Janus Nanoparticles Research Articles

Multifunctional Bioactive Nanozyme Systems for Enhanced Diabetic Wound Healing.

The protracted transition from inflammation to proliferation in diabetic wound healing poses significant challenges, exacerbated by persistent inflammatory responses and inadequate vascularization. To address these issues, a novel nanozymatic therapeutic approach utilizing asymmetrically structured MnO₂-Au-mSiO₂@aFGF Janus nanoparticles is engineered. Nanozymes featuring a mSiO₂ head and MnO₂ extensions, into which acidic fibroblast growth factor (aFGF) is encapsulated, resulting in MnO₂-Au-mSiO₂@aFGF Janus nanoparticles (mSAM@aFGF), are synthesized. This nanozyme system effectively emulates enzymatic activities of catalase (CAT) and superoxide dismutase (SOD), catalyzing degradation of reactive oxygen species (ROS) and generating oxygen. In addition, controlled release of aFGF fosters tissue regeneration and vascularization. In vitro studies demonstrate that mSAM@aFGF significantly alleviates oxidative stress in cells, and enhances cell proliferation, migration, and angiogenesis. An injectable hydrogel based on photocrosslinked hyaluronic acid (HAMA), incorporating the nanozymatic ROS-scavenging and growth factor-releasing system, is developed. The HAMA-mSAM@aFGF hydrogel exhibits multifaceted benefits in a diabetic wound model, including injectability, wound adhesion, hemostasis, anti-inflammatory effects, macrophage polarization from M1 to M2 phenotype, and promotion of vascularization. These attributes underscore the potential of this system to facilitate transition from chronic inflammation to the proliferative phase of wound repair, offering a promising therapeutic strategy for diabetic wound management.

Visualizing mitochondrial ATP fluctuations in single cells during photodynamic therapy by In-Situ SERS three-dimensional imaging

An ultrasensitive strategy for in-situ visual monitoring of ATP in a single living tumor cell during mitochondria-targeted photodynamic therapy (PDT) process with high spatiotemporal resolution was proposed using surface-enhanced Raman scattering (SERS) 3D imaging technique. The nanostructures consisting of Au-Ag2S Janus nanoparticles functionalized with both Au nanoparticles linked by a DNA chain and a mitochondrial-targeting peptide (JMDA NPs) were deliberately employed to target mitochondria. The JMDA NPs exhibit excellent SERS activity and remarkable antitumor activity. The quantization of ATP relies on the intensity of the SERS probes bonded to the DNA, which shows a strong correlation with the generated hot spot between the Janus and the Au. Consequently, spatiotemporally controlled monitoring of ATP in the mitochondria of single living cells during the PDT process was achieved. Additionally, the JMDA NPs demonstrated remarkable capability for mitochondria-targeted PDT, providing significant antitumor effects and superior therapeutic safety both in vitro and in vivo. Our work presents an effective JMDA NPs-based SERS imaging strategy for in-situ and real-time 3D visualization of intracellular ATP in living tumor cells during the mitochondria-targeted PDT process, which enables significant information on the time point of PDT treatment and is beneficial to precious PDT applications in tumor therapy.

Cryoprotective effects of deicing micro/nanomaterials with different sizes and shapes on cells

Extensive studies have been conducted on deicing nanomaterials to improve the cryoprotective effects on cells, tissues, and organs. The nanomaterials with different composition, sizes, and shapes can inhibit the formation and growth of ice crystals, thereby reducing the damage to the cryopreserved samples. In this study, the carbon composite particles (CCPs) with different sizes and shapes were prepared by the hydrothermal method. The results demonstrated that the cryoprotective effect of CCPs enhanced with the decrease in particle size. Compared with spherical CCPs, Janus nanoparticles and WSP nanoflower with special shapes demonstrated improved protective effects on cryopreserved cells. In addition, the combination of deicing micro/nanomaterials at appropriate concentrations with commercial cryoprotectants exerted improved cryoprotective effects on cells. The prepared deicing micro/nanomaterials can improve cell cryopreservation, demonstrating great application potential in biomedical research and cryopreservation.

