School of Chemistry - Research Publications

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    4D Printing of Hydrogels: Innovation in Material Design and Emerging Smart Systems for Drug Delivery
    Tran, TS ; Balu, R ; Mettu, S ; Choudhury, NR ; Dutta, NK (MDPI, 2022-10)
    Advancements in the material design of smart hydrogels have transformed the way therapeutic agents are encapsulated and released in biological environments. On the other hand, the expeditious development of 3D printing technologies has revolutionized the fabrication of hydrogel systems for biomedical applications. By combining these two aspects, 4D printing (i.e., 3D printing of smart hydrogels) has emerged as a new promising platform for the development of novel controlled drug delivery systems that can adapt and mimic natural physio-mechanical changes over time. This allows printed objects to transform from static to dynamic in response to various physiological and chemical interactions, meeting the needs of the healthcare industry. In this review, we provide an overview of innovation in material design for smart hydrogel systems, current technical approaches toward 4D printing, and emerging 4D printed novel structures for drug delivery applications. Finally, we discuss the existing challenges in 4D printing hydrogels for drug delivery and their prospects.
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    Ultrasonic Processing of Food Waste to Generate Value-Added Products
    Wu, Y ; Yao, S ; Narale, BA ; Shanmugam, A ; Mettu, S ; Ashokkumar, M (MDPI, 2022-07)
    Ultrasonic processing has a great potential to transform waste from the food and agriculture industry into value-added products. In this review article, we discuss the use of ultrasound for the valorisation of food and agricultural waste. Ultrasonic processing is considered a green technology as compared to the conventional chemical extraction/processing methods. The influence of ultrasound pre-treatment on the soluble chemical oxygen demand (SCOD), particle size, and cell wall content of food waste is first discussed. The use of ultrasonic processing to produce/extract bioactives such as oil, polyphenolic, polysaccharides, fatty acids, organic acids, protein, lipids, and enzymes is highlighted. Moreover, ultrasonic processing in bioenergy production from food waste such as green methane, hydrogen, biodiesel, and ethanol through anaerobic digestion is also reviewed. The conversion of waste oils into biofuels with the use of ultrasound is presented. The latest developments and future prospective on the use of ultrasound in developing energy-efficient methods to convert food and agricultural waste into value-added products are summarised.
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    The effects of ultrasonic treated whey on the structure formation in food systems based on whey in combination with pectin and agar-agar
    Krasulya, ON ; Dunchenko, N ; Yankovskaya, VS ; Voloshina, ES ; Mettu, S (ELSEVIER, 2022-08)
    We studied the effects of ultrasonicated whey in food systems with the structure-forming additives such as pectin and agar-agar. The high-intensity (45KHz, 40 W with cavitation) ultrasonic treated whey was used. The conditions and optimal modes of cavitation based ultrasonic processing of curd milk whey have been determined. The mechanism of structure formation has been studied in detail. From the studies carried out, the scientific basis for the choice of structure-forming agents in food systems was established along with the range of rational concentrations of pectin and agar-agar. It was shown that in the case of processing milk curd whey by the cavitation method, the concentration of the structure former can be reduced by 2 times compared to using non-sonicated whey in the food system thus saving costs on the raw materials. It was established that high-purity cavity treatment minimizes gel-like food systems set time up to 20% compared to the control within 15 min. The duration of high-purity treatment within 15 min contributes to an increase in penetration pressure, which characterizes the texture of the gel-like food two times.
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    Ultrasonic microencapsulation of oil-soluble vitamins by hen egg white and green tea for fortification of food
    Zhu, H ; Mettu, S ; Cavalieri, F ; Ashokkumar, M (ELSEVIER SCI LTD, 2021-08-15)
    We report the microencapsulation of oil soluble vitamins (A, D and E) using a one pot ultrasonic process and raw egg white proteins as a shell material. Green tea catechin/iron complex coating method was further developed to impart UV filtering property to the microcapsules in order to protect the encapsulated nutrients from photodegradation. The microcapsules showed antibacterial properties and long shelf-life. The encapsulated vitamins were protected from degradation upon heating, UV irradiation, simulated storage/transit and cooking processes. The in-vitro digestion study showed that functional vitamin D can be potentially released in the gastrointestinal tract improving vitamin D availability by more than 2-fold compared to the free vitamin. The vitamin D microcapsules were highly stable and maintained their microstructures once incorporated into staple food products. The low-cost egg white shell encapsulated vitamins can improve the nutritional value of staple food products to combat maternal and child malnutrition.
