Tunable Surface Properties Research Articles

A poly (vinyl alcohol) coated core-shell nanoparticle with a tunable surface for pH and glutathione dual-responsive drug delivery

The surface characteristics of nanoparticles play a pivotal role in modulating the efficiency and functionality of drug delivery systems, particularly when addressing the complex challenges of targeted therapeutics. This study presents the development of a core-shell nanoparticle system (PMAA@DOX-PVA), incorporating poly(vinyl alcohol) (PVA) as a dynamic shell component to establish dual responsiveness to pH and glutathione levels. The hydrophilic PVA shell is covalently conjugated to the poly (methylacrylic acid) (PMAA) core via a boronic ester bond, establishing a robust platform for controlled release with tunable surface properties. Notably, our findings demonstrate a remarkable enhancement in drug loading efficiency from a modest 8% (PMAA@DOX) to an impressive 18% (PMAA@DOX-PVA-0.2). Furthermore, under physiological conditions (pH 7.4), the drug leakage after 62hours is significantly reduced, dropping from 37% (PMAA@DOX) to 21% (PMAA@DOX-PVA-0.2). This suggests a potential improvement in stability during blood circulation. Intriguingly, the PVA ratio was found to influence drug release profiles under different environments distinctly. The possible mechanism was proposed offering insight into this tunable behavior. In vitro cytotoxicity assays on A549 cancer cells reveal that the blank carriers exhibit excellent biocompatibility, while the PVA-coated nanoparticles significantly boost anti-tumor efficacy. Collectively, these results present a promising strategy for designing core-shell nanoparticles with customizable surface properties, paving the way for next-generation, multifunctional drug delivery systems in diverse biomedical applications.

Use of Modified Silica as Selective Adsorbent on Exhaust and Dissolved Gases

Emissions are substances that enter the air, whether or not they have the potential as pollutants. Emission gases can have adverse effects on the health of living beings, especially humans, and can contribute to an increase in the Earth's temperature. Therefore, separation efforts are needed to minimize the negative impacts caused by them. Adsorption method was categorized as absorption, cryogenic distillation, and membrane. Although there were shortcomings in adsorbing emission gases through the method, it remained a promising approach. Adsorption was recognized for its economic viability, technological effectiveness, thermally stability, corrosion resistance, high load capacity, and tunable surface properties. However, adsorption materials were categorized as porous carbon, zeolites, metal-organic frameworks (MOFs), porous polymers, and porous silica. A significant limitation of the method was its susceptibility to decreased capacity in the presence of water vapor. The analysis results showed that porous silica became a superior adsorption material due to its high porosity, which facilitated rapid gas diffusion. To enhance selectivity and adjust pore size, material modifications, particularly silica, became necessary. This showed that surface modification for silicasupported the improvements in selectivity and pore size.

Nanoimprinting of Crosslinked Polyurethane / Polycaprolactone Blends: Scratch Recovery of Surface Topographies.

Scratch recovery of micro-nano-patterned polymer surfaces extends the service life of products that require tunable surface properties and contributes to more sustainable development. Scratch recovery has been widely studied in bulk and 4D-printed polymers via intrinsic self-healing mechanisms. Existing studies on self-healing of micro/nano-scale polymeric surfaces are limited to the recovery of controlled tensile or compressive strain. Scratch recovery requires material transport to close the gap created by a scratch. Here, for the first time, scratch recovery of thermally nanoimprinted polymer surfaces in a heterogeneous polymer is reported. A blend of Polyurethane (TPU) and poly(caprolactone) (PCL) with selectively crosslinked TPU imparts shape-memory properties, and the uncrosslinked PCL retains chain mobility for molecular diffusion during scratch recovery. Scratch recovery of nanoimprinted micro-pillars has been achieved spontaneously and completely by heat and without any pressure input. The healing temperature is determined to be the melting point of PCL at 60°C. Rapid recovery is also achieved at 60 s with complete closure of scratch width of 5µm and topography recovery of the nanoimprinted micro-pillars.

