Effect of packaging method, temperature and storage period on physicochemical and sensory properties of wild almond kernel.

This research was performed to monitor the effect of different temperatures (4, 25 and 35 °C) and atmospheres (vacuum, CO2 and normal air) on physicochemical and sensory properties of wild almond kernel during several weeks' storage. The color, moisture content and sensory analysis of the kernels, peroxide value (PV), 2-thiobarbiotic acid (TBA), conjugated dienes and trienes (CD, CT) and acid value (AV) of the oils were determined in defined time intervals. The results showed that the influence of temperature, time and type of atmosphere on the following parameters were significantly different. At all temperatures studied, AV, PV, TBA and CD/CT of oils from all samples increased with time which was less in the modified atmosphere packaging (MAP) compared with vacuum packaging (VP) and air atmosphere packaging (AAP). At the end of storage, the samples stored under AAP at 35 °C had the highest amount of PV (15.5 meq/kg), TBA (0.056 mg/kg) and CT (0.193 µmol/g), while the samples packaged under MAP at 4 °C had the lowest. Irrespective of packaging type, L* and b* values decreased during storage with a parallel increase of values a* resulting in gradual product darkening, especially in AAP. Sensory analysis also showed the decrease of overall acceptability during the storage among the three packaging systems. In conclusion, the use of MAP was the most effective method for protecting wild almond kernel from deteriorative reactions such as oxidation and hydrolysis.

Antiscaling Pickering Emulsions Enabled by Amphiphilic Hairy Cellulose Nanocrystals.

Nucleation and growth of sparingly soluble salts, referred to as scaling, has posed substantial challenges in industrial processes that deal with multiphase flows, including enhanced oil recovery (EOR). During crude oil extraction/recovery, seawater is injected into oil reservoirs and yields water-in-oil (W/O) emulsions that may undergo calcium carbonate (CaCO3) scaling. Common antiscaling macromolecules and nanoparticles have adverse environmental impacts and/or are limited to functioning only in single-phase aqueous media. Here, we develop a novel antiscaling cellulose-based nanoparticle that enables scale-resistant Pickering emulsions. Cellulose fibrils are rationally nanoengineered to yield amphiphilic hairy cellulose nanocrystals (AmHCNC), bearing hydrophilic dicarboxylate groups and hydrophobic alkyl chains on disordered cellulose chains (hairs) protruding from nanocrystal ends. The unique chemical and structural properties of AmHCNC render them the first dual functional antiscaling and emulsion stabilizing nanoparticle. AmHCNC stabilize W/O Pickering emulsions at a concentration of 1.00 wt % for 1 week while inhibiting CaCO3 scale formation up to 70% by mass at a supersaturation degree of ∼101 compared with the synthetic surfactant Span 80. To the best of our knowledge, this study presents the first biopolymer-based solution for the long-lasting scaling challenge in multiphase media, which may set the stage for developing sustainable scale-resistant multiphase flows in a broad spectrum of industrial sectors.

Multifunctional self-healing hydrogels via nanoengineering of colloidal and polymeric cellulose.

The unique features of self-healing hydrogels hold great potential for biomedical applications including injectable hydrogels for cancer treatment, procedures for tumor removal or resection. However, the fabrication of durable and multifunctional self-healing hydrogels composed of biocompatible, green building blocks via versatile synthetic methodology continues to pose a significant challenge. Here, we engineered dialdehyde cellulose (DAC, as a macromolecular bio-crosslinker), and electrosterically stabilized nanocrystalline cellulose (ENCC, as a ligand-targeted drug carrier) to facilitate a strategy for the construction of self-healing hydrogels. Benefiting from its high carboxyl group density, ENCC was functionalized with folic acid (FA) using a non-toxic DMTMM coupling agent and loaded with doxorubicin (DOX, a model drug) through electrostatic interactions. A natural self-healing hydrogel was prepared from carboxymethyl chitosan (CCTS) and DAC mixed with DOX-loaded FA-ENCC using dynamic Schiff-base and hydrogen linkages. A combination of active supramolecular and vital covalent junctions led to a soft (storage modulus ∼500 Pa) and durable material, with rapid (< 5 min) reconstruction of molecular structure from fractured and injected to intact forms. The DAC-CCTS hydrogel showed an appreciable loading capacity of ∼5 mg g-1. Biocompatibility of the hydrogels was evaluated using cell viability and metabolic activity assays, showing lower metabolic activity due to sustained release of its cargo. These materials offer a versatile, sustainable, and green platform for the efficient construction of hydrogels, based on macro- and nano-engineered cellulose, the most abundant and easily accessible biopolymer.