Metadynamics Simulations of Three-Dimensional Nanocrystals Self-Assembled from Triblock Janus Nanoparticles: Implications for Light Filtering

Metadynamics Simulations of Three-Dimensional Nanocrystals Self-Assembled from Triblock Janus Nanoparticles: Implications for Light Filtering

“Ball-rod” shaped multifunctional magnetic Janus nanoparticles for efficient drug delivery

Magnetic Janus nanoparticles (MJNPs) have attracted extensive attention in the biomedical field due to their asymmetrical composition and independent functional partitioning. In this paper, “ball-rod” shaped drug delivery systems (DDSs) with CoFe2O4 balls and mesoporous silica (mSiO2) rods, which were coated with CDs via imine bonds, were prepared. The DDSs were named CoFe2O4&mSiO2/CDs MJNPs and DOX was used as a model drug to form DOX-CoFe2O4&mSiO2. Capping agent CDs blocked the pore entrance and endowed the carriers with negatively charged surface. CoFe2O4&mSiO2/CDs showed fine magnetic properties and microwave (MW) thermal transition properties contributed to the ball portion of CoFe2O4. The drug release behavior of DOX-CoFe2O4&mSiO2/CDs showed pH/MW dual-responsiveness. The broken of imine bonds resulted in the detachment of CDs and the NPs became positively charged. The new NPs provided new insights for designing multi-functional DDSs.

Lipase grafted on magnetic and CO2 dual-responsive Janus nanoparticles for interfacial catalyzed transesterification

Enzyme-loaded Pickering emulsions are a promising system for biphasic catalytic reactions. The monodisperse core-shell Janus nanoparticles (JNPs) P[xMAOAAO-yDEAEA]@RF@Fe3O4-CRL with magnetic and CO2 dual-responsiveness were synthesized by the wax/water emulsion. The catalysts can perfectly steady the oil/methanol Pickering emulsion and produce biodiesel by static transesterification of soybean oil. There is a synergistic effect between the interfacial activation of CRL realized by amphiphilic Janus supporters and the stability of the Pickering emulsions. Under optimal reaction conditions, the Pickering interfacial biocatalyst exhibits excellent enzymatic activity, reaching a biodiesel yield of 87.33 %. Furthermore, magnetic absorption and introduction of CO2 separate the catalyst P[2MAOAAO-DEAEA]@RF@Fe3O4-CRL from the system, and the biodiesel yield is 86.3 % after 6 cycles.

Green Nanoengineered Fabrics: Waste-Derived Polyphenol-Zinc@ Silica Core-Shell Reactive Janus Nanoparticles for Functional Fabrics.

Fabricating Janus nanoparticle-functionalized fabrics with UV protection, strength enhancement, self-cleaning properties, and wash durability, with a biocompatible nature, is crucial in modern functional fabrics engineering. Particularly, tailoring multifunctional nanoparticles capable of exhibiting several distinct properties, utilizing low-cost raw materials, and adhering to green chemistry principles is pivotal. A fabrication strategy for developing multifunctional reactive Janus nanoparticles, utilizing waste-derived natural polyphenol (quercetin-3-glucuronide, myricetin-3-galactoside, gossypin, phlorizin, kaempferol, myricetin-3-arabinoside)-integrated zinc-silica core-shell Janus nanoparticles with UV protection, strength enhancement, and self-cleaning properties, is proposed. Polyphenols were utilized as sustainable precursors for synthesizing zinc-polyphenol complexes, which were then encapsulated within a silica shell to form a core-shell structure. Furthermore, Janus particles were created by introducing a bifunctional layer with half amine/carboxylic acid and half methyl terminals, imparting reactive hydrophilic and hydrophobic properties. Janus-coated textiles and leather exhibited significant attenuation of harmful UV radiation, with water contact angle measurements confirming improved water repellency. The coexistence of natural phenols and bifunctional groups within a material bolstered textile strength, fostering superior adhesion and markedly enhancing wash durability. This eco-friendly approach, utilizing waste-derived materials, presents a promising solution for sustainable textile engineering with enhanced performance in UV protection and water resistance, thereby contributing to the advancement of green nanotechnology in textile applications.

