Engineering Commons^™

The Role Of Catalytic Residue PKA On The Hydrolysis/Transglycosylation Partition In Family 3 Β-Glucosidases, Inacrist Geronimo, Christina M. Payne, Mats Sandgren

Chemical and Materials Engineering Faculty Publications

β-Glucosidases (βgls) primarily catalyze the hydrolysis of the terminal glycosidic bond at the non-reducing end of β-glucosides, although glycosidic bond synthesis (called transglycosylation) can also occur in the presence of another acceptor. In the final reaction step, the glucose product or another substrate competes with water for transfer to the glycosyl-enzyme intermediate. The factors governing the balance between the two pathways are not fully known; however, the involvement of ionizable residues in binding and catalysis suggests that their pK_a may play a role. Through constant pH molecular dynamics simulations of a glycoside hydrolase Family 3 (GH3) βgl, we …

Layer-By-Layer Assembled Membranes With Immobilized Porins, Sebastián Hernández, Cassandra Porter, Xinyi Zhang, Yinan Wei, Dibakar Bhattacharyya

Chemical and Materials Engineering Faculty Publications

New and advanced opportunities are arising for the synthesis and functionalization of membranes with selective separation, reactivity, and stimuli-responsive behavior. One such advancement is the integration of bio-based channels in membrane technologies. By a layer-by-layer (LbL) assembly of polyelectrolytes, outer membrane protein F trimers (OmpF) or “porins” from Escherichia coli with central pores ∼2 nm in diameter at their opening and ∼0.7 × 1.1 nm at their constricted region are immobilized within the pores of poly(vinylidene fluoride) microfiltration membranes, in contrast to traditional ruptured lipid bilayer or vesicle processes. These OmpF-membranes demonstrate selective rejection of non-charged organics over ionic solutes, …

Synthesis And Characterization Of Thermoresponsive Hydrogels Based On N-Isopropylacrylamide Crosslinked With 4,4′-Dihydroxybiphenyl Diacrylate, Shuo Tang, Martha Floy, Rohit Bhandari, Manjula Sunkara, Andrew J. Morris, Thomas D. Dziubla, J. Zach Hilt

Chemical and Materials Engineering Faculty Publications

A novel crosslinker [4,4′-dihydroxybiphenyl diacrylate (44BDA)] was developed, and a series of temperature-responsive hydrogels were synthesized through free radical polymerization of N-isopropylacrylamide (NIPAAm) with 44BDA. The temperature-responsive behavior of the resulting gels was characterized by swelling studies, and the lower critical solution temperature (LCST) of the hydrogels was characterized through differential scanning calorimetry. Increased content of 44BDA led to a decreased swelling ratio and shifted the LCST to lower temperatures. These novel hydrogels also displayed resiliency through multiple swelling–deswelling cycles, and their temperature responsiveness was reversible. The successful synthesis of NIPAAm-based hydrogels crosslinked with 44BDA has led to a …

A High Quality And Quantity Hybrid Perovskite Quantum Dots (Cspbx3, X= Cl, Br And I) Powders Synthesis Via Ionic Displacement, Yuhang Yin, Weiling Luan, Chengxi Zhang, Fuqian Yang

Chemical and Materials Engineering Faculty Publications

Recently, all-inorganic perovskites CsPbX₃ (X= Cl, Br and I) quantum dots (QDs) have drawn great attentions because of their PL spectra tunable over the whole visible spectral region (400-700 nm) and adjustable bandgap, which revealed a promising potential on the field of photoelectronic devices, such as solar cells, LEDs and sensors. In this paper, CsPbX₃ QDs and hybrid QDs, CsPbClxBr3-x and CsPbBrxI3-x were synthesized via one-step and two-step methods comparably. The optical bandgaps of CsPbCl₃, CsPbBr₃, and CsPbI₃, were calculated as 3.08, 2.36, and 1.73eV, respectively, based on the Tauc's equation and …

Ptfe-Based Microreactor System For The Continuous Synthesis Of Full-Visible-Spectrum Emitting Cesium Lead Halide Perovskite Nanocrystals, Chengxi Zhang, Weiling Luan, Yuhang Yin, Fuqian Yang