Colloidal aspects of calcium carbonate scaling in water-in-oil emulsions: A fundamental study using droplet-based microfluidics.

HYPOTHESIS: As a mainstream process in the extraction and recovery of crude oil, water is injected into reservoirs in the so-called waterflooding process to facilitate the oil displacement through the wellbore, typically generating water-in-oil (W/O) emulsions. Based on economic considerations, sea water is used in the flooding process; however, the ionic incompatibility between the injected water and the formation water inside the reservoir may precipitate sparingly-soluble inorganic salts (scale). We hypothesize that calcium carbonate (CaCO3) scale dynamically interacts with cationic surfactants in W/O emulsions, resulting in (i) scale growth retardation and (ii) emulsion destabilization. EXPERIMENTS: We developed stable W/O emulsions via combining droplet-based microfluidics with multifactorial optimizations to investigate the influence of emulsion properties, such as surfactant type and concentrations, temperature, and pH, as well as calcium ions on the CaCO3 scaling kinetics and emulsion stability. The CaCO3 scale was characterized based on particle size and charge, lattice structure, interactions with the surfactant, and time-dependent effects on emulsion stability. FINDINGS: The interfacial interactions between the cationic surfactant (cetyltrimethylammonium bromide, CTAB) and CaCO3 retarded scale growth rate, decreased crystal size, and destabilized emulsion within hours as a result of surfactant depletion at the water-oil interface. The surfactant did not affect the crystal structure of scale, which was formed as the most thermodynamically stable crystalline polymorph, calcite, at the ambient condition. This fundamental study may open new opportunities for engineering stable W/O emulsions, e.g., for enhanced oil recovery (EOR), and developing scale-resistant multiphase flows.

Mussel-Inspired Nanocellulose Coating for Selective Neodymium Recovery.

Neodymium (Nd) is one of the most in-demand rare earth elements (REEs) for developing the next generation of magnetic medical devices and clean energy. Eco-friendly and sustainable nanotechnology for REE recovery may be highly suitable to address the limited global supply while minimizing the environmental footprints of current practice, such as solvent extraction. Here, we present a novel one-step mussel-inspired nanocellulose coating (MINC) using bifunctional hairy cellulose nanocrystals (BHCNC), bearing dialdehyde and dicarboxylate groups. The dialdehyde groups enable dopamine-mediated orthogonal conjugation of BHCNC to substrates, such as microparticles, while the high content of dicarboxylate groups yields high-capacity and selective Nd removal against ferric, calcium, and sodium ions. To the best of our knowledge, the MINC-treated substrate provides the most rapid selective removal and recovery of Nd ions even at low Nd concentrations with a capacity that is among the highest reported values. We envision that the MINC will provide new opportunities in developing next-generation bio-based materials and interfaces for the sustainable recovery of REEs and other precious elements.

Antibacterial Pickering emulsions stabilized by bifunctional hairy nanocellulose.

HYPOTHESIS: Pickering emulsions, defined as emulsions that are stabilized by colloidal particles, provide dispersion stability by preventing coalescence of the dispersed phase. In this study, we used a bifunctional hairy nanocellulose (BHNC) bearing both aldehyde and carboxylic acid groups as an stabilizer. We hypothesize that these particles as Pickering stabilizers can effectively reside at the oil-water interface, better than hairy nanocelluloses containing only carboxyl groups or aldehyde groups, and provide long-term stability without the need of any surfactants. EXPERIMENTS: Varying concentrations of BHNC were tested to explore the optimal concentration that provides emulsion stability. The effects of various preparation conditions such as salt and pH were also studied. Finally, carvacrol, an antibacterial essential oil, was loaded in the oil phase to develop antibacterial emulsions. FINDINGS: It was shown that a 1% BHNC suspension provides 90% and 80% stability for a duration of 30 and 60 days, respectively. A theoretical model using nuclear magnetic resonance relaxometry data is developed to prove that only a monolayer of BHNC covers oil droplets. Increasing the concentration of BHNC decreased the size of oil droplets, which as a result increases the surface area available for monolayer coverage. It was also shown that the antibacterial emulsions are highly effective against Gram-negative (i.e. E. coli) and Gram-positive (i.e. S. aureus) bacteria. Accordingly, BHNC as a highly functionalized bio-derived colloidal particle opens new opportunities for engineering highly stable Pickering emulsions.

