Chemical and Biomolecular Engineering - Research Publications

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    Energy dissipation during homogeneous wetting of surfaces with randomly and periodically distributed cylindrical pillars
    Kumar, P ; Mulvaney, P ; Harvie, DJE (ACADEMIC PRESS INC ELSEVIER SCIENCE, 2024-04)
    HYPOTHESIS: Understanding contact angle hysteresis on rough surfaces is important as most industrially relevant and naturally occurring surfaces possess some form of random or structured roughness. We hypothesise that hysteresis can be described by the dilute defect model of Joanny & de Gennes [1] and that the energy dissipation occurring during the stick-slip motion of the contact line is key to developing a predictive equation for hysteresis. EXPERIMENTS: We measured hysteresis on surfaces with randomly distributed and periodically arranged microscopic cylindrical pillars for a variety of different liquids in air. The inherent (flat surface) contact angles tested range from lyophilic (θe=33.8°) to lyophobic (θe=112.0°). FINDINGS: A methodology for averaging the measured advancing and receding contact angles on random surfaces is presented. Based on these results correlations for roughness-induced energy dissipation are derived, and an equation for predicting the advancing and receding contact angles during homogeneous (Wenzel) wetting on random surfaces is presented. Equations that predict the onset of the alternate wetting conditions of hemiwicking, split-advancing, split-receding and heterogeneous (Cassie) wetting are also derived, thus defining the range of validity for the homogeneous wetting equation. A 'cluster' concept is proposed to explain the measurably higher hysteresis exhibited by structured surfaces compared to random surfaces.
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    Stratification and film ripping induced by structural forces in granular micellar thin films
    King, JP ; Dagastine, RR ; Berry, JD ; Tabor, RF (ACADEMIC PRESS INC ELSEVIER SCIENCE, 2024-03)
    HYPOTHESIS: Interactions across incredibly thin layers of fluids, known as thin films, underpin many important processes involving colloids, such as wetting-dewetting phenomena. Often in these systems, thin films are composed of complex fluids that contain dispersed components, such as spherical micelles, giving rise to oscillatory structural forces due to preferential layering under confinement. Modelling of thin film dynamics involving Derjaguin-Landau-Verwey-Overbeek (DLVO) type forces has been widely reported using the Stokes-Reynolds-Young-Laplace (SRYL) model, and we hypothesize that this theory can be extended to a concentrated micellar system by including an oscillatory structural force term in the disjoining pressure. EXPERIMENTS: We study the drainage behaviour of thin films comprising sodium dodecyl sulfate (SDS) micelles across a range of concentrations and interaction conditions between an air bubble and a mica disk using a custom-built dual-wave interferometry apparatus. FINDINGS: Early-stage film behaviour is dominated by hydrodynamics, which can be well reproduced by the SRYL model. However, experimental profiles drain significantly faster than predicted, transitioning into a structural force dominated phase characterised by four types of film ripping instabilities that we term 'waving', 'ridging', 'webbing', and 'hole-sheeting'. These instabilities were mapped according to SDS concentration and approach velocity, providing insight into the interplay between structural forces and hydrodynamic conditions.