Impregnation, dehydration and crosslinking of responsive organoboron polymer to generate smart gating membrane for multimolecular gradient separation

Responsive materials have garnered increasing attention in the membrane separation field. However, fabricating smart gating membranes with tunable pore sizes to separate complex systems remains challenging. Herein, gating membranes with boroxine skeleton and temperature-tunable pores were successfully fabricated by fixing lower critical solution temperature (LCST)-type organoboron polymers (poly(N-isopropylacrylamide-co-glycidyl methacrylate/3-aminophenylboronic acid), PNG-APBA) onto the membrane surface via "impregnation-dehydration-crosslinking" strategy. The conformational behavior of the NIPAM-containing polymer chains (shrinking above LCST-stretching below LCST) serves as a functional gate, enabling the membranes to achieve reversibly tunable pore sizes and surface properties. The modified membranes exhibit gradient separation capabilities for small/medium/large molecules in complex polymer systems through temperature-tunable channels. The tunable pores also provided a potential tool for the high-selectivity separation of mixed proteins, such as lysozyme (LZM) and hemoglobin (Hb). Notably, the conformational behavior of the polymer chains endowed the membranes with excellent self-cleaning ability (FRR> 99.5 %), while the boroxine network enhanced the grafting stability of the polymer chains, ensuring effective reversibility and repeatability of membranes.

Solid-Solution MXenes: Synthesis, Properties, and Applications.

ConspectusMXenes, among other two-dimensional (2D) materials such as graphene, hexagonal BN, transition metal dichalcogenides (TMDs), 2D metal-organic frameworks (MOFs), and covalent organic frameworks (COFs), are the fastest growing class discovered thus far. The general formula of MXenes is Mn+1XnTx, where M, X, and Tx represent an early transition metal (Ti, V, Nb, Mo, etc.), C and/or N, and the surface functional groups (typically, O, OH, F, Cl), respectively, and n can be between 1 and 4. MXenes as a class of materials have extraordinary properties, such as high electrical conductivity, nonlinear optical properties, solution processability, scalability and ease of synthesis, redox capability, and tunable surface properties, among others; the specific properties, however, depend on their chemistry. Since the initial report of the first MXene in 2011, the research community has primarily focused on Ti3C2Tx, and the amount of research work to investigate its synthesis and properties has increased exponentially over the years. In materials science, alloying is a useful way of synthesizing new materials to improve the properties of a class of materials. Advancement of steel and synthesis of inorganic semiconductors can be regarded as some of the major historical advancements in the concept of alloying. Thus, just one year after the initial report of MXenes, the first solid-solution MXene, (TiNb)2CTx, was reported, which demonstrates the inherent chemical tunability of this class of materials.MXenes have two sites for compositional variation: elemental substitution on both the metal (M) and carbon/nitrogen (X) sites, presenting promising routes for tailoring their properties. X-site solid-solutions include carbonitride MXenes and are the least studied class of MXenes to date. Comparatively, multi-M MXenes have acquired significant attention, leading to the extreme example of high-entropy solid-solution MXenes. By using multiple M elements, a significant expansion of the structural and chemical diversity is possible, giving rise to novel chemical, magnetic, electronic, and optical properties that cannot be accessed by single-M MXenes. Solid-solution MXenes represent the largest and most tunable class of MXenes; solid-solution MXenes are those that have multiple metals that are randomly distributed on their M sites with no distinct chemical ordering. Using multiple M elements in MXenes, it is possible to synthesize novel MXene structures that cannot be produced otherwise, such as M5X4Tx MXenes. Based on their chemistry, it is possible to rationally control the electronic, optical, mechanical, and chemical properties in a way that no other class of MXenes can. In some cases, the resultant property is linearly related to the chemistry, such as the electrical conductivity, while in other cases the properties are nonlinear or emergent: optical properties, enabling these MXenes to fulfill roles that no other MXene, or 2D material, can.In this Account, we discuss the recent progress in the synthesis, properties, applications, and outlook of solid-solution MXenes. Importantly, we demonstrate how multi-M solid-solutions can be used to tailor properties for specific applications easily.

