental understanding of this new class of polymers, Wu et al. [Z. Wu, J. W. Wu, Q. Michaudel and A. Jayaraman, Macromolecules, 2023, 56, 5033–5049]conducted experiments and coarse-grained (CG) molecular dynamics (MD) simulations to connect the polysulfamide backbone design to the assembled structure of polysulfamides due to hydrogen bonding between sulfamides. Their CG MD simulations qualitatively reproduced experimentally observed trends in crystallinity for analogous variations in polysulfamide backbone designs. To bring chemical specificity to this generic CG model of Wu et al. and to facilitate quantitative agreement with experiments in the future, in this work, we modify this older CG model of Wu et al. using structural information from atomistic simulations. Atomistic angle and dihedral distributions involving the sulfamide functional groups are used to modify the donor and acceptor bead positions in the new CG model. Using MD simulations with this new atomistically informed CG model, we confirm that we obtained the structural trends with varying polysulfamide backbone length, bulkiness, and non-uniformity of the segments in repeat units as seen in the previous work by Wu et al. These key structural trends are as follows: (a) shorter contour lengths of segments between sulfamide groups enhance H-bonding between sulfamides, (b) increased bulkiness in the segment hinders sulfamide–sulfamide H-bonding and reduces orientational order among chains in the assembled structure, and (c) non-uniformity in the segments along the backbone does not affect orientational order in the assembled structure. While the trends qualitatively matched between the two models, we observe quantitatively higher positional order and lower orientational order among the assembled chains in the new CG model as compared to the older CG model. This difference in local chain packing arises from a change in the donor–acceptor H-bonding pattern between the two models. In this work, we also use the new CG model to study mixing and demixing in two types of mixtures of polysulfamides: one mixture has chains with varying segment lengths between sulfamide groups and another mixture has chains with different degrees of bulkiness in the backbone. We find that increasing dissimilarity (bulkiness or length) between the two types of chains promotes demixing despite the presence of sulfamide–sulfamide H-bonding interactions.Item Tailoring the Selective Oxidation of Hydroxyl-Containing Compounds via Precisely Tuning the Hydrogen-Bond Strength of Catalyst H-Bond Acceptors(JACS Au, 2025-02-20) Feng, Xiao; Yang, Piaoping; Wang, Yinwei; Cao, Jieqi; Gao, Jin; Shi, Song; Vlachos, Dionisios G.The unique performance of the enzyme is mainly achieved via weak interactions between the “outer coordination sphere” and the substrate. Inspired by this process, we developed 3D encapsulated-structure catalysts with hydrogen-bond engineering on the shell, which mimics the “outer coordination sphere” of an enzyme. Various hydrogen bond acceptors (C═O, S═O, and N–O groups) are imparted in the shell. Concentration-dependent 1H NMR, inverse-phase gas Chromatography (IGC) measurements, and DFT calculations underscore that the hydrogen bond strength between the acceptor groups and alcohol follows the order of C═O < S═O < N–O. The hydroxyl compound oxidation rate vs the hydrogen bond strength follows a volcano behavior, reminiscent of Sabatier’s principle. The performance variation among catalysts is attributed to the adsorption strength of the substrate. The proposed bioinspired design principle expands the scope of encapsulated catalysts, enabling fine regulation of catalytic activity through precise microenvironment control via weak interactions with substrates.Item A bio-inspired approach to engineering water-responsive, mechanically-adaptive materials(Molecular Systems Design & Engineering, 2025-02-20) Jang, Daseul; Wong, Yu-Tai; Korley, LaShanda T. J.Inspired by a diverse array of hierarchical structures and mechanical function in spider silk, we leverage building blocks that can form non-covalent interactions to develop mechanically-tunable and water-responsive composite materials via hydrogen bonding modulation. Specifically, self-assembling peptide blocks consisting of poly(β-benzyl-l-aspartate) (PBLA) are introduced into a hydrophilic polyurea system. Using these peptide–polyurea hybrids (PPUs) as a hierarchical matrix, cellulose nanocrystals (CNCs) are incorporated to diversify the self-assembled nanostructures of PPUs through matrix–filler interactions. Our findings reveal that higher PBLA content in the PPUs reduces the magnitude of the stiffness differential due to the