Advancing Photodynamic Antimicrobial Strategy: Sustainable Fabrication of Novel Lauryl Gallate-Chitosan Hydrophobic Films with Rapid Bacterial Capture and Biofilms Elimination Capabilities for Promoting Wound Healing.

Bioinspired photoactive composites, in terms of photodynamic inactivation, cost-effectiveness, and biosafety, are promising alternatives to antibiotics for combating bacterial infections while avoiding antibacterial resistance. However, the weak bacterial membrane affinity of the photoactive substrate and the lack of synergistic antibacterial effect remain crucial shortcomings for their antibacterial applications. Herein, we developed a hydrophobic film from food antioxidant lauryl gallate covalently functionalized chitosan (LG-g-CS conjugates) through a green radical-induced grafting reaction that utilizes synergistic bacteria capture, contact-killing, and photodynamic inactivation activities to achieve enhanced bactericidal and biofilm elimination capabilities. Besides, the grafting reaction mechanism between LG and CS in the ascorbic acid (AA)/H2O2 redox system was further proposed. The LG-g-CS films feature hydrophobic side chains and photoactive phenolic hydroxyl groups, facilitating dual bactericidal activities through bacteria capture and contact-killing via strong hydrophobic and electrostatic interactions with bacterial membranes as well as blue light (BL)-driven photodynamic bacterial eradication through the enhanced generation of reactive oxygen species. As a result, the LG-g-CS films efficiently capture and immobilize bacteria and exhibit excellent photodynamic antibacterial activity against model bacteria (Escherichia coli and Staphylococcus aureus) and their biofilms under BL irradiation. Moreover, LG-g-CS films could significantly promote the healing process of S. aureus-infected wounds. This research demonstrates a new strategy for designing and fabricating sustainable bactericidal and biofilm-removing materials with a high bacterial membrane affinity and photodynamic activity.

A smart thermoresponsive macroporous 4D structure by 4D printing of Pickering-high internal phase emulsions stabilized by plasma-functionalized starch nanomaterials for a possible delivery system.

Hierarchically porous structures combine microporosity, mesoporosity, and microporosity to enhance pore accessibility and transport, which are crucial to develop high performance materials for biofabrication, food, and pharmaceutical applications. This work aimed to develop a 4D-printed smart hierarchical macroporous structure through 3D printing of Pickering-type high internal phase emulsions (Pickering-HIPEs). The key was the utilization of surface-active (hydroxybutylated) starch nanomaterials, including starch nanocrystals (SNCs) (from waxy maize starch through acid hydrolysis) or starch nanoparticles (SNPs) (obtained through an ultrasound treatment). An innovative procedure to fabricate the functionalized starch nanomaterials was accomplished by grafting 1,2-butene oxide using a cold plasma technique to enhance their surface hydrophobicity, improving their aggregation, and thus attaining a colloidally stabilized Pickering-HIPEs with a low concentration of each surface-active starch nanomaterial. A flocculation of droplets in Pickering-HIPEs was developed after the addition of modified SNCs or SNPs, leading to the formation of a gel-like structure. The 3D printing of these Pickering-HIPEs developed a highly interconnected large pore structure, possessing a self-assembly property with thermoresponsive behavior. As a potential drug delivery system, this thermoresponsive macroporous 3D structure offered a lower critical solution temperature (LCST)-type phase transition at body temperature, which can be used in the field of smart releasing of bioactive compounds.

3D Printing of Bioactive Gel-like Double Emulsion into a Biocompatible Hierarchical Macroporous Self-Lubricating Scaffold for 3D Cell Culture.