Synthesis and characterization of hairy aminated nanocrystalline cellulose.

HYPOTHESIS: The synthesis and characterization of aminated nanocrystalline cellulose (ANCC), a new member of the hairy nanocellulose family, is reported. Hairy nanocelluloses consist of a crystalline rod-like body with amorphous cellulose chains ("hairs") at both ends, on which various functional groups can be accommodated. In ANCC these groups are reactive primary amine groups, which are useful for bioconjugation- and Schiff base-centered modifications. We hypothesize that a two-step oxidation-reductive amination of cellulose fibers followed by hydrothermal treatment will result in the formation of rod-like hairy ANCC. EXPERIMENTS: ANCC was prepared by converting the aldehyde groups in cellulose, introduced by a periodate oxidation, to primary amines using ammonia and sodium borohydride, followed by a hot water treatment, during which diamine modified cellulose fibers were converted to ANCC. ANCC was characterized by AFM, TEM, DLS, ELS, FTIR, NMR, XPS and conductometric titration. Antibacterial activity of ANCC was assessed by the viable cell counting method. FINDINGS: ANCC, with an amine content of 5.5 mmol g-1 is a bare nanocolloid (i.e. non-coated, without adsorbed polyelectrolytes or surfactants) which, as far as we know, has a positive charge density larger than any other bare cationic nanocolloid. It was observed that ANCC particles have a needle-like morphology with a width of ~ 5 nm and a length ~ 120 nm. DLS results proof that ANCC is hairy. Spectroscopic analysis confirmed the introduction of surface primary amine groups. ANCC showed promising bactericidal activities, against Gram-negative species due to their thinner and penetrable cell wall.

Ion Exchange Biomaterials to Capture Daptomycin and Prevent Resistance Evolution in Off-Target Bacterial Populations.

Daptomycin (DAP), a cyclic anionic lipopeptide antibiotic, is among the last resorts to treat multidrug-resistant Gram-positive bacterial infections, caused by vancomycin-resistant Enterococcus faecium or methicillin-resistant Staphylococcus aureus. DAP is administered intravenously, and via biliary excretion, ∼5-10% of the intravenous DAP dose arrives in the gastrointestinal (GI) tract where it drives resistance evolution in the off-target populations of E. faecium bacteria. Previously, we have shown in vivo that the oral administration of cholestyramine, an ion exchange biomaterial (IXB) sorbent, prevents DAP treatment from enriching DAP resistance in the populations of E. faecium shed from mice. Here, we investigate the biomaterial-DAP interfacial interactions to uncover the antibiotic removal mechanisms. The IXB-mediated DAP capture from aqueous media was measured in controlled pH/electrolyte solutions and in the simulated intestinal fluid (SIF) to uncover the molecular and colloidal mechanisms of DAP removal from the GI tract. Our findings show that the IXB electrostatically adsorbs the anionic antibiotic via a time-dependent diffusion-controlled process. Unsteady-state diffusion-adsorption mass balance describes the dynamics of adsorption well, and the maximum removal capacity is beyond the electric charge stoichiometric ratio because of DAP self-assembly. This study may open new opportunities for optimizing cholestyramine adjuvant therapy to prevent DAP resistance, as well as designing novel biomaterials to remove off-target antibiotics from the GI tract.

Biotemplated Hollow Mesoporous Silica Particles as Efficient Carriers for Drug Delivery.

We designed three types of hollow-shaped porous silica materials via a three-step biotemplate-directed method: porous hollow silica nanorods, hollow dendritic fibrous nanostructured silica (DFNS), and ultraporous sponge-like DFNS. The first step was making a biotemplate, for which we used cellulose nanocrystals (CNCs), consisting of rod-shaped nanoparticles synthesized by conventional acid hydrolysis of cellulose fibers. In a second step, core-shell samples were prepared using CNC particles as hard template by two procedures. In the first one, core-shell CNC-silica nanoparticles were synthesized by a polycondensation reaction, which exclusively took place at the surface of the CNCs. In the second procedure, a typical synthesis of DFNS was conducted in a bicontinuous microemulsion with the assistance of additives. DFNS was assembled on the surface of the CNCs, giving rise to core-shell CNC-DFNS structures. Finally, all of the silica-coated CNC composites were calcined, during which the CNC was removed from the core and hollow structures were formed. These materials are very lightweight and highly porous. All three structures were tested as nanocarriers for drug delivery and absorbents for dye removal applications. Dye removal results showed that they can adsorb methylene blue efficiently, with ultraporous sponge-like DFNS showing the highest adsorption capacity, followed by hollow DFNS and hollow silica nanorods. Furthermore, breast cancer cells show a lower cell viability when exposed to doxorubicin-loaded hollow silica nanorods compared with control or doxorubicin cultures, suggesting that the loaded nanorod has a greater anticancer effect than free doxorubicin.