Chemical and Materials Engineering Faculty Publications

Colloidal perovskite nanocrystals comprised of all inorganic cesium lead halide (CsPbX₃, X = Cl, Br, I or a mixture thereof) have potential as optical gain materials due to their high luminescence efficiency. In this work, cesium lead halide nanocrystals are continuously synthesized via a microreactor system consisting of poly(tetrafluoroethylene) (PTFE) capillaries. The synthesized nanocrystals possess excellent optical properties, including a full width at half maximum of 19–35 nm, high fluorescence quantum yield of 47.8–90.55%, and photoluminescence emission in the range of 450–700 nm. For the same precursor concentrations, the photoluminescence emission peak generally increases with increasing reaction temperature, …

Effect Of Oxide On Surface Tension Of Molten Metal, Chunkai Li, Yu Shi, Yufen Gu, Fuqian Yang

Chemical and Materials Engineering Faculty Publications

Oxides as one of the commonly activating fluxes used in active tungsten inert gas welding (A-TIG welding) can dramatically increase the penetration depth to 2–4 times that of conventional welding. Using the oscillation principle of inviscid fluid, a robust method is developed to measure the average surface tension of molten metal during A-TIG welding for four different oxide activating fluxes of B₂O₃, TiO₂, SiO₂, and MgO. The experimental results suggest that the oxygen released from the decomposition of oxides is the dominant factor contributing to the change of the surface tension, which …

Development Of Novel N-Isopropylacrylamide (Nipaam) Based Hydrogels With Varying Content Of Chrysin Multiacrylate, Shuo Tang, Martha Floy, Rohit Bhandari, Thomas D. Dziubla, J. Zach Hilt

Chemical and Materials Engineering Faculty Publications

A series of novel temperature responsive hydrogels were synthesized by free radical polymerization with varying content of chrysin multiacrylate (ChryMA). The goal was to study the impact of this novel polyphenolic-based multiacrylate on the properties of N-isopropylacrylamide (NIPAAm) hydrogels. The temperature responsive behavior of the copolymerized gels was characterized by swelling studies, and their lower critical solution temperature (LCST) was characterized through differential scanning calorimetry (DSC). It was shown that the incorporation of ChryMA decreased the swelling ratios of the hydrogels and shifted their LCSTs to a lower temperature. Gels with different ChryMA content showed different levels of response to …

Spontaneous Jumping, Bouncing And Trampolining Of Hydrogel Drops On A Heated Plate, Jonathan T. Pham, Maxime Paven, Sanghyuk Wooh, Tadashi Kajiya, Hans-Jürgen Butt, Doris Vollmer

Chemical and Materials Engineering Faculty Publications

The contact between liquid drops and hot solid surfaces is of practical importance for industrial processes, such as thermal spraying and spray cooling. The contact and bouncing of solid spheres is also an important event encountered in ball milling, powder processing, and everyday activities, such as ball sports. Using high speed video microscopy, we demonstrate that hydrogel drops, initially at rest on a surface, spontaneously jump upon rapid heating and continue to bounce with increasing amplitudes. Jumping is governed by the surface wettability, surface temperature, hydrogel elasticity, and adhesion. A combination of low-adhesion impact behavior and fast water vapor formation …

Improving The Thermal Stability Of Cellobiohydrolase Cel7a From Hypocrea Jecorina By Directed Evolution, Frits Goedegebuur, Lydia Dankmeyer, Peter Gualfetti, Saeid Karkehabadi, Henrik Hansson, Suvamay Jana, Vicky Huynh, Bradley R. Kelemen, Paulien Kruithof, Edmund A. Larenas, Pauline J. M. Teunissen, Jerry Ståhlberg, Christina M. Payne, Colin Mitchinson, Mats Sandgren

Chemical and Materials Engineering Faculty Publications

Secreted mixtures of Hypocrea jecorina cellulases are able to efficiently degrade cellulosic biomass to fermentable sugars at large, commercially relevant scales. H. jecorina Cel7A, cellobiohydrolase I, from glycoside hydrolase family 7, is the workhorse enzyme of the process. However, the thermal stability of Cel7A limits its use to processes where temperatures are no higher than 50 °C. Enhanced thermal stability is desirable to enable the use of higher processing temperatures and to improve the economic feasibility of industrial biomass conversion. Here, we enhanced the thermal stability of Cel7A through directed evolution. Sites with increased thermal stability properties were combined, and …

Analysis And Modeling Of The Growth Of Intermetallic Compounds In Aluminum–Steel Joints, Gang Zhang, Manjiao Chen, Yu Shi, Jiankang Huang, Fuqian Yang

