Liquid Metal Nanoparticles Physically Hybridized with Cellulose Nanocrystals Initiate and Toughen Hydrogels with Piezoionic Properties.

Liquid metal (LM) particles can serve as initiators, functional fillers, and cross-linkers for hydrogels. Herein, we show that cellulose nanocrystals (CNCs) stabilize LM particles in aqueous solutions, such as those used to produce hydrogels. The CNC-coated LM particles initiate free-radical polymerization to form poly(acrylic acid) (PAA) hydrogel with exceptional properties─stretchability ∼2000%, excellent toughness ∼1.8 MJ/m3, mechanical resilience, and efficient self-healing─relative to cross-linked PAA networks polymerized using conventional molecular initiators. FTIR spectroscopy, rheology, and mechanical measurements suggest that physical bonds between PAA and both Ga3+ and LM-CNC particles contribute to the excellent mechanical properties. The gels are used to sense a wide range of strains, such as those associated with human motion, via changes in resistance through the gel. The sensitivity at low strains enables monitoring subtle physiological signals, such as pulse. Without significantly compromising the toughness, soaking the gels in salt solution brings about high ionic conductivity (3.8 S/m), enabling them to detect touch via piezoionic principles; the anions in the gel have higher mobility than cations, resulting in significant charge separation (current ∼30 µA, ∼10 µA/cm2) through the gel in response to touch. These attractive properties are promising for wearable sensors, energy harvesters, and self-powered ionic touch panels.

Novel ZIF-8/CNC Nanohybrid with an Interconnected Structure: Toward a Sustainable Adsorbent for Efficient Removal of Cd(II) Ions.

Water pollution, especially by heavy metals, continues to pose significant challenges, emphasizing the urgency to develop sustainable processes to remove pollutants while developing sustainable materials derived from renewable sources. In the present research, a nanoscale adsorbent was prepared to remove cadmium (Cd(II)) ions from wastewater by hybridizing zeolitic imidazolate framework-8 (ZIF-8) with a cellulose nanocrystal (CNC). The prepared nanohybrid exhibited an interconnected structure in which the ZIF-8 particles were connected to each other via CNC nanoneedles. The hybridization of ZIF-8 with CNC caused a significant enhancement in the adsorption performance of the fabricated nanohybrid compared to pure ZIF-8, increasing its adsorption capacity by nearly 36%. The adsorption of ZIF/CNC followed the Langmuir isotherm model and pseudo-second-order kinetics models, remarking homogeneous adsorption onto the surface of ZIF/CNC, where chemisorption controlled the rate of adsorption. The thermodynamic study uncovered that the adsorption is spontaneous, endothermic, and entropy-governed as the randomness was increased at the solid-liquid interface. Additionally, the influence of operating variables, such as temperature, adsorbent dosage, pH, and ionic strength, was studied to mimic the adsorption capabilities of the adsorbent in real conditions. Accordingly, the optimum conditions were found to be at 45 °C and pH = 7 with a dosage of 0.4 g/L for the adsorbent. Moreover, the adsorption in a multimetal solution showed that the ZIF/CNC nanohybrid can remove various heavy metals, including Cd(II), Fe(III), Cu(II), and Pb(II) ions simultaneously. Finally, the regeneration study confirmed the great potential of the ZIF/CNC nanohybrid, which retained 94% of its initial adsorption capacity after 5 consecutive adsorption/desorption cycles.

Eco-Friendly Fumed Nanosilica@Nanodiamond Hybrid Nanoparticles with Dual Sustainable Self-Healing and Barrier Anticorrosive Performances in Epoxy Coating.

Fumed nanosilica@nanodiamond attached by APTES [(3-aminopropyl) triethoxysilane], named FSiO2@sND, was examined as an efficient anticorrosive nanohybrid for epoxy coating. Compared with fumed nanosilica (FSiO2), nanodiamond (ND) moderated the hydrophilic nature of FSiO2@sND and offered additional functional groups to the nanohybrid, i.e., carboxylic groups of ND and functional groups of APTES, while retaining the eco-friendly nature of FSiO2 in the hybrid nanoparticle. The hybrid nanoparticle showed pH-sensitive release behavior in which APTES is released considerably in an alkaline medium, acting as an efficient corrosion inhibitor. A thorough electrochemical impedance spectroscopy (EIS) study of scratched coatings in a 3.5% NaCl solution disclosed that FSiO2@sND nanoparticles (at 0.33 wt % loading) conferred significant active/self-healing anticorrosion properties for the epoxy coatings, thanks to the release of APTES and the presence of carboxylic groups of ND taking part in forming a stable protective film on the substrate. Accordingly, epoxy/FSiO2@sND coatings showed a corrosion improvement efficiency of 138% at an optimum immersion time of 5 h, which was higher than the 96% improvement for epoxy/FSiO2 coating. Epoxy/FSiO2@sND intact coating showed much higher low-frequency impedance, i.e., 7.23 Ω·cm2, compared with epoxy/FSiO2 coating, i.e., 5.44 Ω·cm2, and neat epoxy coating, i.e., 5.71 Ω·cm2, after 22 weeks of immersion in salty solution. This result along with a detailed analysis of EIS data for intact coatings suggested that FSiO2@sND brought about strong barrier anticorrosive performance for epoxy coating. Such behavior was attributed to improved dispersion of nanohybrid in the epoxy matrix, enhanced cross-link density of the epoxy matrix, and improved coating/substrate adhesion caused by APTES and the carboxylic groups of ND.

