Assembly of Metal-Phenolic Networks onto Microbubbles for One-Step Generation of Functional Microcapsules.

The one-step assembly of metal-phenolic networks (MPNs) onto particle templates can enable the facile, rapid, and robust construction of hollow microcapsules. However, the required template removal step may affect the refilling of functional species in the hollow interior space or the in situ encapsulation of guest molecules during the formation of the shells. Herein, a simple strategy for the one-step generation of functional MPNs microcapsules is proposed. This method uses bovine serum albumin microbubbles (BSA MBs) as soft templates and carriers, enabling the efficient pre-encapsulation of guest species by leveraging the coordination assembly of tannic acid (TA) and FeIII ions. The addition of TA and FeIII induces a change in the protein conformation of BSA MBs and produces semipermeable capsule shells, which allow gas to escape from the MBs without template removal. The MBs-templated strategy can produce highly biocompatible capsules with controllable structure and size, and it is applicable to produce other MPNs systems like BSA-TA-CuII and BSA-TA-NiII . Finally, those MBs-templated MPNs capsules can be further functionalized or modified for the loading of magnetic nanoparticles and the pre-encapsulation of model molecules through covalence or physical adsorption, exhibiting great promise in biomedical applications.

NIR Light-Fuse Drug-Free Photothermal Armor-Piercing Microcapsule for Femoral Vein Thrombosis Therapy.

Acute thrombosis and its complications are leading global causes of disability and death. Existing thrombolytic drugs, such as alteplase and urokinase (UK), carry a significant bleeding risk during clinical treatments. Thus, the development of a novel thrombolysis strategy is of utmost urgency. Based on the previous work, the hollow structure of microcapsules (MC) is fabricated. Subsequently, armor-piercing MC, known as Fucoidan/S-Nitrosoglutathione/Melanin@MC (FGM@MC) is obtained, using a layer-by-layer (LBL) self-assembly method. Utilizing near-infrared (NIR) light as a trigger, the FGM@MC demonstrated photothermal thrombolysis at the site of thrombus due to its stable and outstanding photothermal properties. Simultaneously, photothermal stimulation leads to the release of a significant amount of nitric oxide from the FGM@MC, resulting in cavitation effects for mechanical thrombolysis. In vivo experiments confirmed the stable release of nitric oxide under NIR light irradiation. Treatment of femoral vein thrombosis in rats revealed that the thrombolytic effectiveness of FGM@MC+NIR (53.71%) is comparable to that of UK (59.70%). Notably, FGM@MC does not interfere with the coagulation function of rats and exhibits a favorable safety profile. In conclusion, this study demonstrates that the drug-free armor-piercing microcapsule has significant potential in the treatment of thrombosis, offering a safe and effective alternative to traditional thrombolytic therapies.

Analysis of the trend of volatile compounds by HS-SPME-GC-MS and the main factors affecting the formation of rancid odor during the oxidation process of infant nutrition package.

In this study, headspace solid-phase micro-extraction (HS-SPME) coupled with GC-MS was used to analyze the trend of volatile compounds in fresh and oxidative infant nutrition package. Among the volatile compounds, aldehydes and ketones, alcohols, lipids, cycloalkenes, alkanes, alkenes, aromatic hydrocarbons, oxygenated compound were identified. A total of 65 volatile compounds were detected in the fresh nutrition package, whereas 9 new volatile compounds were detected during the accelerated oxidation process, which was oxidized at 45 °C for 4 weeks. The main components of the rancid flavor formed and the relative content of volatile substances gradually changed during the accelerated oxidation process. The volatile substances hexanal, nonanal, and 2-pentylfuran substantially increased. Linalool, α-terpineol, d-limonene, and 1-methoxy-nonane presented an evidently downward trend. The relative content of the newly formed compound 3-hydroxy-2-methylpyran-4-one during the oxidation process was always large, its relative content initially increased, then decreased, and finally increased again. The formation of rancid flavor of the nutrient package was speculated to have been formed by the interaction of hexanal, nonanal, 2-pentylfuran, and 3-hydroxy-2-methylpyran-4-one.

Biomechanical Motion-Activated Endogenous Wound Healing through LBL Self-Powered Nanocomposite Repairer with pH-Responsive Anti-Inflammatory Effect.