Tunable Dual Self-Healing Composite Coatings with Self-Assembled Structures Regulated by Janus Nanoparticles.

The durability of concrete structures can be enhanced in a convenient and permanent manner through the surface protection of cementitious materials with composite polymer coatings. However, polymer coatings are susceptible to various mechanical and physical deterioration in complex and variable environments. In this paper, the theory of polymer microstructure regulation was employed to improve the sustainability of the protective performance of composite coatings. The self-assembled core-shell structure regulated by amphiphilic Janus nanoparticles is employed to modify the tunable polystyrene acrylate-polysiloxane self-healing coatings. The results demonstrate that the adhesion strength of the prepared self-assembled coating reached 3.7 MPa, which is sufficient to resist the damage to the microstructure of cementitious materials caused by physical erosion, seepage, and ionic corrosion. The self-healing coating, regulated by Janus particles, exhibited a residual creep of only 57.03% and a maximum loss angle tangent of 0.381. Furthermore, the material exhibited a superior shape memory function due to the presence of strong hydrogen bonding. The regulated self-healing coating repaired the polymer structural damage under mechanical and thermal deformation by bridging and filling effects. The coating demonstrated a tensile strength recovery of up to 71.23% in a wetted state, accompanied by a rapid restoration of its electrochemical properties and corrosion resistance. Furthermore, the self-healing emulsion penetrates the substrate defects and forms numerous polymer crystalline particles that effectively fill the microcracks.

Facile Synthesis of Novel Magnetic Janus Graphene Oxide for Efficient and Recyclable Demulsification of Crude Oil-in-Water Emulsion.

Nanoparticles have been widely applied to treat emulsion-containing wastewater in the form of chemical demulsifiers, such as SiO2, Fe3O4, and graphene oxide (GO). Owing to their asymmetric structures and selective adsorption, Janus nanoparticles show greater application potential in many fields. In the present work, the novel magnetic Janus graphene oxide (MJGO) nanoparticle was successfully prepared by grafting magnetic Fe3O4 to the surface of the JGO, and its demulsifying ability to treat a crude oil-in-water emulsion was evaluated. The MJGO structure and its magnetic intensity were verified by Fourier-transform infrared spectra (FTIR), transmission electron microscopy (TEM), X-ray diffraction (XRD), and magnetization saturation (MS) tests. Compared with GO and JGO, MJGO displayed the superior efficiency (>96%) to demulsify the crude oil-in-water emulsion, which can be attributed to the reduced electrostatic repulsion between MJGO and the emulsion droplets. Furthermore, the effects of pH and temperature on the demulsification performance of MJGO were also studied. Lastly, the recyclability of MJGO largely reduced the cost of demulsifiers in separating crude oil and water. The current research presents an efficient and recyclable demulsifier, which provides a new perspective for the structural design of nanomaterials and their application in the field of demulsification.

Interface Allocation Precisely Customized Janus Upconversion Nanomotor for Atherosclerosis Amelioration

AbstractSpatial and temporal precisely control of direction and speed is crucial for nanomotors to enable complex operations and applications in microsurgery, drug delivery, isolation of biological targets, and so on. Judicious material design involving Janus nanoparticles has been popular over the past decades, however, precise and customizable modulation of Janus structure with a specific asymmetric ratio for motion control is still challenging. In this study, a universal “interface allocation” strategy is developed for efficient and controllable preparation of Janus mesoporous silica‐coated upconversion nanoparticles (Janus UCNP@mSiO2) with precisely tuned asymmetric ratio to achieve near‐infrared (NIR)‐controlled active mobility for relieving vessel plaque. Mesoporous silica with a thickness of 50 nm is precisely coated onto the nanoparticles’ surface with an optimal coverage ratio of 50% to encapsulate gas propellant. Upon exposure to upconverted blue light, the nanomotors release nitric oxide, facilitating their motion and pathologically improving atherosclerosis through endothelium‐dependent vasodilation. Experimental and theoretical simulation results demonstrate the advantages of NIR‐controlled Janus upconversion nanomotors in atherosclerosis treatment, including enhanced nanoparticle‐transmittance rate (34.83% to 85.57%) and excellent in vivo therapeutic efficacy.