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    Influence of Surfactant Structure on Polydisperse Formulations of Alkyl Ether Sulfates and Alkyl Amidopropyl Betaines
    Williams, AP ; Sokolova, AV ; Faber, JM ; Butler, CSG ; Starck, P ; Ainger, NJ ; Tuck, KL ; Dagastine, RR ; Tabor, RF (AMER CHEMICAL SOC, 2023-12-28)
    Surfactants provide detergency, foaming, and texture in personal care formulations, yet the micellization of typical industrial primary and cosurfactants is not well understood, particularly in light of the polydisperse nature of commercial surfactants. Synergistic interactions are hypothesized to drive the formation of elongated wormlike self-assemblies in these mixed surfactant systems. Small-angle neutron scattering, rheology, and pendant drop tensiometry are used to examine surface adsorption, viscoelasticity, and self-assembly structure for wormlike micellar formulations comprising cocoamidopropyl betaine, and its two major components laurylamidopropyl betaine and oleylamidopropyl betaine, with sodium alkyl ethoxy sulfates. The tail length of sodium alkyl ethoxy sulfates was related to their ability to form wormlike micelles in electrolyte solutions, indicating that a tail length greater than 10 carbons is required to form wormlike micelles in NaCl solutions, with the decyl homologue unable to form elongated micelles and maintaining a low viscosity even at 20 wt % surfactant loading with 4 wt % NaCl present. For these systems, the incorporation of a disperse ethoxylate linker does not enable shorter chain surfactants to elongate into wormlike micelles for single-component systems; however, it could increase the interactions between surfactants in mixed surfactant systems. For synergy in surfactant mixing, the nonideal regular solution theory is used to study the sulfate/betaine mixtures. Tail mismatch appears to drive lower critical micelle concentrations, although tail matching improves synergy with larger relative reductions in critical micelle concentrations and greater micelle elongation, as seen by both tensiometric and scattering measurements.
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    Cascaded compression of size distribution of nanopores in monolayer graphene
    Wang, J ; Cheng, C ; Zheng, X ; Idrobo, JC ; Lu, A-Y ; Park, J-H ; Shin, BG ; Jung, SJ ; Zhang, T ; Wang, H ; Gao, G ; Shin, B ; Jin, X ; Ju, L ; Han, Y ; Li, L-J ; Karnik, R ; Kong, J (NATURE PORTFOLIO, 2023-11-30)
    Monolayer graphene with nanometre-scale pores, atomically thin thickness and remarkable mechanical properties provides wide-ranging opportunities for applications in ion and molecular separations1, energy storage2 and electronics3. Because the performance of these applications relies heavily on the size of the nanopores, it is desirable to design and engineer with precision a suitable nanopore size with narrow size distributions. However, conventional top-down processes often yield log-normal distributions with long tails, particularly at the sub-nanometre scale4. Moreover, the size distribution and density of the nanopores are often intrinsically intercorrelated, leading to a trade-off between the two that substantially limits their applications5-9. Here we report a cascaded compression approach to narrowing the size distribution of nanopores with left skewness and ultrasmall tail deviation, while keeping the density of nanopores increasing at each compression cycle. The formation of nanopores is split into many small steps, in each of which the size distribution of all the existing nanopores is compressed by a combination of shrinkage and expansion and, at the same time as expansion, a new batch of nanopores is created, leading to increased nanopore density by each cycle. As a result, high-density nanopores in monolayer graphene with a left-skewed, short-tail size distribution are obtained that show ultrafast and ångström-size-tunable selective transport of ions and molecules, breaking the limitation of the conventional log-normal size distribution9,10. This method allows for independent control of several metrics of the generated nanopores, including the density, mean diameter, standard deviation and skewness of the size distribution, which will lead to the next leap in nanotechnology.
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    Synthetic peptide branched polymers for antibacterial and biomedical applications
    Shabani, S ; Hadjigol, S ; Li, W ; Si, Z ; Pranantyo, D ; Chan-Park, MB ; O’Brien-Simpson, NM ; Qiao, GG (Springer Science and Business Media LLC, )
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    Nucleation Rate of N2 and O2 in Cryogenic H2 and He
    Song, J ; Berry, JD ; Goudeli, E (AMER CHEMICAL SOC, 2023-11-09)
    The homogeneous nucleation of N2 and O2 in cryogenic H2 and He is investigated by using classical molecular dynamics (MD) simulations. The nucleation kinetics of N2 and O2 clusters, including nucleation rate, critical cluster size, and cluster energy, are elucidated in H2 and He carrier gas at thermalization temperatures of 30-80 K and initial gas densities of 5.65 × 1024-2 × 1027 m-3. The energy released from the clusters during nucleation increases the system temperature by 77-138%, consistent with N2 nucleation experiments in supersonic nozzles and the mean-field kinetic nucleation theory. The nucleation rate derived by MD, Jsim, spans across 2.14 × 1029-5.25 × 1036 m-3 s-1 for both N2 and O2 under all conditions. The MD-obtained homogeneous nucleation rate is in agreement with predictions from the self-consistent classical nucleation theory (CNT) at low temperature (<70 K) but is 3-7 orders of magnitude faster than the CNT when temperature exceeds 70 K, consistent with the literature. Increasing temperature and decreasing concentration of the nucleating vapors leads to larger critical cluster sizes. The CNT underpredicts the critical cluster size at cryogenic temperatures below 60 K by 200-700%. The present MD methodology can be used for the direct determination of the nucleation rate and critical cluster size of N2 and O2 under cryogenic conditions, circumventing the assumptions inherent in CNT.