Wound care is still worthy of concern, and effective measures such as electrical stimulating therapy (EST) have sparked compellingly for wound repair. Especially, portable and point-of-care EST devices get extremely desired but these are often limited by inevitable external power sources, lack of biological functions, and mechanical properties conforming to skin tissue. Herein, a dress-on-person self-powered nanocomposite bioactive repairer of wound is designed. As such, the cooperation of the film prepared by layer-by-layer self-assembling 2-hydroxypropyltrimethyl ammonium chloride chitosan (HTCC), alginate (ALG), and poly-dopamine/Fe3+ nanoparticles (PFNs), with a self-powered nanogenerator (SN) driven by motion into a nanocomposite repairer (HAP/SN-NR) is conducted. The HAP/SN-NR not only guides cell behavior (proliferation and migration rate ≈61.7%, ≈52.3%), but also facilitates neovascularization (enhanced CD31 expression >4-fold) through its self-powered EST, and the endogenous wound closure with no inflammatory in rats owing to reactive oxygen species (ROS)-clearance of HAP/SN-NR in vitro/vivo through responsively releasing poly-dopamine nanoparticles at wound pH. Enormous efforts illustrate that the repairer is endowed with high self-adhesion to tissue, self-healing, and biodegradation, accelerating wound healing (50% closure ≈5 days). This strategy sheds light on novel multifunctional portable sensor-type dressings and propels the development of intelligent medical devices.

Static-Dynamic Fluorescence Patterns Based on Photodynamic Disulfide Reactions for Versatile Information Storage.

Dynamic fluorescence patterns with variable output in response to external stimulus can make the current information storage technologies more flexible and intelligent. Yet it remains a great challenge to create such dynamic patterns because of the complicated synthesis process, high cost, limited stability, and biocompatibility of the functional fluorophores. Herein, a facile approach is presented for creating dynamic fluorescence patterns using the photodynamic surface chemistry based on disulfide bonds. By this method, high-resolution (≈20 µm) multicolor dynamic fluorescence patterns that are low-cost and dynamically rewritable can be easily fabricated using classical fluorophores such as fluorescein, rhodamine, and dansyl acid. Owing to the spatio-temporal controllability of light, the fluorescence patterns can be partly or entirely erased/rewritten on demand, and complex gray-level fluorescence images with increased information capacity can be easily generated. The obtained fluorescence patterns exhibit little changes after storing in air and solvent environments for 100 days, demonstrating their high stability. In addition, static patterns can also be created on the same disulfide surface using irreversible disulfide-ene chemistry, to selectively control the dynamicity of the generated fluorescence patterns. The authors show the successful application of this strategy on information protection and transformation.

Anti-Oxidative and Antibacterial Self-Healing Edible Polyelectrolyte Multilayer Film in Fresh-Cut Fruits.

The consumption of fresh-cut fruits is limited because of the oxidation browning and pathogenic bacteria's growth on the fruit surface. Besides, crack of the fresh-keeping film may shorten the preservation time of fruit. In this work, polyelectrolyte multilayer (PEM) film was fabricated by layer-by-layer (LBL) electrostatic deposition method. The film was made by carboxy methylcellulose sodium (CMC) and chitosan (CS). The as-prepared PEM film had good anti-oxidative and antibacterial capability. It inhibited the growth of Gram-negative bacteria and the antibacterial rate was more than 95%. The stratified structure and linear increase of the absorbance in the film verified a linear increase of film thickness. The slight scratched film could self-heal rapidly after the stimulation of water whatever the layer number was. Moreover, the film could heal cracks whose width was far bigger than the thickness. The application of PEM film on fresh-cut apples showed that PEM film had good browning, weight loss and metabolic activity inhibition ability. These results showed that the PEM film is a good candidate as edible film in fresh-cut fruits applications.

Self-healing multilayer polyelectrolyte composite film with chitosan and poly(acrylic acid).