Carboxylated Cellulose Nanocrystals Developed by Cu-Assisted H2O2 Oxidation as Green Nanocarriers for Efficient Lysozyme Immobilization.

Cellulose nanocrystals (CNCs), having a high specific surface area and versatile surface chemistry, provide considerable potential to interact by various mechanisms with enzymes for nano-immobilization purposes. However, engineering chemically safe CNCs, suitable for edible administrations, presents a significant challenge. A reliable carboxylate form of H-CNCs was formed using H2O2 oxidation of softwood pulp under mild thermal conditions. Negatively charged carboxyl groups (∼0.9 mmol g-1) played a key role in lysozyme immobilization via electrostatic interactions and covalent linkages, as evidenced by Fourier transform infrared and 13C cross-polarization magic angle spinning nuclear magnetic resonance spectroscopies. Adsorption isotherms showed a high loading capacity of H-CNCs (∼240 mg g-1), and fitting the data to the Langmuir model confirmed monolayer coverage of lysozyme on their surface. Using a non-toxic coupling agent, 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride, lysozyme-conjugated H-CNCs were developed with an immobilization yield of ∼65% and relative catalytic activity of ∼60%, similar to lysozyme adsorption on H-CNCs. These H-CNC-lysozyme nanohybrids, rationally processed via safe and green strategies, are specifically exploitable as catalytically active emulsifiers in food and pharmaceutical sectors.

Electroacoustic characterization of trimmed hairy nanocelluloses.

OBJECTIVE: A cellulose-derived nano-toolbox has been developed via the chemical nano-trimming of electrosterically stabilized nanocrystalline celluloses (ENCCs). ENCC is a member of the class of hairy nanocellulose (HNC). The objective of this study is to determine the properties of chemically trimmed HNCs in order to establish whether or not they overcome the surface chemistry and size restrictions of conventional nanocelluloses. The newly "so-called crew-cut ENCCs" emerged by this approach address many technological and environmental challenges in colloidal systems, i.e., drug delivery, anti-scaling and self-assembly. Despite the importance of the crew-cut species, little is known about the systematic changes and the underlying mechanisms of the trimming of their hairs (the chains protruding from both ends of the cylindrical core). EXPERIMENTS: To quantify the effect of the hair trimming on the charge density as well as the kinetics of this process, the carboxylic acid content is determined by conductometric titration as a function of time and reaction conditions. We use electro-acoustic spectroscopy to elucidate the differences in colloidal properties of various crew-cut ENCCs. We focus on the interplay between the time of the acid-catalyzed hydrolysis reaction and tunable parameters, such as size and surface electric charge of ENCC, as well as their microrheological behavior. FINDINGS: We show that a range of hairy ENCCs with various sizes and charge densities is easily obtained by taking advantages of the preferential hydrolysis of the amorphous chains protruding from both ends of the nanocrystals. The trimming mediated by a HCl-catalyzed hydrolysis is initially very fast, but slows down subsequently. The formation of crew-cut species with a smaller particle size and zeta potential was electro-acoustically verified by increasing the reaction time. The longitudinal viscosities of the trimmed ENCC suspensions also decreased with prolonging the reaction time. This research shows how manipulating HNCs enables both scientists and technologists to access a collection of nanocrystals with desired colloidal properties, based on the most abundant biopolymer in the world.

Cellulose-based dispersants and flocculants.

Natural dispersants and flocculants, often referred to as dispersion stabilizers and liquid-solid separators, respectively, have secured a promising role in the bioprocessing community. They have various applications, including in biomedicine and in environmental remediation. A large fraction of existing dispersants and flocculants are synthesized from non-safe chemical compounds such as polyacrylamide and surfactants. Despite numerous advantages of synthetic dispersants and flocculants, issues such as renewability, sustainability, biocompatibility, and cost efficiency have shifted attention towards natural homologues, in particular, cellulose-based ones. Within the past decade, cellulose derivatives, obtained via chemical and mechanical treatments of cellulose fibrils, have successfully been used for these purposes. In this review article, by dividing the functional cellulosic compounds into "polymeric" and "nanoscale" categories, we provide insight into the engineering pathways, the structural frameworks, and surface chemistry of these "green" types of dispersants and flocculants. A summary of their efficiency and the controlling parameters is also accompanied by recent advances in their applications in each section. We are confident that the emergence of cellulose-based dispersing and flocculating agents will extend the boundaries of sustainable green technology.

