Chemical & Biomolecular Engineering

Permanent URI for this communityhttp://hdl.handle.net/1903/2219

Formerly known as the Department of Chemical Engineering.

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Start date: 2018End date: 2020

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Now showing 1 - 10 of 51
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    Shape-Changing Tubular Hydrogels
    (MDPI, 2018-02-22) Raghavan, Srinivasa R.; Fernandes, Neville J.; Cipriano, Bani H.
    We describe the creation of hollow tubular hydrogels in which different zones along the length of the tube are composed of different gels. Our method to create these gels is adapted from a technique developed previously in our lab for creating solid hybrid hydrogels. The zones of our tubular gel are covalently bonded at the interfaces; as a result, these interfaces are highly robust. Consequently, the tube can be picked up, manipulated and stretched without suffering any damage. The hollow nature of these gels allows them to respond 2–30-fold faster to external stimuli compared to a solid gel of identical composition. We study the case where one zone of the hybrid tube is responsive to pH (due to the incorporation of an ionic monomer) while the other zones are not. Initially, the entire tube has the same diameter, but when pH is changed, the diameter of the pH-responsive zone alone increases (i.e., this zone bulges outward) while the other zones maintain their original diameter. The net result is a drastic change in the shape of the gel, and this can be reversed by reverting the pH to its original value. Similar localized changes in gel shape are shown for two other stimuli: temperature and solvent composition. Our study points the way for researchers to design three-dimensional soft objects that can reversibly change their shape in response to stimuli.
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    Effect of a Cationic Surfactant on Microemulsion Globules and Drug Release from Hydrogel Contact Lenses
    (MDPI, 2019-06-06) Torres-Luna, Cesar; Hu, Naiping; Koolivand, Abdollah; Fan, Xin; Zhu, Yuli; Domszy, Roman; Yang, Jeff; Yang, Arthur; Wang, Nam Sun
    The present study evaluates the in vitro release of diclofenac sodium (DFNa) from contact lenses based on poly-2-hydroxyethyl methacrylate (pHEMA) hydrogels containing an embedded microemulsion to extend release duration. The oil (ethyl butyrate)-in-water microemulsion systems are prepared with two non-ionic surfactants, Brij 97 or Tween 80, together with a long-alkyl chain cationic surfactant, cetalkonium chloride (CKC). Without CKC, Brij 97 or Tween 80-based microemulsions showed average droplet sizes of 12 nm and 18 nm, respectively. The addition of CKC decreased the average droplet sizes to 2–5 nm for both non-ionic surfactants. Such significant reduction in the average droplet size corresponds to an increase in the DFNa release duration as revealed by the in vitro experiments. Contact lens characterization showed that important properties such as optical transparency and water content of Brij 97-based contact lenses with cationic microemulsions was excellent. However, the optical transparency of the corresponding Tween 80 based contact lenses was unsatisfactory. The results indicate that cationic microemulsion-laden contact lenses can benefit from combinatory effects of microemulsions and cationic surfactant at low CKC weight percentage, e.g., with the release of 70% of the drug in 45, 10, and 7 h for B97-CKC-0.45%, CKC-0.45%, and control lenses, respectively. However, the microemulsion effect on extending DFNa release became negligible at the highest CKC weight percentage (1.8%).