If self-healing materials can be prepared via simple technology and methods using nontoxic materials, this would be a great step forward in the creation of environmentally friendly self-healing materials. In this paper, the specific structural parameters of the various hydrogen bonds between chitosan (CS) and polyacrylic acid (PAA) were calculated. Then, multilayer polyelectrolyte films were fabricated with CS and PAA based on layer-by-layer (LbL) self-assembly technology at different pH values. The possible influence of pH on the (CS/PAA) × 30 multilayer polyelectrolyte film was investigated. The results show that the interactions between CS and PAA, swelling capacity, microstructure, wettability, and self-healing ability are all governed by the pH of the CS solution. When the pH value of the CS solution is 3.0, the prepared multilayer polyelectrolyte film (CS3.0/PAA2.8) × 30 has fine-tuned interactions, a network-like structure, good swelling ability, good hydrophilicity, and excellent self-healing ability. This promises to greatly widen the future applications of environmentally friendly materials and bio-materials.

All-in-One Self-Powered Microneedle Device for Accelerating Infected Diabetic Wound Repair.

Diabetic wound healing remains a significant clinical challenge due to the complex microenvironment and attenuated endogenous electric field. Herein, a novel all-in-one self-powered microneedle device (termed TZ@mMN-TENG) is developed by combining the multifunctional microneedle carried tannin@ZnO microparticles (TZ@mMN) with the self-powered triboelectric nanogenerator (TENG). In addition to the delivery of tannin and Zn2+, TZ@mMN also effectively conducts electrical stimulation (ES) to infected diabetic wounds. As a self-powered device, the TENG can convert biomechanical motion into exogenous ES to accelerate the infected diabetic wound healing. In vitro experiment demonstrated that TZ@mMN shows excellent conductive, high antioxidant ability, and effective antibacterial properties against both Staphylococcus aureus and Escherichia coli (>99% antibacterial rates). Besides, the TZ@mMN-TENG can effectively promote cell proliferation and migration. In the diabetic rat full-thickness skin wound model infected with Staphylococcus aureus, the TZ@mMN-TENG can eliminate bacteria, accelerate epidermal growth (regenerative epidermis: ≈303.3 ± 19.1 µm), enhance collagen deposition, inhibit inflammation (lower TNF-α and IL-6 expression), and promote angiogenesis (higher CD31 and VEGF expression) to accelerate infected wound repair. Overall, the TZ@mMN-TENG provides a promising strategy for clinical application in diabetic wound repair.

Transformable Magnetic Liquid-Metal Nanoplatform for Intracellular Drug Delivery and MR Imaging-Guided Microwave Thermochemotherapy.

Improved techniques for the administration of chemotherapeutic drugs are required to enhance tumor therapy efficacy and reduce the side effects of chemotherapy due to insufficient targeting and limited intratumoral drug release. Controlled drug delivery systems combined with thermotherapy are expected to play an important role in personalized tumor therapy. Herein, a novel microwave-responsive transformable magnetic liquid-metal (MLM) nanoplatform is designed for effective endosomal escape that facilitates intracellular drug delivery and enhanced anticancer therapy. The MLM nanoplatform exhibits a sensitive magnetic resonance imaging function for imaging-guided therapy and brilliant synergistic effects of chemotherapy with microwave thermal therapy to kill tumor cells. Once endocytosed by targeted tumor cells, the deep penetration of microwave energy can be absorbed by the MLM nanoplatform to convert heat and reactive oxygen species, which induces the shape transformation from nanospheres to large rods, resulting in the physical disruption of the endosomal membrane for intracellular drug release. Furthermore, the MLM nanoplatform synergistic therapy could activate immunomodulatory effects by M1 macrophage polarization and T cell infiltration, thus inhibiting tumor growth and lung metastasis. This work based on microwave-driven transformable magnetic liquid-metal nanoplatform provides novel ways to precisely control drug delivery and high-efficiency cancer therapy.

LBL Noninvasively Peelable Biointerfacial Adhesives for Cutaneo-Inspired pH/Tactility Artificial Receptors.