Ultrasound-assisted preparation of different nanocarriers loaded with food bioactive ingredients.

Developing green and facile approaches to produce nanostructures suitable for bioactives, nanoencapsulation faces some challenges in the nutraceutical and food bioactive industries due to potential risks arising from nanomaterials fabrication and consumption. High-intensity ultrasound is an effective technology to generate different bio-based structures in sub-micron or nanometer scale. This technique owing to some intrinsic advantages such as safety, straightforward operation, energy efficiency, and scale-up potential, as well as, ability to control over size and morpHology has stood out among various nanosynthetic routes. Ultrasonically-provided energy is mainly transferred to the droplets and particles via acoustic cavitation (which is formation, growth, and implosive collapse of bubbles in solvent). This review provides an outlook on the fundamentals of ultrasonication and some applicable setups in nanoencapsulation. Different kinds of nanostructures based on surfactants, lipids, proteins and carbohydrates formed by sonication, along with their advantages and disadvantages are assessed from the viewpoint of stability, particle size, and process impacts on some functionalities. The gastrointestinal fate and safety issues of ultrasonically prepared nanostructures are also discussed. Sonication, itself or in combination with other encapsulation approaches, alongside biopolymers generate nano-engineered carriers with enough stability, small particle sizes, and a low polydispersity. The nano-sized systems improve techno-functional activities of encapsulated bioactive agents including stability, solubility, dissolution, availability, controlled and targeted release profile in vitro and in vivo plus other bioactive properties such as antioxidant and antimicrobial capacities. Ultrasonically prepared nanocarriers show a great potential in fortifying food products with desired bioactive components, especially for the industrial applications.

Characterization of Carboxylated Cellulose Nanocrytals Isolated through Catalyst-Assisted H2O2 Oxidation in a One-Step Procedure.

A green and facile method was designed to isolate a type of cellulose nanocrystal (CNC) with carboxylated surfaces from native cellulose materials. Because isolation and modification processes of cellulosic particles are generally performed separately using harmful chemicals and multiple steps, the one-pot approach employed in this work is interesting from both an economical and ecological point of view. The reaction is carried out by adding hydrogen peroxide as an oxidant and copper(II) sulfate as a catalyst in acidic medium under mild thermal conditions. The charge content of the carboxylated CNC is about 1.0 mmol g-1, measured by a conductometric titration. Fourier transform infrared spectroscopy also proved the presence of carboxyl groups on the CNC particles. Atomic force microscopy along with optical polarized microscopy readily showed a rod shape morphology for the cellulosic particles. An average length of 263 nm and width of 23 nm were estimated by transmission electron microscopy. Dynamic laser scattering on carboxylated CNC suspensions by adding salt confirmed that nanoparticles are electrostatically stable. Carboxylated CNCs were furthermore characterized by solid carbon-13 nuclear magnetic resonance and X-ray spectroscopy.

Physicochemical and functional properties of ultrasonic-treated tragacanth hydrogels cross-linked to lysozyme.

The purpose of this study was to prepare, characterize and investigate physiochemical and functional attributes of hen egg white lysozyme (LZM) cross-linked with ultrasonic-treated tragacanth (US-treated TGC) under mild Maillard reactions conditions. FT-IR spectroscopy together with OPA assay revealed that covalent attachment of LZM with TCG's. Under optimum condition (pH=8.5, 60°C, RH=79%, 8 days), only one of the free amino group of LZM was blocked by TGC whereas under the same condition, US treated-TGC's blocked about three amino groups. The thermal stability of the LZM-TGC conjugates differed depending on the lengths of the main and branch chains. The microstructure of LZM-TGC conjugates was characterized by scanning electron microscopy. US-treated TGC-LZM exhibited improved solubility, emulsion properties, foam capacity and stability as compared with the native LZM. Since this gum is extensively used in food industry and application of LZM as a natural antimicrobial agents in different food systems is recommended and practiced in some countries, the results of this study indicates that a conjugated product of these two polymers combines different properties into one macromolecule and improves the property of each. These properties may make the conjugate an attractive food ingredient.