The interconnected hierarchically porous structures are of key importance for potential applications as substrates for drug delivery, cell culture, and bioscaffolds, ensuring cell adhesion and sufficient diffusion of metabolites and nutrients. Here, encapsulation of a vitamin C-loaded gel-like double emulsion using a hydrophobic emulsifier and soy particles was performed to develop a bioactive bioink for 3D printing of highly porous scaffolds with enhanced cell biocompatibility. The produced double emulsions suggested a mechanical strength with the range of elastic moduli of soft tissues possessing a thixotropic feature and recoverable matrix. The outstanding flow behavior and viscoelasticity broaden the potential of gel-like double emulsion to engineer 3D scaffolds, in which 3D constructs showed a high level of porosity and excellent shape fidelity with antiwearing and self-lubricating properties. Investigation of cell viability and proliferation using fibroblasts (NIH-3T3) within vitamin C-loaded gel-like bioinks revealed that printed 3D scaffolds offered brilliant biocompatibility and cell adhesion. Compared to scaffolds without encapsulated vitamin C, 3D scaffolds containing vitamin C showed higher cell viability after 1 week of cell proliferation. This work represented a systematic investigation of hierarchical self-assembly in double emulsions and offered insights into mechanisms that control microstructure within supramolecular structures, which could be instructive for the design of advanced functional tissues.

γ-Cyclodextrin Metal-Organic Frameworks: Do Solvents Make a Difference?

Conventionally, methanol is the solvent of choice in the synthesis of gamma-cyclodextrin metal-organic frameworks (γ-CD-MOFs), but using ethanol as a replacement could allow for a more food-grade synthesis condition. Therefore, the aim of the study was to compare the γ-CD-MOFs synthesised with both methanol and ethanol. The γ-CD-MOFs were characterised by scanning electron microscopy (SEM), surface area and pore measurement, Fourier transform infrared spectroscopy (FTIR) and powder X-ray diffraction (PXRD). The encapsulation efficiency (EE) and loading capacity (LC) of the γ-CD-MOFs were also determined for curcumin, using methanol, ethanol and a mixture of the two as encapsulation solvent. It was found that γ-CD-MOFs synthesised by methanol and ethanol do not differ greatly, the most significant difference being the larger crystal size of γ-CD-MOFs crystallised from ethanol. However, the change in solvent significantly influenced the EE and LC of the crystals. The higher solubility of curcumin in ethanol reduced interactions with the γ-CD-MOFs and resulted in lowered EE and LC. This suggests that different solvents should be used to deliberately manipulate the EE and LC of target compounds for better use of γ-CD-MOFs as their encapsulating and delivery agents.

Emulsifying properties of plant-derived polypeptide and their conjugates: a self-consistent-field calculation study of the impact of hydrolysis.

By considering the hydrolysates of soy protein produced by trypsin as an example, the emulsion stabilizing properties of plant-based protein fragments have been investigated theoretically. We apply Self-Consistent-Field (SCF) calculations to determine the colloidal interactions induced between a pair of droplets stabilized by adsorbed layers of various soy protein fragments. The study is extended to conjugates of such polypeptides, formed by covalent bonding with a suitable hydrophilic sidechain (e.g. a polysaccharide). Our results show that the relatively longer fragments, with a greater number of hydrophobic amino acids, will display a stronger degree of adsorption affinity compared to the smaller hydrolysates, even where the latter may have a higher overall ratio of hydrophobic residues. This suggested that the degree of protein hydrolysis should be carefully controlled and limited to modest values to avoid the generation of a large number of short polypeptides, while still sufficient to improve solubility. While the emulsion stabilizing performance of a protein fragment type is strongly dependent on the conformation it adopts on the interface, we find this to be less critical for the conjugated polypeptides. However, we argue that with increasing degree of hydrolysis, many small fragments will not have the chance to form bonds with polysaccharides. It is demonstrated that the abundance of these unreacted polypeptides in the system severely reduces the efficiency of the conjugated longer protein fragments, preventing their presence on the surface of the droplets through competitive adsorption process.

Surface adsorption properties of peptides produced by non-optimum pH pepsinolysis of proteins: A combined experimental and self-consistent-field calculation study.