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    Formation of Drug-Participating Catanionic Aggregates for Extended Delivery of Non-Steroidal Anti-Inflammatory Drugs from Contact Lenses
    (MDPI, 2019-10-10) Torres-Luna, Cesar; Koolivand, Abdollah; Fan, Xin; Agrawal, Niti R.; Hu, Naiping; Zhu, Yuli; Domszy, Roman; Briber, Robert M.; Wang, Nam Sun; Yang, Arthur
    This paper focuses on extending drug release duration from contact lenses by incorporating catanionic aggregates. The aggregates consist of a long-chain cationic surfactant, i.e., cetalkonium chloride (CKC), and an oppositely charged anti-inflammatory amphiphilic drug. We studied three non-steroidal anti-inflammatory (NSAID) drugs with different octanol–water partition coefficients; diclofenac sodium (DFNa), flurbiprofen sodium (FBNa), and naproxen sodium (NPNa). Confirmation of catanionic aggregate formation in solution was determined by steady and dynamic shear rheology measurements. We observed the increased viscosity, shear thinning, and viscoelastic behavior characteristic of wormlike micelles; the rheological data are reasonably well described using a Maxwellian fluid model with a single relaxation time. In vitro release experiments demonstrated that the extension in the drug release time is dependent on the ability of a drug to form viscoelastic catanionic aggregates. Such aggregates retard the diffusive transport of drug molecules from the contact lenses. Our study revealed that the release kinetics depends on the CKC concentration and the alkyl chain length of the cationic surfactant. We demonstrated that more hydrophobic drugs such as diclofenac sodium show a more extended release than less hydrophobic drugs such as naproxen sodium.
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    Two-Dimensional Zeolite Materials: Structural and Acidity Properties
    (MDPI, 2020-04-12) Schulman, Emily; Wu, Wei; Liu, Dongxia
    Zeolites are generally defined as three-dimensional (3D) crystalline microporous aluminosilicates in which silicon (Si4+) and aluminum (Al3+) are coordinated tetrahedrally with oxygen to form large negative lattices and consequent Brønsted acidity. Two-dimensional (2D) zeolite nanosheets with single-unit-cell or near single-unit-cell thickness (~2–3 nm) represent an emerging type of zeolite material. The extremely thin slices of crystals in 2D zeolites produce high external surface areas (up to 50% of total surface area compared to ~2% in micron-sized 3D zeolite) and expose most of their active sites on external surfaces, enabling beneficial effects for the adsorption and reaction performance for processing bulky molecules. This review summarizes the structural properties of 2D layered precursors and 2D zeolite derivatives, as well as the acidity properties of 2D zeolite derivative structures, especially in connection to their 3D conventional zeolite analogues’ structural and compositional properties. The timeline of the synthesis and recognition of 2D zeolites, as well as the structure and composition properties of each 2D zeolite, are discussed initially. The qualitative and quantitative measurements on the acid site type, strength, and accessibility of 2D zeolites are then presented. Future research and development directions to advance understanding of 2D zeolite materials are also discussed.
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    Motion of an Elastic Capsule in a Trapezoidal Microchannel under Stokes Flow Conditions
    (MDPI, 2020-05-17) Koolivand, Abdollah; Dimitrakopoulos, Panagiotis
    Even though the research interest in the last decades has been mainly focused on the capsule dynamics in cylindrical or rectangular ducts, channels with asymmetric cross-sections may also be desirable especially for capsule migration and sorting. Therefore, in the present study we investigate computationally the motion of an elastic spherical capsule in an isosceles trapezoidal microchannel at low and moderate flow rates under the Stokes regime. The steady-state capsule location is quite close to the location where the single-phase velocity of the surrounding fluid is maximized. Owing to the asymmetry of the trapezoidal channel, the capsule’s steady-state shape is asymmetric while its membrane slowly tank-treads. In addition, our investigation reveals that tall trapezoidal channels with low base ratios produce significant off-center migration for large capsules compared to that for smaller capsules for a given channel length. Thus, we propose a microdevice for the sorting of artificial and physiological capsules based on their size, by utilizing tall trapezoidal microchannels with low base ratios. The proposed sorting microdevice can be readily produced via glass fabrication or as a microfluidic device via micromilling, while the required flow conditions do not cause membrane rupture.
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    Effects of Protein Unfolding on Aggregation and Gelation in Lysozyme Solutions
    (MDPI, 2020-09-02) Nikfarjam, Shakiba; Jouravleva, Elena V.; Anisimov, Mikhail A.; Woehl, Taylor J.