Chemical and Materials Engineering Faculty Publications

In this work, we experimentally and numerically studied the microstructures and growth of intermetallic compounds (IMCs) formed in Al–Fe (aluminum–steel) joints welded by a pulsed double electrode gas metal arc welding (DE-GMAW)-brazing method. The IMCs consist of Fe₂Al₅ and FeAl₃, with Fe₂Al₅ being the main compound in the joints. The thickness of an IMC layer increases with an increase of the welding current (heat input) into the base metal. EBSD measurement suggests that the preferred crystal orientation of the Fe₂Al₅ IMC likely provides the necessary path for Al atoms …

Glucose Recovery From Different Corn Stover Fractions Using Dilute Acid And Alkaline Pretreatment Techniques, D. Aboagye, N. Banadda, R. Kambugu, Jeffrey Seay, N. Kiggundu, A. Zziwa, I. Kabenge

Chemical and Materials Engineering Faculty Publications

Background: Limited availability of corn stover due to the competing uses (organic manure, animal feed, bio-materials, and bioenergy) presents a major concern for its future in the bio-economy. Furthermore, biomass research has exhibited different results due to the differences in the supply of enzymes and dissimilar analytical methods. The effect of the two leading pretreatment techniques (dilute acid and alkaline) on glucose yield from three corn stover fractions (cob, stalk, and leaf) sourced from a single harvest in Uganda were studied at temperatures 100, 120, 140, and 160 °C over reaction times of 5, 10, 30, and 60 min.

Results: …

Comparison Between Single Loading–Unloading Indentation And Continuous Stiffness Indentation, Yun-Fei Jia, Yuan-Yuan Cui, Fu-Zhen Xuan, Fuqian Yang

Chemical and Materials Engineering Faculty Publications

Experiments are performed on fused silica, Si, and duplex stainless steel to examine whether the CSM (continuous stiffness indentation) method will provide approximately the “same” results of contact modulus and indentation hardness as those measured from the quasi-static single loading–unloading indentation. The experimental results show that the elastic modulus measured by the CSM method is compatible with that by the quasi-static loading–unloading method for hard materials, while there exists a percentage difference of ∼21.3% between the smallest value and the largest vale of the measured indentation hardnesses from the CSM method for fused silica and a percentage difference of ∼15.3% …

Size And Shape Distributions Of Primary Crystallites In Titania Aggregates, Eric A. Grulke, Kazuhiro Yamamoto, Kazuhiro Kumagai, Ines Häusler, Werner Österle, Erik Ortel, Vasile-Dan Hodoroaba, Scott C. Brown, Christopher Chan, Jiwen Zheng, Kenji Yamamoto, Kouji Yashiki, Nam Woong Song, Young Heon Kim, Aleksandr B Stefaniak, D. Schwegler-Berry, Victoria A. Coleman, Åsa K. Jämting, Jan Herrmann, Toru Arakawa, Woodrow W. Burchett, Joshua W. Lambert, Arnold J. Stromberg

Chemical and Materials Engineering Faculty Publications

The primary crystallite size of titania powder relates to its properties in a number of applications. Transmission electron microscopy was used in this interlaboratory comparison (ILC) to measure primary crystallite size and shape distributions for a commercial aggregated titania powder. Data of four size descriptors and two shape descriptors were evaluated across nine laboratories. Data repeatability and reproducibility was evaluated by analysis of variance. One-third of the laboratory pairs had similar size descriptor data, but 83% of the pairs had similar aspect ratio data. Scale descriptor distributions were generally unimodal and were well-described by lognormal reference models. Shape descriptor distributions …

Desulfination By 2′-Hydroxybiphenyl-2-Sulfinate Desulfinase Proceeds Via Electrophilic Aromatic Substitution By The Cysteine-27 Proton, Inacrist Geronimo, Shawn R. Nigam, Christina M. Payne

Chemical and Materials Engineering Faculty Publications

Biodesulfurization is an attractive option for enzymatically removing sulfur from the recalcitrant thiophenic derivatives that comprise the majority of organosulfur compounds remaining in hydrotreated petroleum products. Desulfurization in the bacteria Rhodococcus erythropolis follows a four-step pathway culminating in C–S bond cleavage in the 2′-hydroxybiphenyl-2-sulfinate (HBPS) intermediate to yield 2-hydroxybiphenyl and bisulfite. The reaction, catalyzed by 2′-hydroxybiphenyl-2-sulfinate desulfinase (DszB), is the rate-limiting step and also the least understood, as experimental evidence points to a mechanism unlike that of other desulfinases. On the basis of structural and biochemical evidence, two possible mechanisms have been proposed: nucleophilic addition and electrophilic aromatic substitution. Density …