Metal-organic frameworks: A promising option for the diagnosis and treatment of Alzheimer's disease.

Beta-amyloid (Aß) peptide is one of the main characteristic biomarkers of Alzheimer's disease (AD). Previous clinical investigations have proposed that unusual concentrations of this biomarker in cerebrospinal fluid, blood, and brain tissue are closely associated with the AD progression. Therefore, the critical point of early diagnosis, prevention, and treatment of AD is to monitor the levels of Aß. In view of the potential of metal-organic frameworks (MOFs) for diagnosing and treating the AD, much attention has been focused in recent years. This review discusses the latest advances in the applications of MOFs for the early diagnosis of AD via fluorescence and electrochemiluminescence (ECL) detection of AD biomarkers, fluorescence detection of the main metal ions in the brain (Zn2+, Cu2+, Mn2+, Fe3+, and Al3+) in addition to magnetic resonance imaging (MRI) of the Aß plaques. The current challenges and future strategies for translating the in vitro applications of MOFs into in vivo diagnosis of the AD are discussed.

Adsorption Behavior of a Gd-Based Metal-Organic Framework toward the Quercetin Drug: Effect of the Activation Condition.

A carboxylate gadolinium-based metal-organic framework (Gd-MOF) is an exceptional candidate for magnetic resonance imaging agents, but its low drug adsorption capacity hinders this MOF from being used as a theragnostic agent. In this work, the Gd-MOF was synthesized by a simple solvothermal method. Then, different activation situations, including various solvents over different time periods, were applied to enhance the specific surface area of the synthesized MOF. Different characterization analyses such as X-ray diffraction and Brunauer-Emmett-Teller along with experimental quercetin adsorption tests were done to study the crystalline and physical properties of various activated MOFs. In the following, the MOF activated by ethanol for 3 days (3d-E) was chosen as the best activated MOF due to its crystallinity, highest specific surface area, and drug adsorption capacity. More explorations were done for the selected MOF, including the drug adsorption isotherm, thermodynamics, and pH effect of adsorption. The results show that the activation process substantially affects the crystallinity, morphology, specific surface area, and drug adsorption capacity of Gd-MOFs. An optimized activation condition is proposed in this work, which shows an impressive enhancement of the specific surface area of Gd-MOFs just by simple solvent exchange method employment.

Oxygen Scavenging Hybrid Nanostructure: Localization of Different Iron Nanoparticles on Montmorillonite Clays Host.

According to the great potential of zero-valent iron nanoparticle applications in the environmental, medical, chemical, packaging and many other industries, there is still a need to tailor their production methods. This study reports the production of a hybrid nanostructure based on iron nanoparticles (INPs) produced in/on montmorillonite (MMT) nanoclays as an oxygen scavenger and barrier additive in polymeric packaging materials of oxygen-sensitive products. INPs and MMT were demonstrated to have effective mutual interactions in which the MMT host played a chemophysical trapping role for iron particles, causing smaller particles around 10 nm with 6.2 g/m2 higher specific surface area by limiting particle growth and agglomeration. In return, the embedding of primary iron cations in/on clays and growth of these particles during the reduction reaction pushed the clay layers out and helped further clay intercalation-exfoliation. Effective study of solvent and primary cation (Fe2+/Fe3+) types showed different preferences in interacting with natural and alkylammonium-modified MMT, resulting in the different site selection. Fe2+ cations preferred to migrate to the interlayer space, whereas Fe3+ cations tended to bond to the clay surface. The obtained results in this study suggest tailoring the ultimate oxygen scavenging capacity, shelf life, and migration properties of a hybrid nanoparticle according to the application requirements.

Efficient removal of heavy metal ions from aqueous media by unmodified and modified nanodiamonds.

