Chemical and Biomolecular Engineering - Research Publications

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    The Passive Effect of MXene on Electrocatalysis: A Case of Ti3C2Tx/CoNi-MOF nanosheets for Oxygen Evolution Reaction
    Du, C-F ; Song, Q ; Liang, Q ; Zhao, X ; Wang, J ; Zhi, R ; Wang, Y ; Yu, H (WILEY-V C H VERLAG GMBH, 2021-05)
    Abstract Herein, CoNi bimetallic metal‐organic framework nanosheets (CoNi−MOFNs) in‐situ grown on Ti3C2Tx MXene (CoNi−MOFNs@MX) were explored as a typical nanocomposite to study the impact of MXene on the electrocatalytic activity of MOF for oxygen evolution reaction (OER). In contrast to previous reports, we observed a passive effect of Ti3C2Tx MXene on the OER performance of CoNi−MOFNs although the electronic conductivity of the nanocomposites was improved. The combined analysis of electrochemical results and atomic valence state characterization demonstrates that the decreased OER activity is likely ascribed to the unfavorable electron donation from Ti3C2Tx MXene, which suppresses the formation of active species for OER from the oxidation of Co2+ and Ni2+ to higher valence states in the nanocomposite. Consequently, more attention needs to be paid to the rational design of nanocomposites with MXenes for electrocatalytic applications.
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    The effect of pH on the fat and protein within cream cheese and their influence on textural and rheological properties
    Ong, L ; Pax, AP ; Ong, A ; Vongsvivut, J ; Tobin, MJ ; Kentish, SE ; Gras, SL (Elsevier BV, 2020-12-01)
    The effect of variation in acid gel pH during cream cheese production was investigated. The gel microstructure was denser and cheese texture firmer, as the pH decreased from pH 5.0 to pH 4.3, despite the viscoelasticity of these gels remaining similar during heating. Protein hydration and secondary structure appeared to be key factors affecting both cheese microstructure and properties. Proteins within the matrix appeared to swell at pH 5.0, leading to a larger corpuscular structure; greater β-turn structure was also observed by synchrotron-Fourier transform infrared (S-FTIR) microspectroscopy and the cheese was softer. A decrease in pH led to a denser microstructure with increased aggregated β-sheet structure and a firmer cheese. The higher whey protein loss at low pH likely contributed to increased cheese hardness. In summary, controlling the pH of acid gel is important, as this parameter affects proteins in the cheese, their secondary structure and the resulting cream cheese.
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    Design and characterization of casein-whey protein suspensions via the pH-temperature-route for application in extrusion-based 3D-Printing
    Daffner, K ; Vadodaria, S ; Ong, L ; Nöbel, S ; Gras, S ; Norton, I ; Mills, T (Elsevier BV, 2021-03)
    The current interest in individualized food through additive manufacturing has identified a need for more information on the formulation and printability of potential ingredients. Here, the effect of formulation parameters of casein–whey protein suspensions like the pH (4.8–5.4) as well as the casein content (8.0–12.0% (w/w)) mixed with whey protein (2.0–3.0% (w/w)) and the effect of pre-processing parameters including the denaturation of whey proteins (80 °C, 10 min; adjusted pH 6.55, 6.9 and 7.1) on the gel formation via the pH–temperature (T)-route was studied. Rheological measurements showed that the sol–gel transition temperature (G’ = 1 Pa) decreased and the aggregation rate of the casein–whey protein suspensions increased with increasing heating pH value. The aggregation rate was considered to be a key parameter predicting the printability of formulations. By exceeding a certain aggregation rate (250 Pa/10 K), casein–whey protein suspensions were found to be printable resulting in firm and stable gels.