    In this work, we investigate the role of folding/unfolding equilibrium in protein aggregation and formation of a gel network. Near the neutral pH and at a low buffer ionic strength, the formation of the gel network around unfolding conditions prevents investigations of protein aggregation. In this study, by deploying the fact that in lysozyme solutions the time of folding/unfolding is much shorter than the characteristic time of gelation, we have prevented gelation by rapidly heating the solution up to the unfolding temperature (~80 °C) for a short time (~30 min.) followed by fast cooling to the room temperature. Dynamic light scattering measurements show that if the gelation is prevented, nanosized irreversible aggregates (about 10–15 nm radius) form over a time scale of 10 days. These small aggregates persist and aggregate further into larger aggregates over several weeks. If gelation is not prevented, the nanosized aggregates become the building blocks for the gel network and define its mesh length scale. These results support our previously published conclusion on the nature of mesoscopic aggregates commonly observed in solutions of lysozyme, namely that aggregates do not form from lysozyme monomers in their native folded state. Only with the emergence of a small fraction of unfolded proteins molecules will the aggregates start to appear and grow.
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    Fluorinated solid electrolyte interphase enables highly reversible solid-state Li metal battery
    (AAAS, 2018-12-21) Fan, Xiulin; Ji, Xiao; Han, Fudong; Yue, Jie; Chen, Ji; Chen, Long; Deng, Tao; Jiang, Jianjun; Wang, Chunsheng
    Solid-state electrolytes (SSEs) are receiving great interest because their high mechanical strength and transference number could potentially suppress Li dendrites and their high electrochemical stability allows the use of high-voltage cathodes, which enhances the energy density and safety of batteries. However, the much lower critical current density and easier Li dendrite propagation in SSEs than in nonaqueous liquid electrolytes hindered their possible applications. Herein, we successfully suppressed Li dendrite growth in SSEs by in situ forming an LiF-rich solid electrolyte interphase (SEI) between the SSEs and the Li metal. The LiF-rich SEI successfully suppresses the penetration of Li dendrites into SSEs, while the low electronic conductivity and the intrinsic electrochemical stability of LiF block side reactions between the SSEs and Li. The LiF-rich SEI enhances the room temperature critical current density of Li3PS4 to a record-high value of >2 mA cm−2. Moreover, the Li plating/stripping Coulombic efficiency was escalated from 88% of pristine Li3PS4 to more than 98% for LiF-coated Li3PS4. In situ formation of electronic insulating LiF-rich SEI provides an effective way to prevent Li dendrites in the SSEs, constituting a substantial leap toward the practical applications of next-generation high-energy solid-state Li metal batteries.
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    Dispersing Crude Oils of Varying Viscosities Using a Food-Grade Dispersant
    (2020) Aljirafi, Futoon Osama; Raghavan, Srinivasa R; Chemical Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)
    The mitigation of crude oil spills in the ocean is generally done using chemical dispersants, which convert the oil slick into small droplets. These dispersants are mixtures of surface-active molecules (surfactants) dissolved in a solvent. Questions regarding the toxicity of current commercial dispersants have prompted our lab to develop an eco-friendly alternative based on the food-grade surfactants, soy lecithin (L) and Tween 80 (T). In previous studies, the roles played by L/T and the solvent in a typical dispersant have been studied, but all those studies were done with a light crude oil, i.e., one with a low viscosity. In this thesis, we examine if our food-grade dispersant remains effective at dispersing heavier crude oils, i.e., crudes of higher viscosity. We study a light, a medium, and a heavy crude and compare their dispersion into seawater using a fixed L/T blend in various solvents. As expected, we find that the efficiency of dispersion is lower when the crude is more viscous. Moreover, in line with our previous findings, simply varying the solvent can alter the dispersion efficiency from poor to good. The solvents that promote dispersion can be identified systematically by using a plot of Hansen Solubility Parameters (HSPs). However, there do exist several key differences between the solvents most effective for the three crudes. Our analysis suggests that crude oil composition must be taken into account when optimizing the formulation of a dispersant.