Pickering emulsions stabilized by cellulose nanofibers with tunable surface properties for thermal energy storage

Cellulose nanofibers (CNFs) have been widely used as a renewable emulsifier to stabilize two immiscible liquids due to their intrinsic amphiphilicity and excellent emulsifying ability. However, it remains challenging to fully understand the effects of carboxylate group content and surface charge density on the emulsifying ability of CNFs and the stability of Pickering emulsion. Herein, carboxymethylated CNFs were extracted from bleached kraft pulp using etherification reaction and high-pressure homogenization, allowing for easy surface charge density and size adjustment by changing sodium chloroacetate content and homogenization cycles. The optimizing CNFs possessed a high Zeta potential (−71.2 mV) and a suitable carboxylate group content (1.81 mmol/g), which enabled CNFs to irreversibly adsorb at the hydrophobic paraffin wax (PW) droplet surface and form interfacial steric barriers, providing large electrostatic repulsion between the PW droplets against coalescence. Thus, the CNF-stabilized PW emulsions could be stored for more than 6 months. Moreover, the phase change enthalpy of the freeze-dried emulsion is as high as 193.7 J/g, which provides the emulsion to reversibly store and release heat. This work provides a comprehensive insight into the interfacial stability mechanism of CNFs as stabilizers and facilitates the potential application in thermal energy storage.

Insights into solid-contact ion-selective electrodes based on laser-induced graphene: Key performance parameters for long-term and continuous measurements.

This work aims to serve as a comprehensive guide to properly characterize solid-contact ion-selective electrodes (SC-ISEs) for long-term use as they advance toward calibration-free sensors. The lack of well-defined SC-ISE performance criteria limits the ability to compare results and track progress in the field. Laser-induced graphene (LIG) is a rapid and scalable method that, by adjusting the CO2 laser parameters, can create LIG substrates with tunable surface properties, including wettability, surface chemistry, and morphology. Herein, we fabricate laser-induced graphene (LIG) solid-contact electrodes using different laser settings and subsequently convert them into ion-selective sensors using a potassium-selective membrane. We measure the aforementioned tunable surface properties and correlate them with resultant low-frequency capacitance and water layer formation in an effort to pinpoint their effects on the sensitivity (Nernstian response), reproducibility (E°' variation), and potential stability of the LIG-based SC-ISEs. More specifically, we demonstrate that the surface wettability of the LIG substrate, which can be tuned by controlling the lasing parameters, can be modified to exhibit hydrophobic (contact angle > 90°) and even highly hydrophobic surfaces (contact angle ≈ 130°) to help reduce sensor drift. Recommendations are also provided to ensure proper and robust characterization of SC-ISEs for long-term and continuous measurements. Ultimately, we believe that a comprehensive understanding of the correlation between LIG tunable surface properties and SC-ISE performance can be used to improve the electrochemical behavior and stability of SC-ISEs designed with a wide range of materials beyond LIG.

Tuning Surface Properties of PLA for Capturing Nonpolar Compounds from Water

Tuning Surface Properties of PLA for Capturing Nonpolar Compounds from Water

A Novel Approach for the Synthesis of Responsive Core-Shell Nanogels with a Poly(N-Isopropylacrylamide) Core and a Controlled Polyamine Shell.

Microgel particles can play a key role, e.g., in drug delivery systems, tissue engineering, advanced (bio)sensors or (bio)catalysis. Amine-functionalized microgels are particularly interesting in many applications since they can provide pH responsiveness, chemical functionalities for, e.g., bioconjugation, unique binding characteristics for pollutants and interactions with cell surfaces. Since the incorporation of amine functionalities in controlled amounts with predefined architectures is still a challenge, here, we present a novel method for the synthesis of responsive core-shell nanogels (dh < 100 nm) with a poly(N-isopropylacrylamide) (pNIPAm) core and a polyamine shell. To achieve this goal, a surface-functionalized pNIPAm nanogel was first prepared in a semi-batch precipitation polymerization reaction. Surface functionalization was achieved by adding acrylic acid to the reaction mixture in the final stage of the precipitation polymerization. Under these conditions, the carboxyl functionalities were confined to the outer shell of the nanogel particles, preserving the core's temperature-responsive behavior and providing reactive functionalities on the nanogel surface. The polyamine shell was prepared by the chemical coupling of polyethyleneimine to the nanogel's carboxyl functionalities using a water-soluble carbodiimide (EDC) to facilitate the coupling reaction. The efficiency of the coupling was assessed by varying the EDC concentration and reaction temperature. The molecular weight of PEI was also varied in a wide range (Mw = 0.6 to 750 kDa), and we found that it had a profound effect on how many polyamine repeat units could be immobilized in the nanogel shell. The swelling and the electrophoretic mobility of the prepared core-shell nanogels were also studied as a function of pH and temperature, demonstrating the successful formation of the polyamine shell on the nanogel core and its effect on the nanogel characteristics. This study provides a general framework for the controlled synthesis of core-shell nanogels with tunable surface properties, which can be applied in many potential applications.

