Polysaccharide-Based Adhesive Antibacterial and Self-Healing Hydrogel for Sealing Hemostasis.

Adhesive hydrogels have been considered as one of the most ideal materials for wound dressing. However, most existing adhesive hydrogels still have disadvantages such as low mechanical properties, poor biological activity (antibacterial and hemostatic ability), and low biocompatibility, which largely limit their application. Thus, it is highly desired to prepare a hydrogel-based wound dressing with good self-healing, ideal adhesive properties, rapid hemostasis, and excellent wound infection prevention activity. In this study, a simple method was presented to prepare a PAM-Lignin-CS-Laponite-SA hydrogel for wound dressing. The obtained hydrogel displayed excellent self-healing ability and repeatable adhesive performance, benefiting from the introduction of hydrogen bonding and electrostatic interactions inside the hydrogel network. In addition, the PAM-Lignin-CS-Laponite-SA hydrogel also exhibited low cell cytotoxicity, good antibacterial activity, and outstanding hemostatic properties. In conclusion, the PAM-Lignin-CS-Laponite-SA hydrogel demonstrated good tissue adhesion, excellent self-healing ability, effective bleeding control, and good antibacterial activity to prevent wound infection, which provides a new idea for developing a multifunctional hydrogel-based tissue adhesive hemostatic dressing.

Bioinspired Fabrication of an Insensitive Ammonium Perchlorate Core-Shell Composite with Polydopamine Coating.

In this research, an ammonium perchlorate/polydopamine (AP/PDA) core-shell composite was prepared in a non-aqueous solution to reduce the mechanical sensitivity of ammonium perchlorate (AP). The result showed that the AP/PDA core-shell composite could be successfully constructed in ethyl acetate solution with an AP recovery rate that reached 86%. The mechanical sensitivity of the obtained AP/PDA core-shell composite was significantly reduced with a PDA content of only 0.76%. The DSC and TG also indicated that the coating of PDA showed catalytic activity in the thermal decomposition of AP with a lower decomposition temperature and a decreased Ea value of AP. Thus, this study proposed a simple strategy for achieving a good balanced between harnessing the energy and ensuring the safety of ammonium perchlorate by significantly reducing its mechanical sensitivity by using a very low polydopamine coating layer content, and this shows great potential for the design and fabrication of insensitive energetic composites for use in propellants.

Fabrication of a High-Strength, Tough, Swelling-Resistant, Conductive Hydrogel via Ion Cross-Linking, Directional Freeze-Drying, and Rehydration.

Conductive hydrogels have been in huge demand in biomedical and wearable electronics. However, the application of traditional conductive hydrogels is largely limited due to their poor mechanical properties. Here, a conductive hydrogel with excellent mechanical strength and swelling resistance properties is prepared by ion cross-linking, directional freeze-drying, and rehydration. First, the acrylamide and acrylic acid are polymerized in the κ-carrageenan solution to form the hydrogel. Then, the obtained hydrogel is cross-linked with Fe3+ by soaking in ferric chloride solution. Finally, the ionic cross-linked hydrogels are reinforced by directional freeze-drying and rehydration. The resulting hydrogel has excellent tensile strength (5.67 MPa) and high toughness (7.63 MJ/m3). It is worth noting that the hydrogel also had excellent anti-swelling properties. Its mechanical strength and volume almost show no changes after soaking in deionized water for 40 days. In addition, the hydrogel exhibits good ionic conductivity (0.091 S/m), high sensitivity, and excellent stability when applied as a strain sensor. This work proposes a simple method to fabricate a conductive hydrogel with great mechanical properties and swelling resistance, which displays huge potential in varied fields.

Dynamic exchange of counterions of polystyrene sulfonate.

Adopting a cationic fluorescent molecule, rhodamine 6G, as the probe of the counterions of the model anionic polyelectrolyte (sodium polystyrene sulfonate, PSSNa), the diffusion of the counterion probes inside the solution of PSSNa was studied by fluorescence correlation spectroscopy. Two species of the counterion probes with different diffusion coefficient were discovered--the freely diffusing probes and the probes bound to the PSS(-) chains. The concentration fraction of these two species was found to change with the concentration and molecular weight of PSSNa. The results show that the counterion binding to the PSS(-) chain is enhanced with the increase of polymer concentration, attributed to the result of the lowered translational entropic penalty at higher polymer concentrations. The counterion binding is also enhanced with the increase of molecular weight, and the origin was attributed to the chain end effect to the counterion distribution. The results indicate the dynamic exchange process between the free counterions and the bound ones, which is further evidenced by the replacement of the bound probes by the elevated salt levels in the solution.

Responses of seedling growth and antioxidant activity to excess iron and copper in Triticum aestivum L.