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    Characterising the influence of milk fat towards an application for extrusion-based 3D-printing of casein-whey protein suspensions via the pH-temperature-route
    Daffner, K ; Ong, L ; Hanssen, E ; Gras, S ; Mills, T (ELSEVIER SCI LTD, 2021-09)
    This study presents the design and characterisation of casein−whey protein suspensions (8.0/10.0% (w/w) casein and 2.0/2.5% (w/w) whey protein) mixed with dairy fat (1.0, 2.5 and 5.0% (w/w) total fat) processed via the pH−temperature-route in preparation for 3D-printing. Mechanical treatment was applied to significantly decrease the particle size of the milk fat globules and increase surface area, creating small fat globules (<1 μm) covered with proteins, which could act as pseudo protein particles during gelation. Different proteins covered the fat globule surface after mechanical treatment, as a result of differences in the pH adjusted just prior to heating (6.55, 6.9 or 7.1). The protein-fat suspensions appeared similar by transmission electron cryogenic microscopy and the zeta-potential of all particles was unchanged by the heating pH, with a similar charge to the solution (~−20 mV) occurring after acidification (pH 4.8/5.0) at low temperatures (2 °C). A low heating pH (6.55) resulted in increased sol−gel transition temperatures (G՛ = 1 Pa) and a decreased rate of aggregation for protein−fat suspensions. A higher heating pH (6.9 and 7.1) caused an increased rate of aggregation (aggregation rate ≥ 250 Pa/10 K), resulting in materials more promising for application in extrusion-based printing. 3D-printing of formulations into small rectangles, inclusive of a sol−gel transition in a heated nozzle, was conducted to relate the aggregation rate towards printability.
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    Effects of shredding on the functionality, microstructure and proteolysis of low-moisture mozzarella cheese
    Pax, AP ; Ong, L ; Kentish, SE ; Gras, SL (ELSEVIER SCI LTD, 2021-06)
    Low-moisture mozzarella cheese (LMMC) is commonly shredded before packaging, however, the effects of shredding are not fully understood. Industrially-produced block and shredded LMMC were studied during 8 weeks of storage at 4 °C. Cheese shredded on 15 d and at 8 weeks of age, coated with microcrystalline cellulose and stored in a modified atmosphere (70% N₂ and 30% CO₂), had an altered microstructure after 8 weeks compared with vacuum-packed block cheese. In the latter case the fat formed a more dispersed phase. Proteolysis was higher in shredded samples and a higher level of two bacterial proteases was detected. Despite these differences, the meltability and stretchability of the block and shredded LMMC were similar. The microstructure and functionality of cheese shredded at 15 d and stored for a further 6 weeks was similar to cheese shredded at 8 weeks, suggesting there is a flexible period for performing cheese shredding processes.
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    Structure and functionality of almond proteins as a function of pH
    Devnani, B ; Ong, L ; Kentish, S ; Gras, SL (ELSEVIER, 2021-10)
    Almond proteins have potential utility in a range of food and beverages but it is not clear how pH affects protein structure and function. The behaviour of almond protein isolate was examined under conditions of neutral and acidic pH (pH 7 and 4). The isolate was highly soluble (70–80%) at either pH. An increase in acidity lead to protein unfolding, an increase in random coil structure and the appearance of lower molecular weight proteins due to acidic hydrolysis. These structural changes at pH 4 increased the capacity for foam formation and foam stability, increased viscosity and led to concentration and age dependent thickening. Gels, similar in strength but with distinct microstructures and properties were obtained following heating. At pH 7, a particulate type gel with an interconnected protein network was formed, while the gel at pH 4 had a dense continuous protein matrix. The gels differed in their susceptibility to chemical disruption, suggesting different underlying molecular interactions. The ability to alter protein structure and properties as a function of pH and heating could be used to broaden the application of almond proteins and develop a variety of food products, such as protein supplements and vegan alternatives to traditional products.
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    Pilot scale concentration of cheese whey by forward osmosis: A short-cut method for evaluating the effective pressure driving force
    Artemi, A ; Chen, GQ ; Kentish, SE ; Lee, J (Elsevier, 2020-11-01)
    Cheese whey was concentrated to a concentration factor of 2.7 in a pilot scale forward osmosis filtration system, using a commercial cellulose triacetate membrane in a spiral-wound configuration. The whey was concentrated in a batch mode, using sodium chloride as the draw solution at initial osmotic pressures of 53–75 bar. During the process, flux was shown to reduce due to the simultaneous decrease in the bulk osmotic pressure of the draw solution, increase in the bulk osmotic pressure of the whey and the effect of concentration polarisation on both sides of the membrane. The flux is known to be driven by the effective osmotic pressures of whey and the draw solution on the surface of the membrane active layer. A short-cut approach that requires minimal information in advance about the osmotic pressure of whey and the geometry of the filtration system was implemented, enabling the determination of these effective osmotic pressures. The results obtained were shown to be in agreement with the fundamental forward osmosis flux model. The short-cut approach can be utilised for estimating effective osmotic pressures of other liquid food streams to be concentrated by forward osmosis, without the need of external measurements.
