Degradable Magnetic Nanoplatform with Hydroxide Ions Triggered Photoacoustic, MR Imaging, and Photothermal Conversion for Precise Cancer Theranostic.

Theranostic agents based on inorganic nanomaterials are still suffered from the nonbiodegradable substances with long-term retention in body and unavoidable biological toxicity, as well as nonspecificity biodistribution with potential damage toward normal tissues. Here, we develop magnetic ions (FeIII, FeII, GdIII, MnII, and MnIII) coordinated nanoplatform (MICN) with framework structure and modify them with PEG (MICN-PEG). Notably, MICN-PEG demonstrates hydroxide ions (OH-) triggered the structure collapse along with responsive near-infrared photoacoustic (PA) signal, magnetic resonance imaging (MRI), and photothermal therapy (PTT) performances. Thereby, MICN-PEG is able to remain stable in tumors and exert excellent PA/MRI and PTT effects for multimodal imaging-guided cancer treatment. In contrast, MICN-PEG is gradually collapsed in normal tissues, resulting in the significant improvement of imaging accuracy and treatment specificity. MICN-PEG is gradually cleared after administration, minimizing concerns about the long-term toxicity.

Engineering of magnetic nanoparticles as magnetic particle imaging tracers.

Magnetic particle imaging (MPI) has recently emerged as a promising non-invasive imaging technique because of its signal linearly propotional to the tracer mass, ability to generate positive contrast, low tissue background, unlimited tissue penetration depth, and lack of ionizing radiation. The sensitivity and resolution of MPI are highly dependent on the properties of magnetic nanoparticles (MNPs), and extensive research efforts have been focused on the design and synthesis of tracers. This review examines parameters that dictate the performance of MNPs, including size, shape, composition, surface property, crystallinity, the surrounding environment, and aggregation state to provide guidance for engineering MPI tracers with better performance. Finally, we discuss applications of MPI imaging and its challenges and perspectives in clinical translation.

Tough and Alkaline-Resistant Mussel-Inspired Wet Adhesion with Surface Salt Displacement via Polydopamine/Amine Synergy.

The mussel-inspired catechol-based strategy has been well recognized as a promising alternative to design and exploit new generation adhesive materials applicable in many fields, ranging from biomedical adhesives to coatings of biomedical devices and engineering applications. However, in situ achievement of tough adhesion capability to substrate surfaces (e.g., minerals) is severely limited under the physiological environment or seawater condition (namely, relatively high salinity and mild alkalinity). In this work, a facile and versatile approach is proposed to in situ achieve robust wet adhesion in aqueous solutions of high salinity and mild alkalinity, via integrating primary amines into mussel-inspired polydopamine (PDA). By using a surface forces apparatus (SFA), the corresponding interaction behaviors have been systematically investigated. The strong wet adhesion was demonstrated and achieved via a synergetic effect of amine and PDA to the wet surfaces, including the surface salt displacement assisted by primary amine, strong adhesion to substrates facilitated by the catechol groups on PDA moieties, and enhanced cohesion through their cation-π interactions. Our results provide useful insights into the design and development of high-performance underwater adhesives and water-resistance materials.

Fast Modulation of Surface Amphiphobicity/Amphiphilicity via Bidirectional Substitution between Perfluorinated Surfactants and Polyanions throughout Pre-Assembled Polyelectrolyte Multilayers.