Nitric Oxide‐Actuated Titanium Dioxide Janus Nanoparticles for Enhanced Multimodal Disruption of Infectious Biofilms

AbstractSonodynamic therapy (SDT) is promising for combating deep‐seated infectious diseases by generating substantial reactive oxygen species (ROS) through the profound tissue penetration capabilities of ultrasound. However, the compact protective structures of bacterial biofilms present a formidable challenge, impeding ROS efficacy. Given that ROS have a limited diffusion range and current sonosensitizers struggle to infiltrate biofilms, complete eradication of pathogenic bacteria often remains unachieved. In this study, mesoporous titanium dioxide (TiO2) nanoparticles are engineered asymmetrically coated with a thin layer of Ag and loaded with L‐arginine (LA) to construct ultrasound‐propelled nanomotors. These Ag‐TiO2‐LA Janus nanoparticles demonstrate robust self‐propulsion upon ultrasonic activation, allowing for deeper penetration into biofilm matrices and enhancing localized biofilm disruption through improved SDT outcomes. Additionally, the incorporation of Ag not only broadens TiO2’s absorption spectrum but also confers photothermal capabilities upon NIR laser excitation at 808 nm. The Ag‐TiO2‐LA nanomotor amalgamates TiO2’s sonodynamic potential with Ag's photothermal properties, forging a versatile antimicrobial agent capable of efficient biofilm penetration and a synergistic antibacterial effect when subjected to dual NIR and ultrasound stimuli. This innovative, singularly‐structured nanoparticle stands out as an effective combatant against bacterial biofilms and accelerates the healing process of infected wounds, showcasing potential for multifaceted clinical applications.

Construction of Pickering emulsion and its application in enzymatic synthesis of phytosteryl oleate

In this study, Janus nanoparticles were prepared and used to construct Pickering emulsion as an emulsifier in presence of lipase. The results showed that Janus nanoparticles could be used to stable water phase in emulsion and the average particle size of emulsion was 60 μm. Phytosterol ester was successfully synthesized in Pickering emulsion catalytic system by using oleic acid as acyl accepter, and the phytosterol conversion reached 91.65 ± 2.07% under the following conditions: emulsifier amount of 1.0 wt%, oil-water ratio of 6:1, phytosterol concentration of 110 mmol/L, lipase dosage of 20 g/L, reaction temperature of 45 °C. Compared with biphasic catalytic system, Pickering emulsion catalytic system could enhance the catalytic efficiency and shorten the reaction time due to large interface area and short molecule diffusion distance. At the end of reaction, Janus nanoparticles could be recovered by simple centrifugation, the relative activity of lipase remained 72.89 ± 1.83% after repeated use for 6 times. Overall, this paper provides a novel and high efficiency interfacial biocatalysis technique for the synthesis of phytosteryl oleate.

Molecular insights into the self-assembly of Janus nanoparticles obtained from coarse-grained molecular dynamics simulations