Pore Functionalized Pvdf Membranes With In-Situ Synthesized Metal Nanoparticles: Material Characterization, And Toxic Organic Degradation, Hongyi Wan, Nicolas J. Briot, Anthony Saad, Lindell E. Ormsbee, Dibakar Bhattacharyya

Chemical and Materials Engineering Faculty Publications

Functionalized PVDF membrane platforms were developed for environmentally benign in-situ nanostructured Fe/Pd synthesis and remediation of chlorinated organic compounds. To prevent leaching and aggregation, nanoparticle catalysts were integrated into membrane domains functionalized with poly (acrylic acid). Nanoparticles of 16–19 nm were observed inside the membrane pores by using focused ion beam (FIB). This technique prevents mechanical deformation of the membrane, compared to the normal SEM preparation methods, thus providing a clean, smooth surface for nanoparticles characterization. This allowed quantification of nanoparticle properties (size and distribution) versus depth underneath the membrane surface (0–20 μm). The results showed that nanoparticles were uniformly …

Synthesis Of Graphene Oxide Membranes And Their Behavior In Water And Isopropanol, Ashish Aher, Yuguang Cai, Mainak Majumder, Dibakar Bhattacharyya

Chemical and Materials Engineering Faculty Publications

Graphene oxide (GO) membrane has been synthesized on commercial polysulfone ultrafiltration membranes (Pore size: 17 nm) using the drop casting method followed by baking at 90 C for 24 h. Baking resulted in the reduction of GO and removal of bulk water intercalated in the GO sheets. Deposited GO film showed high stability under shear stress variation. This work shows that water adsorption on the GO membrane determines its permeation performance. Despite the higher viscosity of isopropyl alcohol (IPA), its permeability was 7 times higher than water through the baked (“dry”) GO membranes, which were never contacted with water. However, …

Chemically Stable Artificial Sei For Li-Ion Battery Electrodes, Qinglin Zhang, Lei Han, Jie Pan, Zhi Chen, Yang-Tse Cheng

Chemical and Materials Engineering Faculty Publications

The importance of coating's chemical stability in lithium-ion batteries has been demonstrated by this study. It is well known that the mechanical properties determine the cycle life, and chemical stability or chemical degradation rate determines the calendar life. In this study, we used HfO₂ coatings prepared by atomic layer deposition as an example to show the chemical stability of the coatings for lithium ion battery electrodes.

Synthesis And Catalytic Applications Of Non-Metal Doped Mesoporous Titania, Syed Z. Islam, Suraj R. Nagpure, Doo Young Kim, Stephen E. Rankin

Chemical and Materials Engineering Faculty Publications

Mesoporous titania (mp-TiO₂) has drawn tremendous attention for a diverse set of applications due to its high surface area, interfacial structure, and tunable combination of pore size, pore orientation, wall thickness, and pore connectivity. Its pore structure facilitates rapid diffusion of reactants and charge carriers to the photocatalytically active interface of TiO₂. However, because the large band gap of TiO₂ limits its ability to utilize visible light, non-metal doping has been extensively studied to tune the energy levels of TiO₂. While first-principles calculations support the efficacy of this approach, it is challenging to …

Incorporating Poly(3-Hexyl Thiophene) Into Orthogonally Aligned Cylindrical Nanopores Of Titania For Optoelectronics, Suraj R. Nagpure, James F. Browning, Stephen E. Rankin

Chemical and Materials Engineering Faculty Publications

The incorporation of hole conducting polymer poly(3-hexyl thiophene) (P3HT) into the 8-9 nm cylindrical nanopores of titania is investigated using films with a unique orthogonally oriented hexagonal close packed mesostructure. The films are synthesized using evaporation induced self-assembly (EISA) with Pluronic triblock copolymer F127 as the structure directing agent. The orthogonally oriented cylindrical nanopore structure was chosen over a cubic structure because confinement in uniform cylindrical channels is hypothesized to enhance hole conductivity of P3HT by inducing local polymer chain ordering. Orthogonal orientation of the cylindrical nanopores is achieved by modifying the substrate (FTO-coated glass slides) with crosslinked F127. After …