Pushing Theoretical Potassium Storage Limits of MXenes through Introducing New Carbon Active Sites.

Surface-driven capacitive storage enhances rate performance and cyclability, thereby improving the efficacy of high-power electrode materials and fast-charging batteries. Conventional defect engineering, widely-employed capacitive storage optimization strategy, primarily focuses on the influence of defects themselves on capacitive behaviors. However, the role of local environment surrounding defects, which significantly affects surface properties, remains largely unexplored for lack of suitable material platform and has long been neglected. As proof-of-concept, typical Ti3C2Tx MXenes are chosen as model materials owing to metallic conductivity and tunable surface properties, satisfying the requirements for capacitive-type electrodes. Using density functional theory (DFT) calculations, the potential of MXenes with modulated local atomic environment is anticipated and introducing new carbon sites found near pores can activate electrochemically inert surface, attaining record theoretical potassium storage capacities of MXenes (291 mAh g-1). This supposition is realized through atomic tailoring via chemical scissor within sublayers, exposing new sp3-hybridized carbon active sites. The resulting MXenes demonstrate unprecedented rate performance and cycling stability. Notably, MXenes with higher carbon exposure exhibit a record-breaking capacity over 200 mAh g-1 and sustain a capacity retention higher than 80% after 20 months. These findings underscore the effectiveness of regulating defects' neighboring environment and illuminate future high-performance electrode design.

Standalone Highly Efficient Graphene Oxide as an Emerging Visible Light-Driven Photocatalyst and Recyclable Adsorbent for the Sustainable Removal of Organic Pollutants.

Carbon-based nanostructures are promising eco-friendly multifunctional nanomaterials because of their tunable surface and optoelectronic properties for a variety of energy and environmental applications. The present study focuses on the synthesis of graphene oxide (GO) with particular emphasis on engineering its surface and optical properties for making it an excellent adsorbent as well as a visible light-active photocatalyst. It was achieved by modifying the improved Hummers method through optimizing the synthesis parameters involved in the oxidation process. This controlled synthesis allows for systematic tailoring of structural, optical, and surface functionality, leading to improved adsorption and photocatalytic properties for the sustainable removal of organic pollutants in water treatment. Several spectroscopic and microscopic characterization techniques, such as XRD, SEM, Raman, UV-visible, FTIR, TEM, XPS, BET, etc. were employed to analyze the degree of oxidation, surface chemistry/functionalization, morphological, optical, and structural properties of the synthesized GO nanostructures. The analyses showed excellent surface functionality with surface active sites for better adsorptive removal and a tunable band gap from 2.51 to 2.76 eV exhibiting excellent natural sunlight activity (>99%) for photocatalytic removal of the organic pollutant. Various adsorption isotherms have been studied with excellent adsorption capability (Qmax = 454.54 mg/g) as compared to the literature. The study introduces GO both as a proficient stand-alone (sole) nanoadsorbent as well as a nanophotocatalyst for the efficient removal of organic dye pollutants in water treatment. Additionally, the article highlights the sustainable solar light-induced green chemistry aspects of GO as an excellent recyclable adsorbent as a result of its self-cleaning ability under natural sunlight, demonstrating its potential in real eco-friendly environmental and practical applications.