In the present work, we demonstrate a bidirectional substitution between perfluorooctanoate (PFO) surfactants and polyanions throughout the pre-assembled polyelectrolyte multilayers (PEMs) for a rapid modulation of surface wettability between amphiphobicity and amphiphilicity. Upon incubation of the PEMs made of alternating deposition of poly(diallyldimethylammonium) (PDDA) and poly(styrenesulfonate) (PSS) in PFO solutions at concentrations above or around its critical micelle concentration, the majority (ca. >75%) of PSS molecules throughout the PDDA/PSS PEMs can be substituted by PFO anions within 10 s, generating PFO-substituted PDDA/PSS (PFO-PDDA/PSS) films. This effective substitution of PSS polyanions in PDDA/PSS PEMs by PFO anions is suggested by the mechanism that the stability of PDDA/PFO complexes is higher than that of PDDA/PSS PEMs. Furthermore, PFO anions all the way through the PFO-PDDA/PSS films can be reversibly substituted by PSS polyanions, while the substitution efficiency depends on the ionic strength of the PSS solutions. The processes of bidirectional and reversible substitution between PFO anions and PSS polyanions throughout the PDDA/PSS films can be repeated at least 10 times accompanied with a negligible change in the film thickness and surface morphology. The surface wettability study reveals that the PFO-PDDA/PSS films are amphiphobic with water and oil contact angles (CAs) of 114 ± 2 and 64 ± 2°, respectively, while PSS-substituted PFO-(PDDA/PSS) films are amphiphilic with water and oil CAs of 6 ± 1 and 0°, respectively. These novelties of the films enable switchable surface wettability simply by dipping the PDDA/PSS film-coated objects into PFO solutions for 2 s or PSS solutions for 30 s.

Interaction Mechanisms of Zwitterions with Opposite Dipoles in Aqueous Solutions.

Zwitterionic groups have been widely used in antibiofouling surfaces to resist nonspecific adsorption of proteins and other biomolecules. The interactions among zwitterionic groups have attracted considerable attention in bioengineering, whereas the understanding of their nanomechanical mechanism still remains limited. In this work, the interaction mechanisms between two zwitterionic groups with opposite dipoles, i.e., phosphorylcholine (PC) and sulfobetaine (SB), have been investigated via direct force measurements using an atomic force microscope (AFM) and dynamic adsorption tests using the quartz crystal microbalance with dissipation monitoring technique (QCM-D) in aqueous solutions. The AFM force measurements show that the adhesive forces between contacted zwitterionic surfaces during separation in both symmetric and asymmetric configurations were close, mainly due to the enforced alignment of opposing dipole pairs via complementary orientations under confinement. The solution salinity and pH had almost negligible influence on the adhesion measured during surface separation. The QCM-D adsorption tests of PC-headed lipid on PC and SB surfaces showed some degree of adsorption of lipid molecules on the SB surface, whereas not on the PC surface. The different adsorption behaviors indicate that because the outermost negatively charged sulfonic group on the SB faced the aqueous solution, this configuration could facilitate it to form an attractive electrostatic interaction with the PC head of lipid molecules in the solution. This work shows that in addition to hydration and steric interactions, the zwitterionic dipole-induced interactions play an important role in the adhesion and antifouling behaviors of the zwitterionic molecules and surfaces. The improved fundamental understanding provides useful insights into the development of new functional materials and coatings with antifouling applications.

Probing the Interaction Forces of Phenol/Amine Deposition in Wet Adhesion: Impact of Phenol/Amine Mass Ratio and Surface Properties.

Mussel-inspired phenol/amine deposition in wet adhesion provides a cost-effective strategy to readily fabricate functional coatings for a wide range of applications. The adhesion of phenol/amine to different substrates and the cohesion between phenol/amine are believed to play critical roles during the deposition process. However, the understanding on the correlation between the deposition capability and interaction behavior involved in the coating formation still remains incomplete, which limits further developing phenol/amine-based functional materials and coatings. In this work, we correlated the interaction forces between two phenol/amine coatings and between phenol/amine coating and different substrate surfaces with the deposition capability of phenol/amine using surface forces apparatus and atomic force microscopy. The mass ratio of phenol and amine was found to significantly influence the deposition behavior through regulating the surface properties of phenol/amine aggregates' cohesion strength between phenol/amine coatings. Furthermore, the strong adhesion measured between phenol/amine coating and substrates with varying surface chemistry was demonstrated to be able to effectively initiate the surface-independent phenol/amine deposition as well as the continuous growth of phenol/amine coatings. This work provides useful insights into the fundamental understanding of the interactions and deposition mechanism during phenol/amine deposition process, with implications for developing advanced phenol/amine-based coating materials for a wider range of applications.