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    Perspective on Constructing Cellulose-Hydrogel-Based Gut-Like Bioreactors for Growth and Delivery of Multiple-Strain Probiotic Bacteria
    Mettu, S ; Hathi, Z ; Athukoralalage, S ; Priya, A ; Lam, TN ; Ong, KL ; Choudhury, NR ; Dutta, NK ; Curvello, R ; Garnier, G ; Lin, CSK (AMER CHEMICAL SOC, 2021-05-05)
    The current perspective presents an outlook on developing gut-like bioreactors with immobilized probiotic bacteria using cellulose hydrogels. The innovative concept of using hydrogels to simulate the human gut environment by generating and maintaining pH and oxygen gradients in the gut-like bioreactors is discussed. Fundamentally, this approach presents novel methods of production as well as delivery of multiple strains of probiotics using bioreactors. The relevant existing synthesis methods of cellulose hydrogels are discussed for producing porous hydrogels. Harvesting methods of multiple strains are discussed in the context of encapsulation of probiotic bacteria immobilized on cellulose hydrogels. Furthermore, we also discuss recent advances in using cellulose hydrogels for encapsulation of probiotic bacteria. This perspective also highlights the mechanism of probiotic protection by cellulose hydrogels. Such novel gut-like hydrogel bioreactors will have the potential to simulate the human gut ecosystem in the laboratory and stimulate new research on gut microbiota.
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    Polyphenol-Induced Adhesive Liquid Metal Inks for Substrate-Independent Direct Pen Writing
    Rahim, MA ; Centurion, F ; Han, J ; Abbasi, R ; Mayyas, M ; Sun, J ; Christoe, MJ ; Esrafilzadeh, D ; Allioux, F-M ; Ghasemian, MB ; Yang, J ; Tang, J ; Daeneke, T ; Mettu, S ; Zhang, J ; Uddin, MH ; Jalili, R ; Kalantar-Zadeh, K (WILEY-V C H VERLAG GMBH, 2021-03)
    Abstract Surface patterning of liquid metals (LMs) is a key processing step for LM‐based functional systems. Current patterning methods are substrate specific and largely suffer from undesired imperfections—restricting their widespread applications. Inspired by the universal catechol adhesion chemistry observed in nature, LM inks stabilized by the assembly of a naturally abundant polyphenol, tannic acid, has been developed. The intrinsic adhesive properties of tannic acid containing multiple catechol/gallol groups, allow the inks to be applied to a variety of substrates ranging from flexible to rigid, metallic to plastics and flat to curved, even using a ballpoint pen. This method can be further extended from hand‐written texts to complex conductive patterns using an automated setup. In addition, capacitive touch and hazardous heavy metal ion sensors have been patterned, leveraging from the synergistic combination of polyphenols and LMs. Overall, this strategy provides a unique platform to manipulate LMs from hand‐written pattern to complex designs onto the substrate of choice, that has remained challenging to achieve otherwise.
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    Influence of Poly(ethylene glycol) Molecular Architecture on Particle Assembly and Ex Vivo Particle-Immune Cell Interactions in Human Blood
    Song, J ; Ju, Y ; Amarasena, TH ; Lin, Z ; Mettu, S ; Zhou, J ; Rahim, MA ; Ang, C-S ; Cortez-Jugo, C ; Kent, SJ ; Caruso, F (AMER CHEMICAL SOC, 2021-06-22)
    Poly(ethylene glycol) (PEG) is widely used in particle assembly to impart biocompatibility and stealth-like properties in vivo for diverse biomedical applications. Previous studies have examined the effect of PEG molecular weight and PEG coating density on the biological fate of various particles; however, there are few studies that detail the fundamental role of PEG molecular architecture in particle engineering and bio-nano interactions. Herein, we engineered PEG particles using a mesoporous silica (MS) templating method and investigated how the PEG building block architecture impacted the physicochemical properties (e.g., surface chemistry and mechanical characteristics) of the PEG particles and subsequently modulated particle-immune cell interactions in human blood. Varying the PEG architecture from 3-arm to 4-arm, 6-arm, and 8-arm generated PEG particles with a denser, stiffer structure, with increasing elastic modulus from 1.5 to 14.9 kPa, inducing an increasing level of immune cell association (from 15% for 3-arm to 45% for 8-arm) with monocytes. In contrast, the precursor PEG particles with the template intact (MS@PEG) were stiffer and generally displayed higher levels of immune cell association but showed the opposite trend-immune cell association decreased with increasing PEG arm numbers. Proteomics analysis demonstrated that the biomolecular corona that formed on the PEG particles minimally influenced particle-immune cell interactions, whereas the MS@PEG particle-cell interactions correlated with the composition of the corona that was abundant in histidine-rich glycoproteins. Our work highlights the role of PEG architecture in the design of stealth PEG-based particles, thus providing a link between the synthetic nature of particles and their biological behavior in blood.