The purpose of this study was to analyze phytotoxicity mechanism involved in root growth and to compare physiological changes in the leaves of wheat seedlings exposed to short term iron (Fe) and copper (Cu) stresses (0, 100, 300 and 500µM). All applied Fe or Cu concentrations reduced root and shoot lengths, but seed germination was inhibited by Cu only at 500µM. Analyses using fluorescent dye 2',7'-dichlorodihydrofluorescein diacetate indicated enhanced H(2)O(2) levels in seedling roots under Fe and Cu treatments. Cu stress at the same concentration induced a great reduction in cell viability and a strong damage on membrane lipid in the roots with respect to Fe treatment. Significant increases in the total chlorophyll (chl) content including chl a and chl b were observed in response to higher Fe concentrations, whereas the highest Cu concentration (500µM) led to significant decreases in the total chl content including chl a. Additionally, leaf peroxidase (POD) and ascorbate peroxidase (APX) were stimulated by Fe stress, but the highest Fe concentration exhibited inhibitory effect on leaf APX activity. In contrast, copper treatment resulted in an elevation in leaf catalase and POD activities. Therefore, H(2)O(2) content in the leaves associated with copper was significantly lower than that with iron at the same concentration.

High-Strength, Conductive, Antifouling, and Antibacterial Hydrogels for Wearable Strain Sensors.

Conductive hydrogels have shown great potential in the field of flexible strain sensors. However, their application is greatly limited due to the poor antifouling and low mechanical strength. Unfortunately, it is still a challenge to improve these two distinct properties simultaneously. Herein, a hydrogel with high strength, good conductivity, and excellent antifouling and antibacterial properties was prepared through the synergistic effect of physical and chemical cross-linking. First, acrylic acid (AA), acrylamide (AM), and 2-methacryloyloxyethyl phosphorylcholine (MPC) monomers were polymerized in the presence of chitosan chains to form the hydrogel. Then, the prepared hydrogel was immersed in a ferric ion solution to further strengthen the hydrogel through ion coordination. The obtained CS-P(AM-MPC-AA0.2)-Fe0.13+ hydrogel showed outstanding tensile strength (1.03 MPa), excellent stretchability (1075%), good toughness (7.03 MJ/m3), and fatigue resistance. The CS-P(AM-MPC-AA0.2)-Fe0.13+ hydrogel also demonstrated good ion conductivity (0.42 S/m) and excellent antifouling and antibacterial properties. In addition, the strain sensor constructed by the CS-P(AM-MPC-AA0.2)-Fe0.13+ hydrogel showed high sensitivity and good stability. This work presented a facile method to construct a zwitterionic hydrogel with high-strength, conductive, antifouling, and antibacterial properties, which suggested a promising gel platform for flexible wearable sensors.

Cell-penetrating peptide: A powerful delivery tool for DNA-free crop genome editing.

Genome editing system based on the CRISPR/Cas (clustered regularly interspaced short palindromic repeats) technology is a milestone for biology. However, public concerns regarding genetically modified organisms (GMOs) and recalcitrance in the crop of choice for regeneration have limited its application. Cell-penetrating peptides (CPPs) are derived from protein transduction domains (PTDs) that can take on various cargoes across the plant wall, and membrane of target cells. Selected CPPs show mild cytotoxicity and are a suitable delivery tool for DNA-free genome editing. Moreover, CPPs may also be applied for the transient delivery of morphogenic transcription factors, also known as developmental regulators (DRs), to overcome the bottleneck of the crop of choice regeneration. In this review, we introduce a brief history of cell-penetrating peptides and discuss the practice of CPP-mediated DNA-free transfection and the prospects of this potential delivery tool for improving crop genome editing.

Gold embedded chitosan nanoparticles with cell membrane mimetic polymer coating for pH-sensitive controlled drug release and cellular fluorescence imaging.

In this work, gold embedded chitosan nanoparticles (Au@CS NPs) were fabricated by a one-pot method. The benzaldehyde-terminated poly[(2-methacryloyloxy) ethyl phosphorylcholine] (PMPC) was applied to modification of the gold doped chitosan nanoparticles. The obtained Au@CS-PMPC NPs had the diameter of 135 nm with a narrow distribution. The size of the Au@CS-PMPC NPs, as well as the size of the embedded gold NPs, might be well-controlled by adjusting the feeding ratio between chitosan and HAuCl4. Furthermore, the Au@CS-PMPC NPs showed increased colloidal stability, high drug loading content, pH-responsive drug release, excellent biocompatibility and bright fluorescence emission. The results demonstrated that Au@CS-PMPC NPs showed a great potential for tumor therapy via the combination advantages of pH-sensitive controlled drug release and cellular fluorescence imaging.

Ultrastretchable, Tough, Antifreezing, and Conductive Cellulose Hydrogel for Wearable Strain Sensor.

