Physiological Microenvironment Dependent Self-Cross-Linking of Multifunctional Nanohybrid for Prolonged Antibacterial Therapy via Synergistic Chemodynamic-Photothermal-Biological Processes.

Herein, a multifunctional nanohybrid (PL@HPFTM nanoparticles) was fabricated to perform the integration of chemodynamic therapy, photothermal therapy, and biological therapy over the long term at a designed location for continuous antibacterial applications. The PL@HPFTM nanoparticles consisted of a polydopamine/hemoglobin/Fe2+ nanocomplex with comodification of tetrazole/alkene groups on the surface as well as coloading of antimicrobial peptides and luminol in the core. During therapy, the PL@HPFTM nanoparticles would selectively cross-link to surrounding bacteria via tetrazole/alkene cycloaddition under chemiluminescence produced by the reaction between luminol and overexpressed H2O2 at the infected area. The resulting PL@HPFTM network not only significantly damaged bacteria by Fe2+-catalyzed ROS production, effective photothermal conversion, and sustained release of antimicrobial peptides but dramatically enhanced the retention time of these therapeutic agents for prolonged antibacterial therapy. Both in vitro and in vivo results have shown that our PL@HPFTM nanoparticles have much higher bactericidal efficiency and remarkably longer periods of validity than free antibacterial nanoparticles.

Regulation of the Degradation Properties of Tyrosinase-Catalyzed Crosslinking Silk Membranes for Superficial Wound Repair.

Appropriate biodegradability to meet the demands of wound repair is critical for superficial wound repair membrane applications. Tyrosinase-catalyzed crosslinking SF (c-SF) membranes were constructed and regulated the degradation behavior in this study. The crosslinking degree of the c-SF membranes could be adjusted by reaction ratios of tyrosinase against SF (TYR/SF). Upon reaching a TYR/SF ratio of 20/6000, the degree of crosslinking increased to 88.17 ± 0.20%, without obvious changes in the crystal structure. The degradation behavior was regulated by the TYR/SF ratio and the degradation environment. All c-SF membranes remained stable after immersion without collagenase but showed an adjustable degradation behavior in the presence of collagenase. As the TYR/SF ratio increased, the residual weights increased from 23.31 ± 1.35% to 60.12 ± 0.82% after 7 days of degradation, occurring with low increased amounts of ß-sheet structure and free amino acids. This work provides a new c-SF membrane with controllable rapid degradability and favorable cytocompatibility, which can help to meet requirements for biodegradable superficial wound repair membranes.

Cohering Plasma into Adhesive Gel by Natural Biopolymer-Nanoparticle Hybrid Powder for Efficient Hemostasis and Wound Healing.

Hemostatic powder is commonly used in emergency bleeding control due to its suitability for irregularly shaped wounds, ease of use, and stable storage. However, traditional powder often has limited tissue adhesion and weak thrombus support, which makes it vulnerable to displacement by blood flow. Herein, we have developed a tricomponent hemostatic powder (MQS) composed of mesoporous bioactive glass nanoparticle (MBG), positively charged quaternized chitosan (QCS), and negatively charged catechol-modified alginate (SADA). Upon application to the wound, MBG with its high specific surface area quickly absorbs plasma, concentrating the blood coagulation factor. Simultaneously, the water-soluble QCS and SADA interact with each other and form a net, which can be further cross-linked by MBG. This network efficiently binds and entraps clustered blood coagulation factors, ultimately resulting in the formation of a durable and robust thrombus. Furthermore, the formed net adheres to the injury site, offering protection against thrombus disruption caused by the bloodstream. Benefiting from the synergistic effect of these three components, MQS demonstrates superior hemostatic performance compared to commercial hemostatic powders like Celox in both arterial injuries and noncompressible liver puncture wounds. Furthermore, MQS can effectively accelerate wound healing. In addition, MQS exhibits excellent antibacterial activity, cytocompatibility, and hemocompatibility. These advantages of MQS, including strong blood clotting, wet tissue adherence, antibacterial activity, wound healing ability, biosafety, ease of use, and stable storage, make it a promising hemostatic agent for emergency situations.

Hierarchical Porous Nanocellulose Aerogels Loaded with Metal-Organic Framework Particles for the Adsorption Application of Heterocyclic Aromatic Amines.

This work overcomes the long-standing challenge of cumbersome pretreatment methods in the detection of heterocyclic aromatic amines (HAAs). A UiO-66/nanocellulose composite aerogel (CMC-CNC-UiO-66) with layered pores and low density prepared by a self-cross-linking method is applied as a simple and rapid adsorbent for capturing 14 HAAs via strong electrostatic interactions, van der Waals force, and the steric effect. The adsorption capacity of CMC-CNC-UiO-66 to 14 HAAs reached 98.00-188.00 nmol/mg at equilibrium within 10 min. The adsorption and desorption abilities of CMC-CNC-UiO-66 were retained with values of 93.36 and 97.34% after two cycles. In the meantime, the kinetics study demonstrated the chemisorption between HAA molecules and CMC-CNC-UiO-66 due to the excellent agreement with the pseudo-second-order adsorption models. The fit with the Freundlich isotherm models suggested a multilayer adsorption mechanism between HAA molecules and materials with heterogeneous surfaces. Moreover, coupled with the ultrahigh-performance liquid chromatography-tandem mass spectrometry detection, the CMC-CNC-UiO-66 extraction process can be completed with a high average recovery ranging from 86.68 to 115.33%, indicating a potential application of CMC-CNC-UiO-66 in HAA adsorption for further quantitative analysis.

Organosilane-functionalized carbon quantum dots and their applications to "on-off-on" fluorometric determination of chromate and ascorbic acid, and in white light-emitting devices.