Biomimetic Lubrication and Surface Interactions of Dopamine-Assisted Zwitterionic Polyelectrolyte Coatings.

A bioinspired zwitterionic polyelectrolyte coating with excellent hydration ability has been regarded as a promising lubricating candidate for modifying artificial joint cartilage surface. In physiological fluids, the ubiquitous proteins play an important role in achieving outstanding boundary lubrication; however, a comprehensive understanding of the hydration lubrication between polyelectrolyte coatings and proteins still remains unclear. In this work, a facile fabrication of ultrasmooth polyelectrolyte coatings was developed via codeposition of synthesized poly(dopamine methacrylamide- co-2-methacryloyloxyethyl phosphorylcholine) (P(DMA- co-MPC)) and dopamine (DA) in a mild condition. Upon optimization of the feeding ratio of P(DMA- co-MPC) and DA, the as-fabricated PDA/P(DMA- co-MPC) coatings exhibit excellent lubricating properties when sliding with each other (friction coefficient µ = 0.036 ± 0.002, ∼2.8 MPa), as well as sliding with a model protein (bovine serum albumin (BSA)) layer (µ = 0.041 ± 0.005, ∼4.8 MPa) in phosphate-buffered saline (PBS, pH 7.4). Intriguingly, the lubrication in both systems shows Amontons-like behaviors: the friction is directly proportional to the applied load but independent of the shear velocity. Moreover, the PDA/P(DMA- co-MPC) coatings could resist the protein fouling (i.e., BSA) in PBS, which is crucial to prevent the surfaces from being contaminated when applied in biological media, thus maintaining their lubricating properties. Our results provide a versatile approach for facilely fabricating polyelectrolyte coatings with superior lubrication properties to both polyelectrolyte coatings and protein surfaces, with useful implications into the development of novel lubricating coatings for bioengineering applications (e.g., artificial joints).

Air-Writing Recognition Enabled by a Flexible Dual-Network Hydrogel-Based Sensor and Machine Learning.

Accurate air-writing recognition is pivotal for advancing state-of-the-art text recognizers, encryption tools, and biometric technologies. However, most existing air-writing recognition systems rely on image-based sensors to track hand and finger motion trajectories. Additionally, users' writing is often guided by delimiters and imaginary axes which restrict natural writing movements. Consequently, recognition accuracy falls short of optimal levels, hindering performance and usability for practical applications. Herein, we have developed an approach utilizing a one-dimensional convolutional neural network (1D-CNN) algorithm coupled with an ionic conductive flexible strain sensor based on a sodium chloride/sodium alginate/polyacrylamide (NaCl/SA/PAM) dual-network hydrogel for intelligent and accurate air-writing recognition. Taking advantage of the excellent characteristics of the hydrogel sensor, such as high stretchability, good tensile strength, high conductivity, strong adhesion, and high strain sensitivity, alongside the enhanced analytical ability of the 1D-CNN machine learning (ML) algorithm, we achieved a recognition accuracy of ∼96.3% for in-air handwritten characters of the English alphabets. Furthermore, comparative analysis against state-of-the-art methods, such as the widely used residual neural network (ResNet) algorithm, demonstrates the competitive performance of our integrated air-writing recognition system. The developed air-writing recognition system shows significant potential in advancing innovative systems for air-writing recognition and paving the way for exciting developments in human-machine interface (HMI) applications.

Recent advances in flexible hydrogel sensors: Enhancing data processing and machine learning for intelligent perception.