physical crosslinking induced by the peptide blocks. Additionally, the inclusion of CNCs in the PPU matrix increases the storage modulus in the dry state but also diminishes the wet-state modulus due to the shift of physical associations from peptidic arrangements to PBLA–CNC interactions, resulting in variations in the morphology of the PPU/CNC nanocomposites. This molecular design strategy allows for the development of adaptable materials with a broad range of water-responsive storage modulus switching , spanning from ∼70 MPa to ∼400 MPa. This investigation highlights the potential of harnessing peptide assembly and peptide–cellulose interactions to achieve mechanical enhancement and water-responsiveness, providing insights for engineering next-generation responsive materials.Item Neutrons and Food 7: Bridging Innovation and Measurement Needs(Neutron News, 2024-12-11) Teixeira, SusanaNeutrons and Food have made their inaugural transatlantic journey: the 7th edition of the meeting series was hosted at the University of Delaware, bringing together an international cohort of food and neutron researchers. The event featured presentations and discussions on cutting edge applications in food-related research, as well as the impact of advancements in neutron sources and instrumentation. The need to expand in-situ measurement capabilities to support food processing and engineering, and the importance of automation to enhance throughput and reliability, were highlighted.Item A Flexible Hybrid Site-Specific Integration-Based Expression System in CHO Cells for Higher-Throughput Evaluation of Monoclonal Antibody Expression Cassettes(Biotechnology Journal, 2025-01-20) Szkodny, Alana C.; Lee, Kelvin H.The implementation of site-specific integration (SSI) systems in Chinese hamster ovary (CHO) cells for the production of monoclonal antibodies (mAbs) can alleviate concerns associated with production instability and reduce cell line development timelines. SSI cell line performance is driven by the interaction between genomic integration location, clonal background, and the transgene expression cassette, requiring optimization of all three parameters to maximize productivity. Systematic comparison of these parameters has been hindered by SSI platforms involving low-throughput enrichment strategies, such as cell sorting. This study presents a recombinase-mediated cassette exchange (RMCE)-capable SSI system that uses only chemical selection to enrich for transgene-expressing RMCE pools in less than one month. The system was used to compare eight mAb expression cassettes containing two novel genetic regulatory elements, the Azin1 CpG island and the Piggybac transposase 5’ terminal repeat, in various orientations to improve the expression of two therapeutic mAbs from two genomic loci. Similar patterns of productivity and mRNA expression were observed across sites and mAbs, and the best performing cassette universally increased mAb productivity by 7- to 11-fold. This flexible system allows for higher-throughput comparison of expression cassettes from a consistent clonal and transcriptional background to optimize RMCE-derived cell lines for industrial production of mAbs.Item Developing an alternative medium for in-space biomanufacturing(Nature Communications, 2025-01-16) Lee, Hakyung; Diao, Jinjin; Tian, Yuxin; Guleria, Richa; Lee, Eunseo; Smith, Alexandra; Savage, Millie; Yeh, Daniel; Roberson, Luke; Blenner, Mark; Tang, Yinjie J.; Moon, Tae SeokIn-space biomanufacturing provides a sustainable solution to facilitate long-term, self-sufficient human habitation in extraterrestrial environments. However, its dependence on Earth-supplied feedstocks renders in-space biomanufacturing economically nonviable. Here, we develop a process termed alternative feedstock-driven in-situ biomanufacturing (AF-ISM) to alleviate dependence on Earth-based resupply of feedstocks. Specifically, we investigate three alternative feedstocks (AF)—Martian and Lunar regolith, post-consumer polyethylene terephthalate, and fecal waste—to develop an alternative medium for lycopene production using Rhodococcus jostii PET strain S6 (RPET S6). Our results show that RPET S6 could directly utilize regolith simulant particles as mineral replacements, while the addition of anaerobically pretreated fecal waste synergistically supported its cell growth. Additionally, lycopene production using AF under microgravity conditions achieved levels comparable to those on Earth. Furthermore, an economic analysis shows significant lycopene production cost reductions using AF-ISM versus conventional methods. Overall, this work highlights the viability of AF-ISM for in-space biomanufacturing.