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    Gas-Phase Phenyl Radical + O2 Reacts via a Submerged Transition State
    Shiels, OJ ; Marlton, SJP ; Poad, BLJ ; Blanksby, SJ ; da Silva, G ; Trevitt, AJ (AMER CHEMICAL SOC, 2024-01-04)
    In the gas-phase chemistry of the atmosphere and automotive fuel combustion, peroxyl radical intermediates are formed following O2 addition to carbon-centered radicals which then initiate a complex network of radical reactions that govern the oxidative processing of hydrocarbons. The rapid association of the phenyl radical-a fundamental radical related to benzene-with O2 has hitherto been modeled as a barrierless process, a common assumption for peroxyl radical formation. Here, we provide an alternate explanation for the kinetics of this reaction by deploying double-hybrid density functional theory (DFT), at the DSD-PBEP86-D3(BJ)/aug-cc-pVTZ level of theory, and locate a submerged adiabatic transition state connected to a prereaction complex along the reaction entrance pathway. Using this potential energy scheme, experimental rate coefficients k(T) for the addition of O2 to the phenyl radical are accurately reproduced within a microcanonical kinetic model. This work highlights that purportedly barrierless radical oxidation reactions may instead be modeled using stationary points, which in turn provides insight into pressure and temperature dependence.
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    Hollow Hierarchical Pd/HNC Nanoreactor as a High-Performance Catalyst for CO2 Hydrogenation to Formate
    Wu, C ; Wang, D ; Guo, J ; Zavabeti, A ; Xiao, P ; Li, GK (AMER CHEMICAL SOC, 2024-01-26)
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    Metal–Phenolic‐Mediated Assembly of Functional Small Molecules into Nanoparticles: Assembly and Bioapplications
    Chen, J ; Cortez‐Jugo, C ; Kim, C ; Lin, Z ; Wang, T ; De Rose, R ; Xu, W ; Wang, Z ; Gu, Y ; Caruso, F (Wiley, 2024-03-18)
    Abstract Small molecules, including therapeutic drugs and tracer molecules, play a vital role in biological processing, disease treatment and diagnosis, and have inspired various nanobiotechnology approaches to realize their biological function, particularly in drug delivery. Desirable features of a delivery system for functional small molecules (FSMs) include high biocompatibility, high loading capacity, and simple manufacturing processes, without the need for chemical modification of the FSM itself. Herein, we report a simple and versatile approach, based on metal–phenolic‐mediated assembly, for assembling FSMs into nanoparticles (i.e., FSM‐MPN NPs) under aqueous and ambient conditions. We demonstrate loading of anticancer drugs, latency reversal agents, and fluorophores at up to ~80 % that is mostly facilitated by π and hydrophobic interactions between the FSM and nanoparticle components. Secondary nanoparticle engineering involving coating with a polyphenol–antibody thin film or sequential co‐loading of multiple FSMs enables cancer cell targeting and combination delivery, respectively. Incorporating fluorophores into FSM‐MPN NPs enables the visualization of biodistribution at different time points, revealing that most of these NPs are retained in the kidney and heart 24 h post intravenous administration. This work provides a viable pathway for the rational design of small molecule nanoparticle delivery platforms for diverse biological applications.