This article deals with the adsorption performances of the unmodified nanodiamond (ND) and thermally oxidized nanodiamond (Ox-ND) for the removal of different heavy metal ions such as Fe (III), Cu (II), Cr (VI), and Cd (II) from wastewater. The adsorption capacities of the ions onto adsorbents are higher and follow the order: Ox-ND-3 > Ox-ND-1.5 > ND, which is consistent with their surface areas, zeta potentials, and the presence of carboxyl groups, suggesting that electrostatic attractions between the positive metal ions and the negatively charged adsorbents are the predominant adsorption mechanisms. Adsorption capacities of these adsorbents were found to be 26.8, 31.3, and 45.7 mg/g for Fe (III), 25.2, 30.5, and 44.5 mg/g for Cu (II), 33.6, 44.1, and 55.9 mg/g for Cr (VI), and 40.9, 52.9, and 67.9 mg/g for Cd (II) over ND, Ox-ND-1.5, and Ox-ND-3, respectively. The impact of various operating parameters such as agitation time, initial metal ion concentration, temperature, pH solution, adsorbent dosage, and coexistence of the metal ions on the adsorption performance of Ox-ND-3 towards Cd (II) ions along with the batch adsorption experiments were performed. The equilibrium was reached in 120 min and adsorption data were fitted well with the pseudo-second-order kinetic as well as the Freundlich isotherm models. Adsorption process was spontaneous and exothermic, while the maximum removal efficiency of Cd (II) ions occurred at pH of 6.9 and at 4 g/L dosage. These findings demonstrated that thermally oxidized nanodiamond (Ox-ND) can be a versatile adsorbent to remove the Cd (II) ions from wastewater.

A review on the features, performance and potential applications of hydrogel-based wearable strain/pressure sensors.

Over the past few years, development of wearable devices has gained increasing momentum. Notably, the demand for stretchable strain sensors has significantly increased due to many potential and emerging applications such as human motion monitoring, prosthetics, robotic systems, and touch panels. Recently, hydrogels have been developed to overcome the drawbacks of the elastomer-based wearable strain sensors, caused by insufficient biocompatibility, brittle mechanical properties, complicated fabrication process, as the hydrogels can provide a combination of various exciting properties such as intrinsic electrical conductivity, suitable mechanical properties, and biocompatibility. There are numerous research works reported in the literature which consider various aspects as preparation approaches, design strategies, properties control, and applications of hydrogel-based strain sensors. This article aims to present a review on this exciting topic with a new insight on the hydrogel-based wearable strain sensors in terms of their features, strain sensory performance, and prospective applications. In this respect, we first briefly review recent advances related to designing the materials and the methods for promoting hydrogels' intrinsic features. Then, strain (both tensile and pressure) sensing performance of prepared hydrogels is critically studied, and alternative approaches for their high-performance sensing are proposed. Subsequently, this review provides several promising applications of hydrogel-based strain sensors, including bioapplications and human-machine interface devices. Finally, challenges and future outlooks of conductive and stretchable hydrogels employed in the wearable strain sensors are discussed.

Highly biocompatible multifunctional hybrid nanoparticles based on Fe3O4 decorated nanodiamond with superior superparamagnetic behaviors and photoluminescent properties.

The multifunctional nanostructures with superparamagnetic and luminescent properties undergo revolution in the field of bio-nanotechnology. In this article, we reported a facile and efficient one-step modified co-precipitation method to load superparamagnetic Fe3O4 nanoparticle on oxidized nanodiamond (Ox-ND). Subsequently, the as-prepared Ox-ND/Fe3O4 hybrid nanoparticle was surface functionalized with vinyltrimethoxysilane (VTMS) to enhance its compatibility with organic media. The structure, morphology, magnetic, and optical properties of the nanohybrid were systematically investigated. The results confirmed successful loading of crystalline Fe3O4 on the surface of Ox-ND. Ox-ND/Fe3O4 multifunctional hybrid nanoparticle presented strong superparamagnetism (with a saturation magnetization of 67 emu/g at room temperature) and photoluminescence (blue emission) with good chemical reactivity. PrestoBlue assay indicated great biocompatibility of silanized Ox-ND/Fe3O4 in MCF-7 cells even at high concentrations, e.g. 7.2 mg/mL. The hybrid nanoparticle synthesized in this study potentially opens doors for high contrast imaging and targeted delivery applications.

Ultrafast and simultaneous removal of anionic and cationic dyes by nanodiamond/UiO-66 hybrid nanocomposite.