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    Estimation of the stability of skeletal muscle myoglobin of chilled pork treated with brine activated by low-frequency high-intensity ultrasound
    Krasulya, O ; Smirnova, A ; Bogush, V ; Shlenskaya, N ; Vostrikova, N ; Mettu, S (ELSEVIER, 2021-03)
    We studied the effect of ultrasonic activation of brine (3%) during salting on the degree of stability of colour parameters of pork with normal (NOR) and abnormal course of autolysis in the CIE Lab colour space. The mechanism of stabilisation of the colour of meat is attributed to donor-acceptor bonds of metmyoglobin (MetMb). The accumulation of excessive number of free electrons in the medium are capable of activating MetMb. This reduces the activity of meat, when the native participants of the metmyoglobin reductase system and their own antioxidant systems of meat are depleted. Based on the additive calculation of deviations (increase / decrease) by the coordinates L*, a*, b* in the CIE Lab system, and the total colour difference (ΔE) in control and experimental samples, recommendations were developed. To optimize the colour characteristics of all types of meat, both on the surface and in the thickness of the meat, the preliminary activation of a 3% brine in a low-frequency submersible ultrasonic unit is recommended. Moreover, preliminary cavitation activation of a 3% is more preferable to stabilise the colour of PSE - meat (pale, soft, exudative (watery),) brine in a flow-through installation.
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    Precise measurements of capsule mechanical properties using indentation
    Berry, JD ; Mettu, S ; Dagastine, RR (ROYAL SOC CHEMISTRY, 2017-03-14)
    Application of elastic theory to experimental data of capsule and particle compression under-predicts the value of material properties such as the Young's modulus by up to 100% when the effect of the rigid substrate is neglected, as is commonly done in the literature. Results of numerical simulations, spanning the range from thin-shelled capsules to solid particles, are presented in terms of correction factors that account for the substrate. In addition, the scaling relationship between indentation force and displacement is characterised for arbitrary shell thicknesses and indenter radii.
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    The effect of high-intensity ultrasound on cell disruption and lipid extraction from high-solids viscous slurries of Nannochloropsis sp biomass
    Yao, S ; Mettu, S ; Law, SQK ; Ashokkumar, M ; Martin, GJO (ELSEVIER SCIENCE BV, 2018-11-01)
    The effect of ultrasonication on the cell rupture of marine microalgae Nannochloropsis sp. was studied as a function of the slurry solids concentration and treatment time. The concentrated viscous wet-biomass (~12 to 25% solids concentration) was subjected to ultrasonication (20 kHz) at 3.8 W/mL for up to 5 min. Compared to extraction without cell rupture, sonication led to a significant increase in lipid yield from ~11% to about 70% within 5 min of sonication. The extraction yield was found to decrease with increased solids concentration, with a large decrease between 20% to 25% solids. This is attributed to the increase in viscosity and decrease in speed of sound with increase in solids. The ultrasound attenuation coefficient increased 320-fold as the solids increased from 20 to 25%. Such a large attenuation of ultrasound places a limit of 20% solids to be used for cell rupture by ultrasound. The specific energy requirements per unit mass of extracted lipid were lowest at 20% solids. At lower concentrations energy was wasted heating water, at higher concentrations the lipid yields were reduced due to ultrasound attenuation.