With the advent of flexible electronics and sensing technology, hydrogel-based flexible sensors have exhibited considerable potential across a diverse range of applications, including wearable electronics and soft robotics. Recently, advanced machine learning (ML) algorithms have been integrated into flexible hydrogel sensing technology to enhance their data processing capabilities and to achieve intelligent perception. However, there are no reviews specifically focusing on the data processing steps and analysis based on the raw sensing data obtained by flexible hydrogel sensors. Here we provide a comprehensive review of the latest advancements and breakthroughs in intelligent perception achieved through the fusion of ML algorithms with flexible hydrogel sensors, across various applications. Moreover, this review thoroughly examines the data processing techniques employed in flexible hydrogel sensors, offering valuable perspectives expected to drive future data-driven applications in this field.

Recent Development of MOF-Based Photothermal Agent for Tumor Ablation.

Metal-organic frameworks (MOFs) are 3D-architecture compounds of metal ions and organic molecules with sufficient and permanent porosity, showing great potential as a versatile platform to load various functional moieties to endow the hybrid materials with specific applications. Currently, a variety of photothermal nanometals have been embedded into organic ligands for integrating the unique photothermal effects with the merits of MOFs to improve their performances for cancer therapy. In this review, we have summarized a series of novel MOF-based photothermal materials for this unique therapeutic modality against tumors from three main aspects according to their chemical compositions and structures, i) metal-doped MOF, ii) organic-doped MOF, and iii) polymer-coated MOF. In addition, we have summarized the latest developments and characteristics of MOF-based photothermal agents, such as good biocompatibility, low toxicity, and responsive photothermal conversion without destroying the structure of hybrid photothermal agent. At last, we addressed the future perspectives of MOF-based photothermal agent in the field of phototherapy.

Turing patterns with high-resolution formed without chemical reaction in thin-film solution of organic semiconductors.

Regular patterns can form spontaneously in chemical reaction-diffusion systems under non-equilibrium conditions as proposed by Alan Turing. Here, we found that regular patterns can be generated in uphill-diffusion solution systems without a chemical reaction process through both in-situ and ex-situ observations. Organic semiconductor solution is confined between two parallel plates with controlled micron/submicron-meter distance to minimize convection of the liquid and avoid spinodal precipitation at equilibrium. The solvent evaporation concentrates the solution gradually into an oversaturated non-equilibrium condition, under which a phase-transition occurs and ordered concentration-waves are generated. By proper tuning of the experimental parameter, multiple regular patterns with micro/nano-meter scaled features (line, square-grid, zig-zag, and fence-like patterns etc.) were observed. We explain the observed phenomenon as Turing-pattern generation resulted from uphill-diffusion and solution oversaturation. The generated patterns in the solutions can be condensed onto substrates to form structured micro/nanomaterials. We have fabricated organic semiconductor devices with such patterned materials to demonstrate the potential applications. Our observation may serve as a milestone in the progress towards a fundamental understanding of pattern formation in nature, like in biosystem, and pave a new avenue in developing self-assembling techniques of micro/nano structured materials.

Improved Estimation of Bio-Oil Yield Based on Pyrolysis Conditions and Biomass Compositions Using GA- and PSO-ANFIS Models.

This paper incorporates the adaptive neurofuzzy inference system (ANFIS) technique to model the yield of bio-oil. The estimation of this parameter was performed according to pyrolysis conditions and biomass compositions of feedstock. For this purpose, this paper innovates two optimization methods including a genetic algorithm (GA) and particle swarm optimization (PSO). Primary data were gathered from previous studies and included 244 data of biodiesel oils. The findings showed a coefficient determination (R 2) of 0.937 and RMSE of 2.1053 for the GA-ANFIS model, and a coefficient determination (R 2) of 0.968 and RMSE of 1.4443 for PSO-ANFIS. This study indicates the capability of the PSO-ANFIS algorithm in the estimation of the bio-oil yield. According to the performed analysis, this model shows a higher ability than the previously presented models in predicting the target values and can be a suitable alternative to time-consuming and difficult experimental tests.

Graphene-based materials for adsorptive removal of pollutants from water and underlying interaction mechanism.