Ni3C nanosheets and PVA nanocomposite based memristor for low-cost and flexible non-volatile memory devices

Two-dimensional (2D) MXenes have gained extensive attention in the field of memristors due to their high ion mobility, chemical stability and tunable electrical and surface properties. Moreover, MXenes have tunable interlayer bonding which enables enhancement in memristor performance. In this work, we synthesize a novel nanocomposite of Ni3C nanosheets and polyvinyl alcohol (PVA) and fabricate a flexible memristor with Ag/Ni3C-PVA/ITO/PET configuration for non-volatile memory applications. Ni3C nanosheets were synthesized from Ni-MAX (Ni3AlC2) through a solvothermal etching and exfoliation process. The nanosheet like structure of Ni3C is confirmed through Scanning Electron Microscopy (SEM) and Transmission Electron microscopy (TEM). Characterization techniques like X-ray diffraction (XRD), Raman spectroscopy and Fourier Transform Infrared Spectroscopy (FTIR) reveal the crystalline phases, surface functional groups and chemical bonds present in Ni3C nanosheets and Ni3C-PVA nanocomposite. The memristor was fabricated through a facile low cost solution processed based fabrication technique. The Ag/Ni3C-PVA/ITO/PET memristor exhibits bipolar non-volatile switching characteristics. The device with optimised mass ratio of 4:3 (Ni3C: PVA) shows a decent off/on ratio of 2.09 × 102, long retention time of 104 s, and an endurance of 102 DC cycles. The SET voltage of the as-fabricated device is 2.8 V and the RESET voltage is −5.33 V. The flexible memristor exhibits outstanding mechanical robustness over 500 bending cycles. The high charge carrier mobility of Ni3C results in lower switching voltage and the dielectric property of PVA improves data retention and off/on ratio of the memristor. The resistive switching behaviour is explained through conductive metallic bridge mechanism. The conduction mechanism follows Ohmic conduction in ON state and trap controlled space charge limited current (TCSCLC) mechanism in OFF state. The results demonstrate that the nanocomposite with its superior resistive switching effects is suitable for cost-effective, high-performance, flexible non-volatile memory devices.

From Synthesis to Functionality: Tailored Ionic Liquid-Based Electrospun Fibers with Superior Antimicrobial Properties.

Herein, we report an efficient and facile strategy for the preparation of imidazolium-based ionic liquid (IL) monomers ([CnVIm][Br], n = 2, 4, 6, 8, 10, and 12) and their corresponding polymeric ionic liquids (PILs) with potent antimicrobial activities against Gram-negative and Gram-positive bacteria and fungi. The electrospinning technique was utilized to tailor the polymers with the highest antimicrobial potency into porous membranes that can be easily implemented into diverse systems and extend their practical bactericidal application. The antimicrobial mechanism of obtained ILs, polymers, and nanomaterials is considered concerning the bearing chain length, polymerization process, and applied processing technique that provides a unique fibrous structure. The structure composition was selected due to the well-established inherent amphiphilicity that 1-alkylimidazolium ILs possess, coupled with proven antimicrobial, antiseptic, and antifungal behavior. The customizable nature of ILs and PILs complemented with electrospinning is exploited for the development of innovative antimicrobial performances born from the intrinsic polymer itself, offering solutions to the increasing challenge of bacterial resistance. This study opens up new prospects toward designer membranes providing a complete route in their designing and revolutionizing the approach of fabricating multi-functional systems with tunable physicochemical, surface properties, and interesting morphology.

Fluorescent carbon dots for discriminating cell types: a review.

Carbon dots (CDs) are quasi-spherical carbon nanoparticles with excellent photoluminescence, good biocompatibility, favorable photostability, and easily modifiable surfaces. CDs, serving as fluorescent probes, have emerged as an ideal tool for cellular differentiation owing to their outstanding luminescence performance and tunable surface properties. In this review, we summarize the recent research progress with CDs in the differentiation of cancer/normal cells, Gram-positive/Gram-negative bacteria, and live/dead cells, as well as the cellular differences used for differentiation. Additionally, we summarize the preparation methods, raw materials, and properties of the CDs used for cell discrimination. The differentiation mechanisms and the advantages or limitations of the differentiation methods are also introduced. Finally, we propose several research challenges in this field and future research directions that require extensive investigation. It is hoped that this review will help researchers in the design of new CDs as ideal fluorescent probes for realizing diverse cell differentiation applications.