HYPOTHESIS: Partial hydrolysis of large molecular weight (Mw), highly aggregated plant proteins is frequently used to improve their solubility. However, if this hydrolysis is extensive, random or nonselective, it is unlikely to improve functional properties such as surface activity, emulsion, or foam-stabilising capacity. EXPERIMENTS AND SIMULATION: Soy protein isolate (SPI) was hydrolysed by pepsin under optimal (pH 2.1) and non-optimal (pH 4.7) conditions. The surface activity and emulsion stabilising capacity of the resultant peptides were measured and compared. The colloidal interactions between a pair of emulsion droplets were modelled via Self-Consistent-Field Calculations (SCFC). FINDINGS: Hydrolysis at pH 2.1 and 4.7 resulted in a considerable increase in measured surface activity compared to the native (non-hydrolysed) SPI, but the hydrolysate from pH 2.1 was not as good an emulsion stabiliser as the hydrolysate (particularly the fraction Mw > 10 kDa) at pH 4.7. Furthermore, peptide analysis of the latter suggested it was dominated by a fragment of one of the major soy proteins ß-conglycinin, with Mw ≈ 25 kDa. SCFC calculations confirmed that interactions mediated by adsorbed layers of this peptide point to it being an excellent emulsion stabiliser.

Transforming sustainable plant proteins into high performance lubricating microgels.

With the resource-intensive meat industry accounting for over 50% of food-linked emissions, plant protein consumption is an inevitable need of the hour. Despite its significance, the key barrier to adoption of plant proteins is their astringent off-sensation, typically associated with high friction and consequently poor lubrication performance. Herein, we demonstrate that by transforming plant proteins into physically cross-linked microgels, it is possible to improve their lubricity remarkably, dependent on their volume fractions, as evidenced by combining tribology using biomimetic tongue-like surface with atomic force microscopy, dynamic light scattering, rheology and adsorption measurements. Experimental findings which are fully supported by numerical modelling reveal that these non-lipidic microgels not only decrease boundary friction by an order of magnitude as compared to native protein but also replicate the lubrication performance of a 20:80 oil/water emulsion. These plant protein microgels offer a much-needed platform to design the next-generation of healthy, palatable and sustainable foods.

"Sounding" out crystal nuclei-A mathematical-physical and experimental investigation.

We outline techniques for the control and measurement of the nucleation of crystalline materials. Small angle x-ray scattering/wide angle x-ray scattering x-ray diffraction measurements are presented that demonstrate the impact of low power, continuous, non-cavitational ultrasound on the nucleation and crystallization of a wax-n-eicosane dissolved in a heptane/toluene solvent. A mathematical-physical approach based on the rectification of heat and mass transport by such a low power oscillating pressure field is outlined, and it is suggested that this approach be combined with dissipative particle dynamics computational modeling to develop a predictive method capable of modeling the impact of low power oscillating pressure fields (acoustics and ultrasonics) on a wide range of nucleating systems. Combining the ultrasound pitch and catch speed of sound measurements with low power harmonically oscillating pressure fields to monitor and control nucleation presents the prospect of entirely new industrially significant methods of process control in crystallization. It also offers new insights into nucleation processes in general. However, for the acoustic control technique to be widely applied , further theoretical and modeling work will be necessary since, at present, we are unable to predict the precise effect of low power ultrasound in any given situation.

Effect of polymer architecture on the adsorption behaviour of amphiphilic copolymers: A theoretical study.

HYPOTHESIS: Polymer architecture is known to have significant impact on its adsorption behaviour. Most studies have been concerned with the more concentrated, "close to surface saturation" regime of the isotherm, where complications such as lateral interactions and crowding also additionally affect the adsorption. We compare a variety of amphiphilic polymer architectures by determining their Henry's adsorption constant (kH), which, as with other surface active molecules, is the proportionality constant between surface coverage and bulk polymer concentration in a sufficiently dilute regime. It is speculated that not only the number of arms or branches, but also the position of adsorbing hydrophobes influence the adsorption, and that by controlling the latter the two can counteract each other. METHODOLOGY: The Self-consistent field calculation of Scheutjens and Fleer was implemented to calculate the adsorbed amount of polymer for many different polymer architectures including linear, star and dendritic. Using the adsorption isotherms at very low bulk concentrations, we determined the value of kH for these. FINDINGS: It is found that the branched structures (star polymers and dendrimers) can be viewed as analogues of linear block polymers based on the location of their adsorbing units. Polymers containing consecutive trains of adsorbing hydrophobes in all cases showed higher level of adsorption compared to their counterparts, where the hydrophobes were more uniformly distributed on the chains. While increasing the number of branches (or arms for star polymers) also confirmed the known result that the adsorption decreased with the number of arms, this trend can be partially offset by the appropriate choice of the location of anchoring groups.