Toxicity Evaluation Of Magnetic Hyperthermia Induced By Remote Actuation Of Magnetic Nanoparticles In 3d Micrometastasic Tumor Tissue Analogs For Triple Negative Breast Cancer, Nathanael A. Stocke, Pallavi Sethi, Amar Jyoti, Ryan Chan, Susanne M. Arnold, J. Zach Hilt, Meenakshi Upreti

Chemical and Materials Engineering Faculty Publications

Magnetic hyperthermia as a treatment modality is acquiring increased recognition for loco-regional therapy of primary and metastatic lung malignancies by pulmonary delivery of magnetic nanoparticles (MNP). The unique characteristic of magnetic nanoparticles to induce localized hyperthermia in the presence of an alternating magnetic field (AMF) allows for preferential killing of cells at the tumor site. In this study we demonstrate the effect of hyperthermia induced by low and high dose of MNP under the influence of an AMF using 3D tumor tissue analogs (TTA) representing the micrometastatic, perfusion independent stage of triple negative breast cancer (TNBC) that infiltrates the lungs. …

Field-Induced Formation And Growth Of Pillars On Films Of Bisphenol-A-Polycarbonate, Yu-Fan Chuang, Jyun-Siang Peng, Fuqian Yang, Donyau Chiang, Sanboh Lee

Chemical and Materials Engineering Faculty Publications

An electric field is used to construct pillars on films of bisphenol-A-polycarbonate (BPAPC) between two parallel electrodes. Both the size and density of the pillars are dependent on the film thickness. For the same experimental conditions, thicker films will lead to the formation of pillars of larger sizes and smaller densities. The time dependence of the average diameter of the pillars is found to be a linear function of the square root of the difference between the annealing time and incubation time. The temperature dependence of the temporal evolution of the pillars follows the Arrhenius relation with an activation enthalpy …

Fatigue Properties And Damage Mechanism Of A Cr-Mn Austenite Steel, Z. Q. Lv, Pei Cai, T. Yu, Yan Jin, H. F. Zhang, Tongguang Zhai, W. T. Fu

Chemical and Materials Engineering Faculty Publications

The fatigue properties and the damage mechanism of a Cr-Mn austenite steel were investigated using four-point bend fatigue testing. The stress-number of cycles to failure (S-N) curve of the Cr-Mn austenite steel was measured at room temperature, at the frequency of f=20 Hz and the stress ratio of R=0.1. The fatigue strength of this Cr-Mn austenite steel was measured to be 503 MPa in the maximum stress. Multiple cracks are initiated on the sample surface after fatigue failure tests, and usually only one or two of them can lead to the final failure of the samples. Most of the cracks …

Interplay Of Composition, Structure, And Electron Density Of States In W-Os Cathode Materials And Relationship With Thermionic Emission, Qunfei Zhou, Thomas John Balk, Matthew J. Beck

Chemical and Materials Engineering Faculty Publications

The presence and composition of W-Os alloys have been found to significantly affect the thermionic emission properties of Os-coated tungsten dispenser cathodes. However, the comprehensive understanding of structure–property relationships needed to design improved tungsten cathodes with larger thermionic emission is still lacking. In this study, composition–structure–property relationships governing thermionic emission from W-Os alloys were investigated using quantum mechanical calculations. Low-energy W-Os atomic configurations at various compositions were determined from first-principles calculations based on density functional theory in combination with cluster expansion calculations. Electronic properties were investigated in terms of the electron density of states. The relative position of the Fermi …

Inhibition Of Mammalian Glycoprotein Ykl-40 Identification Of The Physiological Ligand, Abhishek A. Kognole, Christina M. Payne

Chemical and Materials Engineering Faculty Publications

YKL-40 is a mammalian glycoprotein associated with progression, severity, and prognosis of chronic inflammatory diseases and a multitude of cancers. Despite this well documented association, identification of the lectin′s physiological ligand and, accordingly, biological function has proven experimentally difficult. YKL-40 has been shown to bind chito-oligosaccharides; however, the production of chitin by the human body has not yet been documented. Possible alternative ligands include proteoglycans, polysaccharides, and fibers like collagen, all of which makeup the extracellular matrix. It is likely that YKL-40 is interacting with these alternative polysaccharides or proteins within the body, extending its function to cell biological roles …