Besides barrier functions, skin possesses multiple sentiences to external stimuli (e.g., temperature, force, and humidity) for human-outside interaction. Thus, skincare should be taken very seriously, especially by patients with sensory disorders. However, currently available skin-mimicking devices are always limited by so much insufficient response functions and nontunable interface behaviors so as not to realize precise health monitoring and self-defense against injury. Herein, a bioinspired cutaneous receptor-perceptual system (CRPS) patch is presented, integrating hybrid pH indicators and triboelectric nanogenerators into biointerface film-adhesives that are fabricated through facile layer-by-layer (LBL) self-assembly of amide and Schiff-base linkages between alginate grafted with N-hydroxysuccinimide ester (AN), tannic acid (TA), and polyethylenimine (PEI). This CRPS patch is adhered robustly to the soft-curved skin surface without failure via "molecular suturing," and amino acid enables its benign peel-on-demand from tissue interfaces. Postdamage self-healing brings it without surgical reoperation, avoiding extra cost, pain, as well as infection risks. Significantly, CRPS patches as artificial chemo/mechanoreceptors can remotely visualize skin physiological status by pH-induced chromism using smartphones and prevent skin contact injury by tactility-driven self-powered electrical signals. Overall, the LBL-based strategy to create controllably biointerface-adhesive CRPS patches will usher in a new era of the mobihealth care platform supporting smart diagnosis and self-protection.

Biointerfacial giant capsules with high paclitaxel loading and magnetic targeting for breast tumor therapy.

High drug loading, targeted delivery, prolonged drug release, and low systemic toxicity are effective weapons for hydrophobic drug delivery systems to solve serious concerns in poor water-solubility and toxicity of paclitaxel (PTX). Herein, we reported that biointerfacial giant multilayer microcapsules (BGMs) with the feature of high-density drug loading and high-efficiency magnetic delivery were fabricated templated by PTX-liposome-microbubble complex using the layer-by-layer self-assembly (LbL) technique. The drug loading capacity of BGMs was improved by optimizing the structure of microbubbles and capsules to increase the PTX-contained layers, and the resultant BGMs exhibited high drug loading content (50.56 ± 0.09 %) and sustained drug release properties. The BGMs with an average diameter of 74.1 ± 12.1 µm and an average thickness of 275.5 ± 48.4 nm contained abundant magnetic nanoparticles (MNPs) in their cavity, which endowed these capsules with outstanding magnetic properties and fast magnetophoretic velocity in the blood (∼0.3 mm/s, ▽B = 1 T/mm). Moreover, both in vitro and in vivo studies demonstrated that the biocompatible PTX-loaded magnetic BGMs (Capsule@PLMPPL) caused notable death (71.3 ± 2.9 %) of 4 T1 breast cancer cells through PTX diffusion, capsules degradation, and subsequent endocytosis by cancer cells, and ultimately effectively inhibited tumor growth. In general, the developed BGM with good deformability and degradation was the first reported giant polyelectrolyte capsule to be used in tumor therapy, which could notably improve the therapeutic efficacy of PTX while reducing its side effects.

Layer-by-layer microneedle patch with antibacterial and antioxidant dual activities for accelerating bacterial-infected wound healing.

Bacterial-infected wound healing has always been a huge challenge to humans. Owing to the appearance of antibiotic resistance, there is an emergency need to design antibiotic-free wound dressings to treat such wounds. Herein, a novel antibiotic-free microneedle patch was designed, which its backing layer with antioxidant effect was coated with sodium carboxymethyl cellulose, 2-O-α-D-glucopyranosyl-L-ascorbic acid (GLAA), and 2-hydroxypropyltrimethyl ammonium chloride chitosan through electrostatic interaction based on layer-by-layer self-assembly technique, and its tips consisted of gelatin and tannic acid (TA) via hydrogen bonding interaction (CGH/GTA MN patch). The obtained CGH/GTA MN patch could effectively puncture the skin, and exhibit properties of pH-responsive TA and GLAA release. In vitro experiments showed that the obtained CGH/GTA MN patch has excellent antioxidative (scavenging DPPH efficacy is above 80 %, and scavenging ABTS efficiency reaches about 100 %), antibacterial (antibacterial rates of nearly 100 % for both Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli)), biodegradable, and biocompatible properties. In the S. aureus-infected rat wounds, the CGH/GTA MN patch could efficiently accelerate infected-wound healing by eliminating S. aureus infection, inhibiting inflammation, promoting angiogenesis, and accelerating epidermal regeneration. Thus, this study will provide a promising strategy to heal bacterial-infected wounds.

Layer-by-Layer Microneedle-Mediated rhEGF Transdermal Delivery for Enhanced Wound Epidermal Regeneration and Angiogenesis.