Spatial Localization of Two Enzymes at Pickering Emulsion Droplet Interfaces for Cascade Reactions.

Developing biocatalytic cascades in abiological conditions is of utmost significance, but such processes often suffer from low reaction efficiency because of incompatible reaction environments and suppressed intermediate transportation. Herein we report a new type of biocatalytic cascade by localizing two different enzymes separately in the outer and inner interfacial layers of Pickering emulsion droplets. This versatile approach enables the localization of two enzymes in their preferred reaction microenvironments and simultaneously in nanoscale proximity of each other. The thus-designed interfacial biocatalytic cascades show outstanding catalytic efficiency in alkene epoxidation and thioether oxidation with in situ generation of hydrogen peroxide under mild conditions, 6.9-13.6 times higher than the catalytic efficiency of the free enzymes in solution and their multi-enzymatic counterparts. The remarkable interfacial effect of Pickering droplets was found to be responsible for the significantly enhanced cascading efficiency.

Insights into the Supramolecular Structure and Degradation Mechanisms of Starch from Different Botanical Sources as Affected by Extrusion-based 3D Printing.

Extrusion-based 3D printing has emerged as the most versatile additive manufacturing technique for the printing of practically any material. However, 3D printing of functional materials often activates thermo-mechanical degradation, which affects the 3D shape quality. Herein, we describe the structural changes of eight different starch sources (normal or waxy) as a consequence of the temperature of an extrusion-based 3D printing system through in-depth characterization of their molecular and structural changes. The combination of size-exclusion chromatography, small-angle X-ray scattering, X-ray diffraction, dynamic viscoelasticity measurements, and in vitro digestion has offered an extensive picture of the structural and biological transformations of starch varieties. Depending on the 3D printing conditions, either gelatinization was attained ("moderate" condition) or single-amylose helix formation was induced ("extreme" condition). The stiff amylopectin crystallites in starch granules were more susceptible to thermo-mechanical degradation compared to flexible amorphous amylose. The crystalline morphology of the starch varieties varied from B-type crystallinity for the starch 3D printing at the "moderate" condition to a mixture of C- and V-type crystallinity regarding the "extreme" condition. The "extreme" condition reduced the viscoelasticity of 3D-printed starches but increased the starch digestibility rate/extent. In contrast, the "moderate" condition increased the viscoelastic moduli, decreasing the starch digestion rate/extent. This was more considerable mainly regarding the waxy starch varieties. Finally, normal starch varieties presented a well-defined shape fidelity, being able to form a stable structure, whereas waxy starches exhibited a non-well-defined structure and were not able to maintain their integrity after printing. The results of this research allow us to monitor the degradability of a variety of starch cultivars to create starch-based 3D structures, in which the local structure can be controlled based on the 3D printing parameters.

A supraparticle-based biomimetic cascade catalyst for continuous flow reaction.

Robust millimeter-sized spherical particles with controlled compositions and microstructures hold promises of important practical applications especially in relation to continuous flow cascade catalysis. However, the efficient fabrication methods for producing such particles remain scare. Here, we demonstrate a liquid marble approach to fabricate robust mm-sized porous supraparticles (SPs) through the bottom-up assembly of silica nanoparticles in the presence of strength additive or surface interactions, without the need for the specific liquid-repellent surfaces used by the existing methods. As the proof of the concept, our method was exemplified by fabricating biomimetic cascade catalysts through assembly of two types of well-defined catalytically active nanoparticles. The obtained SP-based cascade catalysts work well in industrially preferred fixed-bed reactors, exhibiting excellent catalysis efficiency, controlled reaction kinetics, high enantioselectivity (99% ee) and outstanding stability (200~500 h) in the cascades of ketone hydrogenation-kinetic resolution and amine racemization-kinetic resolution. The excellent catalytic performances are attributed to the structural features, reconciling close proximity of different catalytic sites and their sufficient spatial isolation.