In this research, UiO-66 and its composite nanoparticles with thermally oxidized nanodiamond (OND) were synthesized via a simple solvothermal method and utilized as solid adsorbent for the removal of anionic methyl red (MR) dye and cationic malachite green (MG) dye from contaminated water. The synthesized adsorbents were analyzed by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), thermogravimetric analysis (TGA), N2 adsorption-desorption, and zeta potential analyzer. The influences of various factors such as initial concentrations of the dyes, adsorption process time, solution pH, solution temperature and ionic strength on adsorption behavior of MR dye onto OND-UiO hybrid nanoparticle were investigated. The adsorption of MR onto OND-UiO hybrid nanoparticle could be well described by Langmuir isotherm model. Meanwhile, pseudo-second order kinetic model was found to be suitable for illustration of adsorption kinetics of MR onto OND-UiO. Thermodynamic investigation suggested that the adsorption process was spontaneous and endothermic, and controlled by an entropy change instead of enthalpy effect. The experimental adsorption results indicated that OND-UiO hybrid nanoparticle could simultaneously adsorb 59% of MR and 43% of MG from the mixture of both dyes in only 2 min showing synergistic effect compared with single UiO-66 and OND nanoparticles in terms of adsorption rate and removal capacity of anionic dyes. The appropriate removal efficiency, rapid adsorption kinetic, high water stability, and good reusability make OND-UiO hybrid nanoparticle attractive candidate for simultaneously removal of both anionic MR and cationic MG dyes from wastewater.

Polymer/nanodiamond composites - a comprehensive review from synthesis and fabrication to properties and applications.

Nanodiamond (ND) is an allotrope of carbon nanomaterials which exhibits many outstanding physical, mechanical, thermal, optical and biocompatibility characteristics. Meanwhile, ND particles possess unique spherical shape containing diamond-like structure at the core with graphitic carbon outer shell which intuitively contains many oxygen-containing functional groups at the outer surface. Such superior properties and unique structural morphology of NDs are essentially attractive to develop polymer composites with multifunctional properties. However, despite a long history from the discovery of NDs, which is dated back to the1960s, this nanoparticle has been less explored in the field of polymer (nano)composites compared with other carbon nanomaterials, e.g. carbon nanotube (CNT) and graphene. However, open literature indicates that research works in the field of polymer/ND (PND) composites have gained great momentum in the past half a decade. The present article provides a comprehensive review on recent achievements in ND based polymer composites. This review covers a very broad aspect from the synthesis, purification and functionalization of NDs to dispersion, preparation and fabrication of polymer/ND (PND) composites with a look in their recent applications for both structural and functional basis. Therefore, the review would be useful to pave the way for researchers to take some advancing steps in this respect.

Mixed-Matrix Composite Membranes Based on UiO-66-Derived MOFs for CO2 Separation.

We demonstrated a novel mixed-matrix composite membrane (MMCM) based on acrylated polyurethane (APU) and UiO-66 nanoparticles to separate CO2/N2 mixture. UiO-66 and functionalized UiO-66 including NH2-UiO-66 and glycidyl methacrylate (GMA)-UiO-66 were loaded into APU/2-hydroxyethyl methacrylate (APUH) matrix at variable concentrations between 3 and 30 wt %. APUH/GMA-UiO-66 MMCMs exhibited strong adhesion with a support layer of polyester/polysulfone, which was not deteriorated after immersion in water for a long time (20 days). Incorporation of UiO-66 and its functionalized forms increased simultaneously permeability and CO2/N2 selectivity, which were indeed superior in comparison with those of MMCMs reported previously. GMA-UiO-66-filled MMCM displayed a CO2 permeance of 14.5 Barrer and a CO2/N2 selectivity of 53 at a critical concentration (25 wt %). This attractive separation performance of APUH/UiO-66 offered an exciting platform for the development of composite membranes for sustainable CO2 separations.

Rapid and tunable selective adsorption of dyes using thermally oxidized nanodiamond.