Graphene-based materials have received much attention as attractive candidates for the adsorptive removal of pollutants from water due to their large surface area and diverse active sites for adsorption. The design of graphene-based adsorbents for target pollutants is based on the underlying adsorption mechanisms. Understanding the adsorption performance of graphene-based materials and its correlation to the interaction mechanisms between the pollutants and adsorbents is crucial to the further development of graphene-based functional materials and their practical applications. This review summarizes recent advances on the development of graphene-based materials for the adsorption of heavy metal ions, dyes, and oils, and the co-adsorption of their mixture from water. The material design, performance, regeneration and reuse of adsorbents, and the associated adsorption mechanisms are discussed. Various techniques for mechanistic studies of the adsorption of heavy metal ions, dyes, and oils on graphene-based materials are highlighted. The remaining challenges and perspectives for future development and investigation of graphene-based materials as adsorbents are also presented.

In-situ probing of electrochemical dissolution and surface properties of chalcopyrite with implications for the dissolution kinetics and passivation mechanism.

HYPOTHESIS: The anodic dissolution of chalcopyrite (CuFeS2) encounters the problem of surface passivation, which significantly affects the copper extraction efficiency. So far, there is no agreement on the passivation mechanism and composition of passive layer, which could be studied by using in-situ scanning electrochemical microscopy (SECM). EXPERIMENTS: SECM was applied for the in-situ probing of chalcopyrite dissolution under mild oxidation potentials. The surface hydrophobicity and nanoscale distribution of hydrophobic domains were analyzed by static water contact angle measurement and atomic force microscope (AFM) force mapping, respectively. The surface conductivity was characterized by SECM feedback mode. FINDINGS: The concentrations of released species Fe2+, Cu2+ and soluble copper sulfide species (CuxS) generally increased with the potential of chalcopyrite. In the active region (low potentials), Fe2+ was preferentially released, and the metal-deficient sulfide layer that was rich in copper relative to iron started to form as the passive layer. While the release of Fe2+ and Cu2+ was impeded in the passive region, the detected CuxS became pronounced in this region and the following transpassive region, which suggested that the existence of CuxS was a result of passive layer dissolution. The nanoscale distribution of hydrophobic domains suggested that the formation of hydrophobic passive layer initiated in the active region and this layer almost completely covered the chalcopyrite surface at the beginning of passive region. The surface conductivity of chalcopyrite decreased with potential due to the formation of less conductive metal-deficient sulfide layer and possibly insulating elemental sulfur (in the transpassive region). This work provides a new approach for the in-situ probing of chalcopyrite dissolution and useful insights into its dissolution kinetics and passivation mechanisms, with implications for similar electrochemical processes of other mineral surfaces.

Probing the intermolecular interaction mechanisms between humic acid and different substrates with implications for its adsorption and removal in water treatment.

Humic substance is a ubiquitous class of natural organic matter (NOM) in soil and aquatic ecosystems, which severely affects the terrestrial and aquatic environments as well as water-based engineering systems by adsorption on solids (e.g., soil minerals, nanoparticles, membranes) via different interaction mechanisms. Herein, the chemical force microscopy (CFM) technique was employed to quantitatively probe the intermolecular forces of humic acid (HA, a representative humic substance) interacting with self-assembled monolayers (SAMs, i.e., OH-SAMs, CH3-SAMs, NH2-SAMs and COOH-SAMs) in various aqueous environments at the nanoscale. The interaction forces measured during approach could be well fitted by the extended Derjaguin-Landau-Verwey-Overbeek (DLVO) theory by incorporating the hydrophobic interaction. The average adhesion energy followed the trend as: NH2-SAMs (∼3.11 mJ/m2) > CH3-SAMs (∼2.03 mJ/m2) > OH-SAMs (∼1.38 mJ/m2) > COOH-SAMs (∼0.52 mJ/m2) in 100 mM NaCl at pH 5.8, indicating the significant role of electrostatic attraction in contributing to the HA adhesion, followed by hydrophobic interaction and hydrogen bonding. The adhesion energy was found to be dependent on NaCl concentration, Ca2+ addition and pH. For the interaction between NH2-SAMs and HA, their electrostatic attraction at pH 5.8 turned to repulsion under alkaline condition which led to the sudden drop of adhesion energy. Such results promised the adsorption and release of HA using the recyclable magnetic Fe3O4 nanoparticles coated with (3-aminopropyl)tiethoxysilane (APTES). This work provides quantitative information on the molecular interaction mechanism underlying the adsorption of HA on solids of varying surface chemistry at the nanoscale, with useful implications for developing effective chemical additives to remove HA in water treatment and many other engineering processes.