Co-compartmentalization of Enzymes and Cofactors within Pickering Emulsion Droplets for Continuous-Flow Catalysis.

Co-immobilization of enzymes and cofactors in a manner suitable for use in continuous flow catalysis remains a great challenge because of the difficulty in ensuring the free accessibility of immobilized enzymes and cofactors. Herein, we present a continuous flow catalysis system based on co-compartmentalization of enzymes and cofactors within Pickering emulsion droplets, enabling regeneration of cofactors within the droplets. As exemplified by enzyme-catalyzed ketone enantioselective reduction and enantioselective transamination, our systems exhibit long-term stability (300-400 h), outstanding total turnover number (TTN, 59204 mol mol-1 ) and several-fold enhancement in the enzyme catalytic efficiency (CEe ) in comparison to conventional biphasic reactions. As well as giving insight into the co-compartmentalization effects, our system will provide the opportunity to significantly advance continuous-flow biocatalysis towards the level of practical applications.

Dual-Grafting of Microcrystalline Cellulose by Tea Polyphenols and Cationic ε-Polylysine to Tailor a Structured Antimicrobial Soy-Based Emulsion for 3D Printing.

An imperative processing way to produce 3D printed structures with enhanced multifunctional properties is printing inks in the form of a gel-like colloidal emulsion. The surface-modified microcrystalline cellulose (MCC) is an excipient of outstanding merit as a particulate emulsifier to manufacture a stable Pickering emulsion gel. The tuning of the MCC structure by cationic antimicrobial compounds, such as ε-polylysine (ε-PL), can offer a surface activity with an antimicrobial effect. However, the MCC/ε-PL lacks the appropriate emulsifying ability due to the development of electrostatic complexes. To overcome this challenge, (i) a surface-active MCC conjugate was synthesized by a sustainable dual-grafting technique (ii) to produce a highly stable therapeutic soy-based Pickering emulsion gel (iii) for potential application in 3D printing. In this regard, the tea polyphenols were initially introduced into MCC by the free-radical grafting method to decrease the charge density of anionic MCC. Then, the antioxidative MCC-g-tea polyphenols were reacted by ε-PL to produce a dual-grafted therapeutic MCC conjugate (micro-biosurfactant), stabilizing the soy-based emulsion system. The results indicated that the dual-grafted micro-biosurfactant formed a viscoelastic and thixotropic soy-based emulsion gel with reduced droplet size and long-term stability. Besides, there was an improvement in the interfacial adsorption features of soy-protein particles after micro-biosurfactant incorporation, where the interfacial pressure and surface dilatational viscoelastic moduli were enhanced. Consequently, it was revealed that the therapeutic Pickering emulsion gel was more suitable to manufacture a well-defined 3D architecture with high resolution and retained permanent deformation after unloading (i.e., a recoverable matrix). This work established that the modification of the MCC backbone by tea polyphenols and ε-PL advances its bioactive properties and emulsifying performance, which finally obtains a soy-based 3D printed structure with noteworthy mechanical strength.

A Promising Therapeutic Soy-Based Pickering Emulsion Gel Stabilized by a Multifunctional Microcrystalline Cellulose: Application in 3D Food Printing.