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    Mechanochemical simulations of in vivo actin architectures
    (2020) Ni, Qin; Klauda, Jeffery B; Papoian, Garegin A; Chemical Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)
    Actin cytoskeleton arranges into distinct architectures to enable cell functions under different mechanochemical environments. Although recent works have revealed the key components and processes involved in actin network dynamics, how actin cytoskeleton responds to mechanical and chemical cues to assemble higher-order in vivo structures is still poorly understood. In this thesis, we use an advanced computer simulation platform to explore the mechanochemical dynamics and the physical principles underlying the formation of three ubiquitous actin scaffolds in vivo: actin bundles, dendritic lamellipodia, as well as actin rings and shell-like cortices. We first investigate the adaptive remodeling of actomyosin networks induced by a tensile external force. The application of tensile force rapidly alters filaments' orientation, followed by slower myosin motor driven contractility that gradually consolidates the structure into a thick actin bundle. These distinct actin remodeling mechanisms at short versus long timescale provide new insights to the formation of stress-fiber like actin architectures. Then, we investigate the dynamics underlying branched actin filament assembly in networks similar to lamellipodia. By varying actin branching factors and polymerization termination proteins, we reveal how individual filament assembly is related to large scale network turnover, and discuss how it affects lamellipodia driven membrane protrusion and cell migration. Lastly, we explore the question of why actomyosin networks often form ring-like or shell-like structures in cells but condense into clusters in reconstituted networks, where this structural discrepancy is regulated by a balance between myosin driven contraction and actin polymerization speed. Our works provide potential "recipes" for the assembly of cellular actin structures, in the hope of revealing the fundamental biophysical principles underlying active cytoskeleton self-organization.
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    BEYOND LI ION: INTERFACE ENGINEERING ENABLES HIGH ENERGY DENSITY LI AND NA METAL BATTERIES
    (2020) DENG, TAO; Wang, Chunsheng; Chemical Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)
    The ever-increasing demand from electric vehicles and consumer electronics, as well as the expanding market of intermittent renewable energy storage, has sparked extensive research on energy-storage devices with low cost, high energy density, and safety. Although the state-of-the-art Li-ion battery (LIB) based on highly reversible intercalation chemistry has approached its theoretical limit after several decades’ incremental improvement, there is still no great progress in the exploration of alkaline metal chemistry (Li & Na) for next-generation batteries. Compared with Li-ion chemistry, alkaline metal anode is more attractive due to the extremely high capacity (3860/1166 mA g-1 for Li/Na) and low negative electrochemical potential (-3.04/-2.71 V for Li/Na vs. the standard hydrogen electrode), thus enables next-generation batteries with high energy density. To achieve this, significant advances have been made in liquid or solid-state electrolytes that cater to the high capacity Li/Na anodes and high-voltage cathodes, but performance of the battery is still not comparable to that of commercial LIB due to dendrite formation and unstable interphase formation. Such situation requires a deep exploration on the rational design of electrolytes and interfacial stability between the electrolytes and electrodes for realizing next-generation batteries. In this dissertation, I detailed our efforts in exploring new electrolyte systems and proposed some interface engineering strategies or methods to stabilize the electrolyte-electrode interfaces, thus supporting the next-generation battery chemistries beyond LIB technology. They include nonflammable fluorinated electrolytes, polymer composites electrolytes, as well as solid-state garnet-type (Li6.75La3Zr1.75Ta0.25O12) and Na-beta-alumina (β''-Al2O3) electrolytes for Li/Na metal batteries. We studied the dendrite formation and electrode-electrolyte interface stability in the corresponding chemistry, thermodynamics, as well as kinetics. Based on the learned mechanisms, we also proposed our strategies to suppress dendrite formation and realize good performance Li/Na metal batteries by forming stable electrolyte-electrode interphases. Being enabled by the fundamental and scientific breakthroughs in terms of electrochemical mechanisms, interface chemistry, as well as interface modification techniques, this work has provided insights into the development of high-energy Li/Na metal batteries for both academic and industrial communities.