Controlling CO2 hydrogenation selectivity by tuning surface properties of Cu/ZnxAlyOz catalysts

CO2 hydrogenation to methanol and/or dimethyl ether (DME) holds promise for mitigating greenhouse gas effects and addressing energy scarcity. However, the relationship between product selectivity and the collective nature of the catalysts remains ambiguous due to the intricate reaction network. Here, a series of Cu/ZnxAlyOz catalysts with different surface properties have been engineered by manipulating the Zn/Al ratio to achieve product controllability for CO2 hydrogenation. The results unveil the pivotal role of the H2 dissociation capability in governing CO2 conversion, which is regulated by the concentration of Cu0 species. Furthermore, the number of surface hydroxyl groups, the proportion of moderately strong basic sites and moderately strong acidic sites show desirable linear correlations with the selectivity of CO, CH3OH, and DME, respectively. Importantly, the ZnAl2O4-Al2O3 or Cu-ZnAl2O4-Al2O3 interface notably enhances moderately strong acidic sites, aiding methanol dehydration to DME. This work offers a comprehensive guide to the rational design of catalysts for oriented product synthesis from CO2 hydrogenation.

Reshapable bio-based thiol-ene vitrimers for nanoimprint lithography: Advanced covalent adaptability for tunable surface properties

Taking inspiration from natural surfaces known for their ability to adaptively remodel their shape, we fabricated stimuli-responsive microstructures by using UV-induced nanoimprint lithography. For this, a fully bio-based dynamic thiol-ene photopolymer was synthetized by the radical mediated addition of a trifunctional eugenol-based thiol (SH3E) crosslinker across an allylated linseed oil (ALELO). To catalyze the bond exchange reactions between the hydroxyl and ester groups within the network, a bio-based eugenol phosphate ester was introduced as a transesterification catalyst. Pure eugenol was further added as a reactive diluent to increase the number of hydroxyl groups and thus, accelerate the thermo-activated bond exchange reactions. Once cured by UV exposure, the dynamic photopolymer is thermally stable up to 250 °C and is able to relax 63% of the original stress within 62 min at 160 °C. Subsequently, films with micropillars, having an aspect ratio of 1:2.5 were prepared by using nanoimprint lithography. The macroscopic reflow capability of the dynamic network enabled a reorientation of the imprinted structures during a thermal reshaping step. The imprints were characterized by 2D/3D optical microscopy, μCT imaging and static water contact angle measurements. Based on the orientation of the micropillars, the water contact angle was varied between 118° and 95°, giving rise to a possible application in microfluidic devices.

Design and Construction of Furan‐Based and Thiophene‐Based Salicyladazine Bisbenzoxazine Resins with High Thermal Stability and Tunable Surface Properties

Design and Construction of Furan‐Based and Thiophene‐Based Salicyladazine Bisbenzoxazine Resins with High Thermal Stability and Tunable Surface Properties

Multi-dimensional MoS2/S-doped-CoP heterostructure nanoarrays as an efficient electrocatalyst for hydrogen evolution reaction

Developing efficient and economical electrocatalysts for hydrogen evolution reaction (HER) over a broad pH range has received considerable attention. In this work, we prepared multi-dimensional MoS2/S-CoP heterojunction catalysts by utilizing the carbon clothes supported ZIF-67 array as templates combining with Mo-ion exchange and high-temperature phosphorization-sulfidation strategy. The introduction of MoS2 into S-CoP results in electron redistribution and the formation of a distinctive space charge region at the two-phase contact interface, thereby effectively tuning surface properties, enhancing electron conductivity, and improving electrocatalytic activity. According to Density Functional Theory (DFT) calculations, the introduction of MoS2 is advantageous for the adsorption and desorption of H*, resulting in the value of ΔGH* very close to zero. Furthermore, the adsorbed water molecules are more readily activated, rendering the ΔGH2O-dis decrease, thus significantly promoting HER activity. These features contribute to robust HER electrocatalytic performance in a wide pH range and even in seawater, which is also beneficial for industrial applications. In particular, MoS2/S-CoP exhibits superior HER performance in alkaline seawater, requiring only 197 and 228 mV to reach the current densities of 100 and 200 mA cm-2, respectively. This study offers novel perspectives on high-performance heterostructures for HER electrocatalysts in alkaline seawater environments.