The feasible application of additive manufacturing in the food and pharmaceutical industries strongly depends on the development of highly stable inks with bioactive properties. Surface-modified microcrystalline cellulose (MCC) shows the potential of being a useful particulate (i.e., Pickering)-type emulsifier to stabilize emulsions. To attain desired therapeutic properties, MCC can also be tuned with cationic antimicrobial compounds to fabricate an antimicrobial printable ink. However, due to the formation of complex coacervates between the two, the Pickering emulsion is very susceptible to phase separation with an insufficient therapeutic effect. To address this drawback, we reported a green method to produce antioxidant and antimicrobial three-dimensional (3D)-printed objects, illustrated here using a printable ink based on a soy-based particulate-type emulsion gel stabilized by a surface-active MCC conjugate (micro-biosurfactant). A sustainable method for the modification of MCC is investigated by grafting gallic acid onto the MCC backbone, followed by in situ reacting via lauric arginate through Schiff-base formation and/or Michael-type addition. Our results show that the grafted micro-biosurfactant was more efficient in providing the necessary physical stability of soy-based emulsion gel. The grafted micro-biosurfactant produced a multifunctional ink with viscoelastic behavior, thixotropic property, and outstanding bioactivities. Following the 3D printing process, highly porous 3D structures with a more precise geometry were fabricated after addition of the micro-biosurfactant. Dynamic sensory evaluation showed that the micro-biosurfactant has a remarkable ability to improve the temporal perceptions of fibrousness and juiciness in printed meat analogue. The results of this study showed the possibility of the development of a therapeutic 3D-printed meat analogue with desired sensory properties, conceiving it as a promising meat analogue product.

Pickering emulsion droplet-based biomimetic microreactors for continuous flow cascade reactions.

A continuous flow cascade of multi-step catalytic reactions is a cutting-edge concept to revolutionize stepwise catalytic synthesis yet is still challenging in practical applications. Herein, a method for practical one-pot cascade catalysis is developed by combining Pickering emulsions with continuous flow. Our method involves co-localization of different catalytically active sub-compartments within droplets of a Pickering emulsion yielding cell-like microreactors, which can be packed in a column reactor for continuous flow cascade catalysis. As exemplified by two chemo-enzymatic cascade reactions for the synthesis of chiral cyanohydrins and chiral ester, 5 - 420 fold enhancement in the catalysis efficiency and as high as 99% enantioselectivity were obtained even over a period of 80 - 240 h. The compartmentalization effect and enriching-reactant properties arising from the biomimetic microreactor are theoretically and experimentally identified as the key factors for boosting the catalysis efficiency and for regulating the kinetics of cascade catalysis.

Ultra-efficient antimicrobial photodynamic inactivation system based on blue light and octyl gallate for ablation of planktonic bacteria and biofilms of Pseudomonas fluorescens.

Pseudomonas fluorescens is a Gram-negative spoilage bacterium and dense biofilm producer, causing food spoilage and persistent contamination. Here, we report an ultra-efficient photodynamic inactivation (PDI) system based on blue light (BL) and octyl gallate (OG) to eradicate bacteria and biofilms of P. fluorescens. OG-mediated PDI could lead to a > 5-Log reduction of viable cell counts within 15 min for P. fluorescens. The activity is exerted through rapid penetration of OG towards the cells with the generation of a high-level toxic reactive oxygen species triggered by BL irradiation. Moreover, OG plus BL irradiation can efficiently not only prevent the formation of biofilms but also scavenge the existing biofilms. Additionally, it was shown that the combination of OG/poly(lactic acid) electrospun nanofibers and BL have great potential as antimicrobial packagings for maintaining the freshness of the salamander storge. These prove that OG-mediated PDI can provide a superior platform for eradicating bacteria and biofilm.

New Horizons in Microbiological Food Safety: Ultraefficient Photodynamic Inactivation Based on a Gallic Acid Derivative and UV-A Light and Its Application with Electrospun Cyclodextrin Nanofibers.