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    The relevance of critical flux concept in the concentration of skim milk using forward osmosis and reverse osmosis
    Artemi, A ; Chen, GQ ; Kentish, SE ; Lee, J (Elsevier BV, 2020-10-01)
    Skim milk was concentrated at 10 °C using forward osmosis (FO), reverse osmosis (RO) and pressure-assisted forward osmosis (PAFO). A pressure of 40 bar, in the form of draw solution osmotic pressure (FO and PAFO modes) or transmembrane hydraulic pressure (RO mode) was applied; an additional hydraulic pressure of 2 bar was applied in the PAFO mode. More severe protein fouling was observed in RO, followed by PAFO and then FO. This was credited to the difference in the initial permeate flux, induced by the different effective driving pressures, with RO having a greater deviation of the initial flux from the critical flux value. The critical flux was determined for the FO and RO modes using a step-wise increase of draw solution osmotic pressure or hydraulic pressure, at a constant milk solids content. The critical flux was between 5.4 L/m2h (1.5 × 10−6 m3/m2s) and 7.2 L/m2h (2 × 10−6 m3/m2s) for both the FO and RO modes at a cross flow velocity of 0.2 m/s. The similarities in the critical flux for FO and RO suggests that the critical flux does not depend on the nature of pressure applied on the system (hydraulic or osmotic). Therefore, when operated at the same flux and crossflow velocity, FO would not fundamentally provide a lower fouling environment compared to RO. An increase of the solids content from 8.7% to 17.3% caused a reduction in the critical flux from 5.4 L/m2h to 3.1 L/m2h (8.5 × 10−7 m3/m2s).
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    Incorporating whey protein aggregates produced with heat and ultrasound treatment into rennet gels and model non-fat cheese systems
    Gamlath, CJ ; Leong, TSH ; Ashokkumar, M ; Martin, GJO (Elsevier, 2020-12-01)
    Native whey proteins (WP) are expulsed from cheese coagulation during syneresis. Although incorporating denatured WP aggregates into cheese gels has been previously proposed to improve the overall cheese yield, the effects of WP aggregate properties on gelation kinetics and protein retention are not yet fully understood. In this study, heat and power ultrasound were used to produce denatured whey protein aggregates with a wide range of sizes. The effects of size and hydrophobicity differences in WP aggregates produced by heat and heat coupled with ultrasound were investigated in relation to the kinetics of rennet gelation and protein retention in model non-fat cheddar cheeses. Rheological measurements showed that sufficiently large, denatured WP aggregates could avoid impairment of rennet gelation caused by native WP, irrespective of changes in the soluble calcium concentration or the surface hydrophobicity of the aggregates. WP aggregates formed by the combined heat and ultrasound treatment were more hydrophobic than the larger heat-treated aggregates and were better retained in the cheese. However, inclusion of sufficiently large aggregates in cheese milk conferred an openness to the cheese microstructure and showed promise in improving the otherwise rigid non-fat cheese.
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    A two-dimensional metallosupramolecular framework design based on coordination crosslinking of helical oligoamide nanorods (vol 1, pg 1134, 2020)
    West, NG ; Seoudi, RS ; Barlow, AJ ; Qi, D ; Puskar, L ; Del Borgo, MP ; Kulkarni, K ; Adda, CG ; Pan, J ; Aguilar, M-I ; Perlmutter, P ; Mechler, A (ROYAL SOC CHEMISTRY, 2020-12-01)

    Correction for ‘A two-dimensional metallosupramolecular framework design based on coordination crosslinking of helical oligoamide nanorods’ by Norton G. West et al., Mater. Adv., 2020, 1, 1134–1141, DOI: 10.1039/D0MA00123F.