Biocompatibility of intraperitoneally implanted TEMPO-oxidized cellulose nanofiber hydrogels for antigen delivery in Atlantic salmon (Salmo salar L.) vaccines

Disease outbreaks are a major impediment to aquaculture production, and vaccines are integral for disease management. Vaccines can be expensive, vary in effectiveness, and come with adjuvant-induced adverse effects, causing fish welfare issues and negative economic impacts. Three-dimensional biopolymer hydrogels are an appealing new technology for vaccine delivery in aquaculture, with the potential for controlled release of multiple immunomodulators and antigens simultaneously, action as local depots, and tunable surface properties. This research examined the intraperitoneal implantation of a cross-linked TEMPO cellulose nanofiber (TOCNF) hydrogel formulated with a Vibrio anguillarum bacterin in Atlantic salmon with macroscopic and microscopic monitoring to 600-degree days post-implantation. Results demonstrated a modified passive integrated transponder tagging (PITT) device allowed for implantation of the hydrogel. However, the Atlantic salmon implanted with TOCNF hydrogels exhibited a significant foreign body response (FBR) compared to sham-injected negative controls. The FBR was characterized by gross and microscopic external and visceral proliferative lesions, granulomas, adhesions, and fibrosis surrounding the hydrogel using Speilberg scoring of the peritoneum and histopathology of the body wall and coelom. Acutely, gross monitoring displayed rapid coagulation of blood in response to the implantation wound with development of fibrinous adhesions surrounding the hydrogel by 72 h post-implantation consistent with early stage FBR. While these results were undesirable for aquaculture vaccines, this work informs on the innate immune response to an implanted biopolymer hydrogel in Atlantic salmon and directs future research using cellulose nanomaterial formulations in Atlantic salmon for a new generation of aquaculture vaccine technology.

Simultaneous adsorption of anionic and cationic species on UiO-66 and MIL-125 MOFs: Mechanisms & selectivity

Metal-organic frameworks (MOFs) have attractive properties, including regular pore structure, high specific surface area, tunable surface properties, and abundant active sites. Such properties have boosted their recent development in many fields, including water treatment. In this study, MOFs composed of tetravalent metals (Ti4+ and Zr4+) and dicarboxylate linker (terephthalate – BDC) were modified using surface functionalization and/or pore structure through defect engineering to enhance adsorption properties. It has been shown that the Ti-containing materials (MIL-125) show a greater affinity for cationic species, while the Zr-containing samples (UiO-66) have a higher affinity for anionic species. Surface charge and electrostatic interactions could account for such a difference in adsorption properties. Zeta potential measurements showed that MIL-125 has a more negative surface charge for both non-functionalized and amino-functionalized versions, which favors the interaction with cationic molecules. On the other hand, UiO-66 has a more positive surface, which facilitates interactions with anionic molecules. Within each MOF family, the non-functionalized structures emerged as the best-performing materials. Specifically, MIL-125(H) and UiO-66(H)_5eq, with 5eq denoting the amount of H2O added during synthesis, showed superior performance. Furthermore, by performing simultaneous adsorption experiments with anionic and cationic contaminants, it was found that the adsorption of the anionic dye acid orange 7 (AO7) onto the UiO-66 framework is primarily based on specific interactions between the sulfonic group (-SO3-) within the AO7 molecule and the inorganic core Zr6O4(OH)4 of UiO-66. The interaction between MIL-125 and the cationic dye methylene blue (MB) was found to be more delocalized, based on electrostatic and π-π interactions between the benzene domains. Finally, except for MIL-125(H), all the tested MOFs showed high stability in water and in the adsorption process. The higher stability of UiO-66 over MIL-125 materials can be attributed to steric effects and lower metal electronegativity. Compared to MIL-125(H), the higher stability of MIL-125(NH2) is probably related to the formation of intramolecular hydrogen bonds.