Rapid Dewatering and Consolidation of Concentrated Colloidal Suspensions: Mature Fine Tailings via Self-Healing Composite Hydrogel.

Billions of tonnes of thick waste streams with highly concentrated colloidal suspensions from different origins have accumulated worldwide, exampled as over 220 km2 mature fine tailings (MFT) from oil sands production in north Alberta. Current treatment technologies are limited by slow yet insufficient water release and sludge consolidation. Herein, a self-healing composite hydrogel system is designed to convert concentrated aqueous colloidal suspensions (e.g., MFT with colloidal solid content >30 wt %) into a dynamic double cross-linked network for rapid dewatering and consolidation. The resultant composite hydrogel demonstrates an excellent dewatering performance so that over 50% of water could be rapidly released within 30 min by vacuum filtration. Furthermore, the formed infinite cross-linked network with self-healing ability can effectively trap fine particles of all sizes and capture small flocs during mechanical mixing, thereby enabling a low solid content at the ppm level in the released water. This new strategy outperforms all the previously reported treatment methods; under mechanical compression, over 80% of water is removed from the MFT, thereby generating a stackable material with >70 wt % solids within an hour. These results demonstrate a highly effective approach and provide insight into the development of advanced materials to tackle the challenging environmental slurry issues.

Universal Mussel-Inspired Ultrastable Surface-Anchoring Strategy via Adaptive Synergy of Catechol and Cations.

An outstanding anchoring ligand with robust anchoring ability and universal applicability is highly desirable in materials science and surface engineering. This work reports a novel and universal mussel-inspired anchoring strategy based on a cationic amine-modified catechol ligand coupled with the 2-methacryloyloxyethyl phosphorylcholine moiety. The ligand shows substrate-independent anchoring capability, and the deposited film possesses excellent antifouling properties and superior ultrasonic stability as compared to the conventional catechol ligand. Single-molecule force spectroscopy based on atomic force microscopy reveals that the enhanced ultrastable anchoring is attributed to the synergistic binding effect of cationic amine and catechol. Our results provide new nanomechanical insights into the development of novel coating strategies underwater based on amine-incorporated catechol derivatives for a wide range of materials engineering, bioengineering, and environmental applications.

Duplicating Dynamic Strain-Stiffening Behavior and Nanomechanics of Biological Tissues in a Synthetic Self-Healing Flexible Network Hydrogel.

Biological tissues can accurately differentiate external mechanical stresses and actively select suitable strategies (e.g., reversible strain-stiffening, self-healing) to sustain or restore their integrity and related functionalities as required. Synthetic materials that can imitate the characteristics of biological tissues have a wide range of engineering and bioengineering applications. However, no success has been demonstrated to realize such strain-stiffening behavior in synthetic networks, particularly using flexible polymers, which has remained a great challenge. Here, we present one such synthetic hydrogel material prepared from two flexible polymers (polyethylene glycol and branched polyethylenimine) that exhibits both strain-stiffening and self-healing capabilities. The developed synthetic hydrogel network not only mimics the main features of biological mechanically responsive systems but also autonomously self-heals after becoming damaged, thereby recovering its full capacity to perform its normal physiological functions.