An excellent bactericidal effect of octyl gallate (OG)-mediated photodynamic inactivation (PDI) against foodborne pathogens (Escherichia coli and Staphylococcus aureus) was evaluated in relation to the mode of action. UV-A irradiation (wavelength, 365 nm; irradiance, 8.254 ± 0.18 mW/cm2) of the bacterial suspension containing 0.15 mM OG could lead to a >5-log reduction of viable cell counts within 30 min for E. coli and only 5 min for S. aureus. Reactive oxygen species (ROS) formation was considered the main reason for the bactericidal effect of OG + UV-A light treatment because toxic ROS induced by OG-mediated PDI could attack the cellular wall, proteins, and DNA of microbes. Moreover, the bactericidal effect, as well as the yields of ROS, depended on OG concentrations, irradiation time, and laser output power. Furthermore, we prepared an edible photodynamic antimicrobial membrane comprising electrospun cyclodextrin nanofibers (NFs) by embedding OG. The resultant OG/HPßCD NFs (273.6 µg/mL) under UV-A irradiation for 30 min (14.58 J/cm) could cause a great reduction (>5-log) of viable bacterial counts of E. coli. The in situ photodynamic antibacterial activity of OG/HPßCD NF-based packaging was evaluated during the Chinese giant salamander storage. Overall, this research highlights the dual functionalities (antibacterial and photodynamic properties) of OG as both an antibacterial agent and photosensitizer and the effectiveness of electrospun NFs containing OG as an active antibacterial packaging material for food preservation upon UV light illumination.

Development of an Antioxidative Pickering Emulsion Gel through Polyphenol-Inspired Free-Radical Grafting of Microcrystalline Cellulose for 3D Food Printing.

The manufacture of next-generation 3D-printed foods with personalized requirements can be accelerated by in-depth knowledge of the development of a multifunctional biopolymeric-based ink. As a fat replacer in the food industry, microcrystalline cellulose (MCC) has the potential to address the growing need for sustainable healthy reduced-fat 3D printed foods. The modification of MCC structure by polyphenols gives the way to produce a multifunctional antioxidative Pickering emulsion with improved emulsifying properties. In this study, different types of polyphenols, including gallic acid (GA), tannic acid (TA), and cyanidin-3-O-glucoside (C3G), were individually used to synthesize the grafted MCC-g-polyphenol conjugates by the free-radical grafting method. Then, the antioxidative grafted microconjugates were added to a soy protein-based emulsion gel to partially substitute its oil, and each Pickering emulsion gel variant was printed through an extrusion-based 3D printing system. Emulsifying properties and antioxidant character of MCC were proven to be enhanced after the fabrication of grafted microconjugates. Compared to MCC-g-TA, MCC-g-GA and MCC-g-C3G could efficiently improve the stability of a reduced-fat soy-based emulsion gel upon storage. Moreover, the reduced-fat soy-based emulsion gel containing grafted microconjugates endowed a characteristic shear-thinning behavior with a gel-like structure and superlative thixotropic properties. Following the printing, the antioxidative Pickering emulsion gels containing grafted microconjugates produced well-defined 3D structures with superior lubrication properties. This study demonstrated that the grafting of polyphenols onto MCC could enhance bioactive properties and improve emulsifying performance of MCC, making it a useful component in the development of personalized functional foods.

Dual metal nanoparticles within multicompartmentalized mesoporous organosilicas for efficient sequential hydrogenation.

Controlling localization of multiple metal nanoparticles on a single support is at the cutting edge of designing cascade catalysts, but is still a scientific and technological challenge because of the lack of nanostructured materials that can not only host metal nanoparticles in different sub-compartments but also enable efficient molecular transport between different metals. Herein we report a multicompartmentalized mesoporous organosilica with spatially separated sub-compartments that are connected by short nanochannels. Such a unique structure allows co-localization of Ru and Pd nanoparticles in a nanoscale proximal fashion. The so designed cascade catalyst exhibits an order of magnitude activity enhancement in the sequential hydrogenation of nitroarenes to cyclohexylamines compared with its mono/bi-metallic counterparts. Crucially, an interesting phenomenon of neighboring metal-assisted hydrogenation via hydrogen spillover is observed, contributing to the significant enhancement in catalytic efficiency. The multicompartmentalized architectures along with the revealed mechanism of accelerated hydrogenation provide vast opportunity for designing efficient cascade catalysts.