Abstract Grafting polymeric chains onto surfaces of nanoparticles generates amphiphilic Janus nanoparticles (JNPs) that can self-assemble into a variety of well-ordered and/or functional nanostructures. The self-assembly structures of JNPs can be designed by the manipulation of grafting schemes, but only if the self-assembly rule can be well understood. By using coarse-grained molecular dynamics (CGMD) simulations, we investigated the self-assembly process and morphology of triblock JNPs with varying chain lengths, chain ratios, and grafting topology. The HTH type of JNPs which possesses a middle hydrophobic block and two terminal hydrophilic blocks tends to aggregate into film structures via a shoulder-by-shoulder packing mode. The THT (Hydrophobic-Hydrophilic-Hydrophobic) type of JNPs is likely to form string structures via a head-to-head packing mode. The self-assembled film structures and string structures can be further regulated by the hydrophilic-hydrophobic chain ratio and length, forming rigid flakes, vesicles, porous structures, and so forth. Based on the molecular insights revealed by the example models, some plausible rules and strategies for tuning the self-assembly of nanoparticles are discussed in this paper. They are expected to facilitate future studies on the application of chemical self-assembly in materials science.

Oppositely Charged Interfacial Janus Nanoparticles Induce the Formation of Highly Ferroelectric Poling-Free PVDF Films for Piezoelectric Energy Generation

Oppositely Charged Interfacial Janus Nanoparticles Induce the Formation of Highly Ferroelectric Poling-Free PVDF Films for Piezoelectric Energy Generation

Self-propelled enzyme-controlled IR-mesoporous silica Janus nanomotor for smart delivery

Here, we report the preparation of a novel Janus nanoparticle with opposite Ir and mesoporous silica nanoparticles through a partial surface masking with toposelective modification method. This nanomaterial was employed to construct an enzyme-powered nanomachine with self-propulsion properties for on-command delivery. The cargo-loaded nanoparticle was provided with a pH-sensitive gate and unit control at the mesoporous face by first attaching boronic acid residues and further immobilization of glucose oxidase through reversible boronic acid esters with the carbohydrate residues of the glycoenzyme. Addition of glucose leads to the enzymatic production of H2O2 and gluconic acid, being the first compound catalytically decomposed at the Ir nanoparticle face producing O2 and causing the nanomachine propulsion. Gluconic acid leads to a pH reduction at the nanomachine microenvironment causing the disruption of the gating mechanism with the subsequent cargo release. This work demonstrates that enzyme-mediated self-propulsion improved release efficiency being this nanomotor successfully employed for the smart release of Doxorubicin in HeLa cancer cells.

Magnetic targeting and pH-microwave dual responsive Janus mesoporous silica nanoparticles for drug encapsulation and delivery

In this paper, a new Janus-structured nano drug delivery carrier Fe3O4@TiO2&mSiO2 was designed and synthesized, which consisted of a spherical head and a closely connected rod. The head was a nanocomposite of core/shell structure with magnetic spinel ferric tetraoxide core and anatase titanium dioxide shell (Fe3O4@TiO2), and the rod was ordered mesoporous silica (mSiO2). The nanocarriers showed excellent magnetic targeting capability (saturation magnetization, 25.18 emu g−1). The core/shell heads endowed the carriers with fine microwave responsiveness. The pore volume of mesoporous nanocarriers was 0.101 cm3 g−1, and the specific surface area was 489.0 m2 g−1. Anticancer drug doxorubicin could be loaded in the mesoporous of the carriers to form Fe3O4@TiO2&mSiO2-DOX. The drug loading capacity was 10.4%. Fe3O4@TiO2&mSiO2-DOX exhibited acid-sensitive and microwave-sensitive release properties along with good bio-compatibility. Fe3O4@TiO2&mSiO2 Janus nanoparticles are expected to be ideal drug carriers.

Amphiphilic Janus Nanoparticles with Enhanced Sealing Properties as Follower Sealants

Amphiphilic Janus Nanoparticles with Enhanced Sealing Properties as Follower Sealants

Beta cyclodextrin conjugated Au[sbnd]Fe3O4 Janus nanoparticles with enhanced chemo-photothermal therapy performance