Appropriate treatments for acute traumas tend to avoid hemorrhages, vascular damage, and infections. However, in the homeostasis-imbalanced wound microenvironment, currently developed therapies could not precisely and controllably deliver biomacromolecular drugs, which are confronted with challenges due to large molecular weight, poor biomembrane permeability, low dosage, rapid degradation, and bioactivity loss. To conquer this, we construct a simple and effective layer-by-layer (LBL) self-assembly transdermal delivery patch, bearing microneedles (MN) coated with recombinant human epidermal growth factor (LBL MN-rhEGF) for a sustained release to wound bed driven by typical electrostatic force. Pyramidal LBL MN-rhEGF patches hold so enough mechanical strength to penetrate the stratum corneum, and generated microchannels allow rhEGF direct delivery in situ. The administrable delivery of biomacromolecular rhEGF through hierarchically coated MN arrays follows the diffusion mechanism of Fick's second law. Numerous efforts further have illustrated that finger-pressing LBL MN-rhEGF patches could not only promote cell proliferation of normal human dermal fibroblasts (NHDF) and human umbilical vein endothelial cells (HUVEC) in vitro but also take significant effects (regenerative epidermis: ∼144 µm; pro-angiogenesis: higher CD31 expression) in accelerating wound healing of mechanically injured rats, compared to the traditional dressing, which relies on passive diffusion. Our proof-of-concept features novel LBL biomacromolecular drug-delivery systems and self-administrated precision medicine modes at the point of care.

Biocompatible Self-Healing Coating Based on Schiff Base for Promoting Adhesion of Coral Cells.

Layer-by-layer self-assembly (LBL) technique is a very efficient and convenient method to modify the substrate surface. In this study, we report a self-repairing surface coating that can promote cell adhesion, especially for enhancing the adhesion of coral cells on the basal surface. The results confirmed that the modified chitosan-dialdehyde starch film based on Schiff base has good biocompatibility for common mammalian cells, such as normal human dermal fibroblasts (NHDFs) and relatively special cells (coral cells). The cytotoxicity test indicated that the optical density values of the experimental group films at 490 nm were higher than those of the control group in this study. In addition, the self-repairing coating modified by phase transition lysozyme can maintain its adhesion ability underwater for a period of time. Therefore, they have great application on substrates requiring underwater adhesion. Our results confirmed that the modified chitosan-dialdehyde starch self-healing films could provide a biocompatible coating material to promote the adhesion of normal human epidermal fibroblasts or coral cells.

Isothermal crystallization kinetics study on aqueous solution of poly(vinyl methyl ether) by FTIR and optical microscopy method.

A study on the isothermal crystallization kinetics of aqueous solution of poly (vinyl methyl ether) (PVME) was carried out by Fourier transform infrared (FTIR) and optical microscopy respectively. IR spectra of PVME solution were measured as a function of time under the isothermal crystallization conditions. With the process of crystallization, the phase of solution changes from transparent state to opaque one within around 1-2 min for 40 or 45 wt % PVME sample, the C-H symmetric stretching bands (nus(CH3)) shift to lower wave number 2823 cm(-1). The red shift of nus(CH3) absorption band was not observed in the transparent noncrystallization area. Using the temperature jump method, we determined the growth rate of ice crystal between the glass transition temperature Tg and the melting temperature Tm. At the different crystallization temperatures Tc, the different morphologies and dimension of ice crystal are also observed.

Hydrogen-bonding layer protecting polyelectrolyte capsules and its mechanical property study with atomic force microscope.

The hydrogen-bonding multilayered polyelectrolyte capsules with sizes around 6 microm were fabricated by layer-by-layer self-assembly method. The morphology of the obtained capsules was observed with Scanning Electron Microscope (SEM), Confocal Laser Scanning Microscope (CLSM) and Atomic Force Microscope (AFM), respectively. The elastic properties of the capsules were studied with AFM. The capsule was pressed by cantilever with different lengths, a glass bead glued at the end of the cantilever. The force curves were measured on the capsule in air. The Young's modulus of the capsule was obtained (E = 170 MPa for the loading). Results show that this model can predict the elastic deformation of the microcapsule. The accuracy of the elastic deformation of polymer capsule can be ensured using a cantilever of mediate stiffness. Our results show that the existence of the hydrogen-bonding layer makes the multilayered polyelectrolyte harder in comparison with the pure multilayered polyelectrolyte capsules.

A label-free aptamer-based cytosensor for specific cervical cancer HeLa cell recognition through a g-C3N4-AgI/ITO photoelectrode.