Organosilane-functionalized carbon quantum dots (Si-CQDs) were synthesized by reacting glucosamine and 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane in acetone. The surface morphology, crystal structure, functional groups, elemental composition, and optical properties of the Si-CQDs were characterized using TEM (HRTEM), XRD, FT-IR, XPS, UV-vis absorption and fluorescence spectroscopy. They show that N-containing groups including C=N and C-N, and Si-containing groups including Si-O-C and Si-O-Si have been formed on the surface of Si-CQDs. The element doping and surface functionalization of Si-CQDs endow their novel chemical, physical and optical properties. The Si-CQDs dispersed in acetone are almost monodisperse with an average particle diameter of 3.6 nm. The Si-CQDs dispersed in acetone display blue fluorescence (excitation/emission maxima of 380/460 nm). In contrast, the solid-state Si-CQDs exhibited yellow fluorescence (with excitation/emission maxima of 470/595 nm). The fluorescence emission spectra of acetone-suspended Si-CQDs are concentration-dependent, and the emission peak becomes red-shifted as the concentration is increased. The Si-CQDs are sensitive and selective fluorescent "on off on" nanoprobes for chromate [Cr(VI)] and ascorbic acid (AA). Fluorescence is quenched by Cr(VI) via an inner filter effect from the absorption of Si-CQDs excitation at 380 nm by Cr(VI). Upon addition of AA, fluorescence is restored because of reduction of Cr(VI) by AA. Under optimal conditions (excitation/emission wavelength of 380/460 nm), the response is linear in the 0.4-160 µM Cr(VI) concentration range, and the detection limit is 34 nM. The respective data for AA are 1-80 µM and 84.6 nM. The practical use of the nanoprobe for Cr(VI) determination in real river water samples is also demonstrated successfully. Their concentration-dependent fluorescence, good thermal stability and self-crosslinking behavior also make the Si-CQDs a candidate material for white light-emitting diodes that displays color conversion and can act as an encapsulation layer in a blue light-emitting diode (LED) chip. Graphical abstract One-pot solvothermal synthesis of organosilane-functionalized carbon quantum dots (Si-CQDs) with blue fluorescence in solution, yellow fluorescence in solid state and concentration-dependent fluorescence property, and their applications for chromate (Cr(VI)) and ascorbic acid dual determinations and white light-emitting device. Graphical Abstract contains poor quality and small text inside the artwork. Please do not re-use the file that we have rejected or attempt to increase its resolution and re-save. It is originally poor, therefore, increasing the resolution will not solve the quality problem. We suggest that you provide us the original format. We prefer replacement figures containing vector/editable objects rather than embedded images. Preferred file formats are eps, ai, tiff and pdf.We have changed the poor quality graphical abstract into the jpg and pdf.

Two-component cross-linkable gels for fabrication of solid oral dosage forms.

Current three-dimensional (3D) printing techniques involve the solidification of the injected materials by means of UV irradiation, evaporation of organic solvents, or harsh heating and cooling processes. These methods limit the printing of many sensitive bio-active molecules such as proteins. We describe a novel 3D printing technique based on two complementary liquid copolymers, PEG4-PCL-SC and PEG4-PCL-NH2, that are injected in a coordinated fashion and react with each other to form a pre-designed 3D pill. Printed pills swelled about 400% over 3 h, followed by moderate disintegration. Both prednisone and bovine serum albumin were incorporated into the printed pill, but while most of the prednisone was released depending on the ratio between the two complementary pre-polymers, only 40% of the bovine serum albumin was released from the pill. This unique 3D printing apparatus can be used to produce pills at home when the required medication does not handle current production techniques well and may have other possible biomedical applications. However, before this system can be considered for pharmaceutical applications, the low printing resolution, attributable to the slow gelation kinetics and the viscosity of the pre-polymers, should be addressed.

Tunable Hydrophilic or Amphiphilic Coatings: A "Reactive Layer Stack" Approach.

Thin films with tunable properties are very interesting for potential applications as functional coatings with, for example, anti-icing or improved easy-to-clean properties. A novel "reactive layer stack" approach was developed to create covalently grafted mono- and multilayers of poly(glycidyl methacrylate)/poly(tert-butyl acrylate) diblock copolymers. Because these copolymers contain poly(glycidyl methacrylate) blocks they behave as self-cross-linking materials after creation of acrylic acid functionalities by splitting off the tert-butyl units. The ellipsometrically determined coating thickness of the resulting hydrophilic multilayers depended linearly on the number of applied layers. Amphiphilic films with tunable wettability were prepared using triblock terpolymers with an additional poly(methyl methacrylate) block. The mechanism of the formation of the (multi)layers was investigated in detail by studying the acidolysis of the surface-linked tert-butyl acrylate blocks by infrared reflection absorbance spectroscopy, accompanied by surface analysis using atomic force microscopy and contact angle measurements. In the case of the amphiphilic and switchable terpolymer layers this reaction was very sensitive to the used acidic reagent.

Bioreducible nanocapsules prepared from the self-assembly of branched polymer in nanodroplet.

Though great attention has been paid in constructing well-defined nano-structures via the self-assembly of amphiphilic macromolecules, the self-assembly of non-amphiphilic macromolecules in nanodroplet has drawn less attention up to now. Recently, we prepared a temperature-responsive PEG-based branched polymer with disulfide bonds in its backbone via reversible addition-fragmentation chain transfer (RAFT) polymerization of 2-(2-methoxyethoxy) ethyl methacrylate, oligo(ethylene glycol) methacrylate, and N,N'-cystamine bisacrylamide. Subsequently, we loaded the branched polymer into nanodroplets, and have found that the self-assembly behaviors of this branched poly-mer in the nanodroplet are different from those in common solution. Bioreducible nanocapsules with tunable size can easily formed in nanodroplet even at high concentration.