The strategic integration of multi-functionalities within a singular nanoplatform has received growing attention for enhancing treatment efficacy, particularly in chemo-photothermal therapy. This study introduces a comprehensive concept of Janus nanoparticles (JNPs) composed of Au and Fe3O4 nanostructures intricately bonded with β-cyclodextrins (β-CD) to encapsulate 5-Fluorouracil (5-FU) and Ibuprofen (IBU). This strategic structure is engineered to exploit the synergistic effects of chemo-photothermal therapy, underscored by their exceptional biocompatibility and photothermal conversion efficiency (∼32.88 %). Furthermore, these β-CD-conjugated JNPs enhance photodynamic therapy by generating singlet oxygen (1O2) species, offering a multi-modality approach to cancer eradication. Computer simulation results were in good agreement with in vitro and in vivo assays. Through these studies, we were able to prove the improved tumor ablation ability of the drug-loaded β-CD-conjugated JNPs, without inducing adverse effects in tumor-bearing nude mice. The findings underscore a formidable tumor ablation potency of β-CD-conjugated Au-Fe3O4 JNPs, heralding a new era in achieving nuanced, highly effective, and side-effect-free cancer treatment modalities. Statement of significanceThe emergence of multifunctional nanoparticles marks a pivotal stride in cancer therapy research. This investigation unveils Janus nanoparticles (JNPs) amalgamating gold (Au), iron oxide (Fe3O4), and β-cyclodextrins (β-CD), encapsulating 5-Fluorouracil (5-FU) and Ibuprofen (IBU) for synergistic chemo-photothermal therapy. Demonstrating both biocompatibility and potent photothermal properties (∼32.88 %), these JNPs present a promising avenue for cancer treatment. Noteworthy is their heightened photodynamic efficiency and remarkable tumor ablation capabilities observed in vitro and in vivo, devoid of adverse effects. Furthermore, computational simulations validate their interactions with cancer cells, bolstering their utility as an emerging therapeutic modality. This endeavor pioneers a secure and efficacious strategy for cancer therapy, underscoring the significance of β-CD-conjugated Au-Fe3O4 JNPs as innovative nanoplatforms with profound implications for the advancement of cancer therapy.

Highly Ordered Nanoassemblies of Janus Spherocylindrical Nanoparticles Adhering to Lipid Vesicles.

In recent years, there has been a heightened interest in the self-assembly of nanoparticles (NPs) that is mediated by their adsorption onto lipid membranes. The interplay between the adhesive energy of NPs on a lipid membrane and the membrane's curvature energy causes it to wrap around the NPs. This results in an interesting membrane curvature-mediated interaction, which can lead to the self-assembly of NPs on lipid membranes. Recent studies have demonstrated that Janus spherical NPs, which adhere to lipid vesicles, can self-assemble into well-ordered nanoclusters with various geometries, including a few Platonic solids. The present study explores the additional effect of geometric anisotropy on the self-assembly of Janus NPs on lipid vesicles. Specifically, the current study utilized extensive molecular dynamics simulations to investigate the arrangement of Janus spherocylindrical NPs on lipid vesicles. We found that the additional geometric anisotropy significantly expands the range of NPs' self-assemblies on lipid vesicles. The specific geometries of the resulting nanoclusters depend on several factors, including the number of Janus spherocylindrical NPs adhering to the vesicle and their aspect ratio. The lipid membrane-mediated self-assembly of NPs, demonstrated by this work, provides an alternative cost-effective route for fabricating highly engineered nanoclusters in three dimensions. Such structures, with the current wide range of material choices, have great potential for advanced applications, including biosensing, bioimaging, drug delivery, nanomechanics, and nanophotonics.

Effect of Janus nanoparticles on foam snap off in porous media

Abstract Nanoparticles can be adsorbed at the gas-liquid interface to improve the stability of foam. However, homogeneous nanoparticles exhibit low surface activity, and their migration to the gas-liquid interface requires significant energy input. This leads to harsh foaming conditions and severely limits the application of homogeneous nanoparticles in foam stability. A microfluidic visualisation model for the study of Janus nanoparticle complex systems was used to investigate the formation behaviour of trapped bubbles in a single connected pore-throat model. The foam generated in the pore showed reduced quantities, sizes, improved quality, and enhanced stability compared to both surfactant systems and hydrophilic nanoparticle complex systems.