Facile and efficient detection of cancer cells in the early phases of the disease is one of the main challenges in cancer diagnostics. It has been found that photoactive materials and bio-recognition elements are two key factors in the development of promising photoelectrochemical (PEC) biosensors for cancer cell detection, which can play significant roles for realizing early cancer diagnostics with high sensitivity and selectivity. In this study, we designed a novel label-free PEC aptamer-based cytosensor for the specific detection of cancer cells such as HeLa cells by using water-dispersible g-C3N4-AgI nanocomposites as visible light-sensitive materials and anti-CEM/PTK7 aptamer as the bio-recognition element. It was observed that when a suitable amount of AgI nanoparticles was doped in two-dimensional graphite-like carbon nitride nano-sheets (g-C3N4 NSs), the visible light photocurrent response could be significantly improved. The PEC response of the as-prepared biosensor based on the g-C3N4-AgI/ITO photoelectrode was linearly proportional to the relevant cancer cells such as HeLa cells at concentrations ranging from 10 to 106 cells per mL with a limit of detection of 5 cells per mL. In addition, the g-C3N4-AgI/ITO photoelectrode and the fabricated cytosensor exhibited long-term stability, good reproducibility, excellent selectivity, and high sensitivity, demonstrating the successful conjugation of g-C3N4-AgI NSs with the aptamer and target cancer cells in the high performance PEC cytosensor.

A facile photoelectrochemical sensor for high sensitive ROS and AA detection based on graphitic carbon nitride nanosheets.

Photoactive material is one of the main challenges for fabrication of sensitive and selective photoelectrochemical (PEC) sensor. Herein, a facile PEC sensor is constructed using graphitic carbon nitride nanosheets (g-C3N4 NSs) coated on the surface of ITO electrode, where electron donor properties of potassium ferrocyanide and ascorbic acid is utilized for the tracing of hydrogen peroxide (H2O2), hypochlorite (ClO-), and ascorbic acid (AA). Our designed PEC sensor exhibits a good linear range to H2O2 concentrations from 12.5 to 875 µM in pH = 7.4 and 2.5-400 µM in pH = 10, while that for AA is in the range from 0.25 to 100 µM in pH = 7.4, and with the same pH for ClO- concentrations in the range from 0.5 to 19 × 10-3% (V/V) in a bleach sample. Owing to the good responses towards the traces of H2O2, AA, and ClO-, our designed system may be used as H2O2, ClO-, and AA sensor for outdoor applications with high specificity, long-time stability and good reproducibility.

Self-healing polyelectrolyte multilayered coating for anticorrosion on carbon paper.

Ideally, if the corrosion resistance coating on carbon paper (CP) can be endowed with the self-healing property, the service life and the reliability of the carbon paper will be greatly increased as the gas diffusion layer. In this paper, different cycles of s branched poly (ethyleneimine) (bPEI) and poly (acrylic acid) (PAA) were modified on the surface of the carbon paper via layer-by-layer (LbL) self-assembly technology. The prepared polyelectrolyte multilayered coatings can not only protect the carbon fiber from corrosion, but also take advantages of the surrounding water to quickly repair themselves after damaged. The effects of the assembly cycles on morphology, resistance, air permeability and the contact angle of carbon papers were investigated, then the differences of the carbon papers in electrolysis process were explored. The results reveal that all the prepared coatings can protect carbon papers from corrosion, while when the assembly cycles was 10, the coatings are most efficient.

Mechanical property of lipid-coated polyelectrolyte microcapsules.

The deformations of lipid coated polyelectrolyte capsules induced by osmotic pressure were determined in poly(styrene sulfonate, sodium salt) (PSS) solution by making use of the fact that PSS molecules with a molecular weight 70000 will not penetrate into the capsules. At a critical osmotic pressure the initial spherical capsules changed their shape and became an invagination. The measurements of single particle light scattering provided the wall thickness of the lipid-coated capsules with 25.6 nm while the thickness for pure polyelectrolyte capsules in solution is about 21.6 nm, indicating that the coating lipid layer has about 4 nm thickness. It demonstrates that DMPA forms a bilayer on the surface of polyelectrolyte capsules. With these data, that the elasticity coefficient of the lipid-coated capsules is about 426 Mpa can be obtained.