In the present study, capability of nanodiamond (ND) for the adsorption of anionic (methyl orange, MO) and cationic (methylene blue, MB) dyes from aqueous solution was investigated. Employing fourier transform infrared (FTIR) spectroscopy, Boehm titration method and zeta potential, it was found that the simple thermal oxidation of ND at 425 °C, increased the content of carboxylic acid of ND and accordingly the zeta potential of ND decreased considerably. Therefore, a series of oxidized NDs (OND) at various oxidation times and as-received untreated ND (UND) was used as adsorbents of MO and MB. The adsorption experiments exhibited that UND had large adsorption capacity, very fast adsorption kinetics and excellent selectivity for MO over MB. These results suggested that the adsorption tendency of UND toward anionic MO dye followed not only by electrostatic interactions but also via the chemical interaction caused by the strong hydrogen bond between the sulfonate groups of MO and the oxygen containing groups on the surface of UND. In contrast, ONDs exhibited higher adsorption capacity for cationic MB whose tendency toward MB increased by increasing the thermal oxidation time due to the promotion of the negative charge on the surface of OND leading to the higher electrostatic attraction. The adsorption rate of MB on ONDs was also very high. Kinetics data was well fitted with the pseudo- second-order model for most of the adsorbents. The adsorption selectivity analysis revealed that ONDs displayed more adsorption capacity for MB compared with MO which was also attributed to high electrostatic interactions of cationic dye with negative charges of ONDs. Finally, the release behavior of NDs was also demonstrated after soaking in ethanol and acetone.

Enhanced mechanical properties of chitosan/nanodiamond composites by improving interphase using thermal oxidation of nanodiamond.

Polymer composite films based on chitosan (CS) and nanodimaond (ND) were prepared using solution casting method. ND with variable contents of carboxylic functional group was prepared using thermal oxidation at temperature of 420°C under air atmosphere at various durations of 1.5 and 4.5h. The interfacial interaction between NDs and CS and morphological evolution of CS in presence of NDs were investigated by Fourier transform infrared (FTIR), differential scanning calorimeter (DSC) and X-ray diffraction (XRD) analyses. A significant improvement in tensile strength (∼85%) and tensile modulus (∼125%) of CS was achieved by oxidized ND (OND) obtained at higher oxidation time of 4.5 at low concentrations (below 1.5wt%). Theoretical analyses based on micromechanical models showed that the ND with higher degree of carboxylic functionality provided thicker and stronger interphase region which was reflected in higher mechanical properties. The equilibrium water uptake of CS decreased by incorporating ND and increasing its degree of carboxyl functionality.

Molecularly imprinted polydopamine nano-layer on the pore surface of porous particles for protein capture in HPLC column.

Bio-inspired Human Serum Albumin (HSA) imprinted polydopamine nano-layer was produced through oxidative polymerization of dopamine on the pore surface of HSA modified porous silica particles. The coating thickness was controlled by the reaction time and thereby varied within 0-12 nm. The samples were characterized by elemental analysis, FT-IR, DSC, SEM, TEM, TGA, physisorption and thermoporometry. The characterization confirmed the success of evolution and deposition of polydopamine layer on the silica pore surface. Batch rebinding experiment showed that the molecularly imprinted polymer (MIP) with 8.7 nm coating thickness, in comparison with the thinner and thicker coatings, displays the highest uptake of the target protein. The chromatographic evaluation of the materials packed in HPLC columns showed that the HSA imprinted polydopamine offers good mechanical stability and retains practically all the target protein from an HSA solution or human plasma. Affinity of the imprinting column was examined by using Bovine Serum Albumin (BSA) and Immunoglobulin G (IgG) as competitive proteins. The results showed that the template, HSA, was the most adsorbed protein by the imprinted polydopamine layer.

On the viscosity of composite suspensions of aluminum and ammonium perchlorate particles dispersed in hydroxyl terminated polybutadiene--New empirical model.

The rheological properties of fuel suspensions with various solid loadings up to close their maximum packing fraction and suspending media having different viscosities are investigated using the rotational viscometer at relatively low shear rates in which suspensions behave as Newtonian fluids. Aluminum (Al) and ammonium perchlorate (AP) particles are major solid components of any solid fuel system which should be distributed uniformly inside a polymeric binder based on hydroxyl terminated polybutadiene (HTPB). The experimental data generated in this investigation indicates that the relative viscosity of the suspensions is independent of viscosity of polymer binder, but in addition to solid content, geometrical aspects of the solid particles affect strongly the relative viscosity of suspensions. Maximum packing fraction of filler is found to be suitable quantitative measure of filler characteristics such as size, size distribution, shape and structure. Consequently, it is revealed that the relative viscosity of fuel suspension is a unique function of reduced volume fraction (Phi). Based on analogy of viscosity enhancement of reactive resin with cure conversion and suspension with filler content, an empirical model with two adjustable parameters originated from resin gelation model is suggested. According to this model and experimental results obtained in this investigation, a generalized model is proposed to describe the relative viscosity as a function of solid content in which the adjustable parameters are found to be general constants. The generalized model which is expressed as mu(r) = (1-Phi)(0.3 Phi-2) is found to be quite accurate to predict the experimental data. Furthermore, the applicability and accuracy of the generalized model are evaluated using the viscosity data of some suspension systems reported in the literature.