Conductive hydrogels have shown great potential in the field of flexible strain sensors. However, their application is greatly limited due to the low conductivity and poor mechanical properties at subzero temperatures. Herein, an ultrastretchable, tough, antifreezing, and conductive cellulose hydrogel was fabricated by grafting acrylonitrile and acrylamide copolymers onto the cellulose chains in the presence of zinc chloride using ceric ammonium nitrate as the initiator. The resulting hydrogel exhibited ultrastretchability (1730%), excellent tensile strength (160 kPa), high elasticity (90%), good toughness (1074.7 kJ/m3), and fatigue resistance property due to the existence of dipole-dipole and multiple hydrogen-bonding interactions on the hydrogel network. In addition, the introduced zinc chloride endowed the cellulose-based hydrogel with remarkable electric conductivity (1.54 S/m) and excellent antifreezing performance (-33 °C). Finally, the hydrogel showed high sensitivity and stability to monitor human activities. In summary, this work presented a facile strategy to construct conductive hydrogel with excellent antifreezing and mechanical properties simultaneously, which showed great potential for wearable strain sensors.

Single chain contraction and re-expansion of polystyrene sulfonate: a study on its re-entrant condensation at single molecular level.

Single chain conformation of a polyelectrolyte (polystyrene sulfonate, PSS(-)Na(+)) during its re-entrant condensation was studied by fluorescence correlation spectroscopy (FCS) with single molecule sensitivity. The contraction and re-expansion of PSS(-)Na(+) chain were observed with the addition of counterions of different valencies. The formation of aggregation and precipitation of PSS(-)Na(+) and its redissolution were observed in accordance with the chain contraction and re-expansion process for the PSS(-)Na(+) chain upon the addition of trivalent La(3+) ion. Chain contraction and re-expansion of the PSS(-)Na(+) chain were also observed with the addition of monovalent Cs(+) and divalent Ca(2+) ions, under which condition, the re-entrant condensation was not observed. The results demonstrate that the high sensitivity of FCS can really study single PSS(-)Na(+) chain under extremely dilute situation.

A negative correlation between water content and protein adsorption on polymer brushes.

The correlation between the water content and protein adsorption on the surface of polymer brushes is investigated quantitatively. Using a number of model systems such as poly N-isopropylacrylamide (PNIPAM), polyethylene glycol (PEG), poly(2-(methacryloyloxy)ethyl phosphorylcholine) (PMPC), poly(2-hydroxyethyl methacrylate) (PHEMA), and poly(2,2,3,4,4,4-hexafluorobutyl)methacrylate (PHFBMA) polymer brushes with various grafting densities, the amount of water hydrodynamically coupled inside the brushes and its correlation with protein adsorption (BSA and Fg proteins as model systems) were determined by quartz crystal microbalance with dissipation (QCM-D) and surface plasma resonance (SPR). The results demonstrate the negative correlation between the water content and protein adsorption - the more water is coupled inside the brushes, the more protein adsorption is suppressed. In particular for PNIPAM brushes with a high enough grafting density and with a water content greater than 250 ng cm-2, the protein adsorption is negligible.

Cell membrane mimetic copolymer coated polydopamine nanoparticles for combined pH-sensitive drug release and near-infrared photothermal therapeutic.

In this study, we modified the well-known photothermal polydopamine nanoparticles with the poly[(2-methacryloyloxy)ethyl phosphorylcholine-b-(2-dimethylamino)ethyl methacrylate] (PMPC-b-PDMAEMA) diblock copolymers, containing both biocompatible cell membrane phosphorylcholine zwitterions segments and pH-responsive dimethylaminoethyl units on the polymer chains, to achieve both the photothermal property and pH-responsive release behavior. The results showed that the obtained nanoparticles had a narrow size distribution with the diameter about 220 nm. Besides, the modified polydopamine nanoparticles showed enhanced colloidal stability, pH-sensitive drug release behavior, excellent biocompatibility and remarkable near-infrared photothermal property. Thus, it is highly anticipated that PMPC-b-PDMAEMA modified polydopamine nanoparticles can serve as a powerful drug delivery system for combined pH-sensitive drug release and near-infrared photothermal therapeutic.

Biocompatible magnetite nanoparticles synthesized by one-pot reaction with a cell membrane mimetic copolymer.

In this paper, a series of random copolymers poly(methacrylic acid -co-2-methacryloyloxyethyl phosphorylcholine) P(MAA-co-MPC) were synthesized firstly via RAFT living polymerization. The P(MAA-co-MPC) copolymer side chains bear cell membrane phosphorylcholine zwitterions to endow biocompatibility and carboxylic groups to confer coordination with metal ions. Thus, the copolymer was adopted to modify Fe3O4 nanoparticle by a one-pot coprecipitation approach. The effects of the copolymer composition as well as the ratio between the copolymers and iron ions on the performances of the magnetite nanoparticles were researched. The diameters of the nanoparticles could be easily tuned by changing the initial copolymer amount. Moreover, a long-term colloidal stability of magnetite particles was obtained after P(MAA-co-MPC) modification. Biocompatibility of the P(MAA-co-MPC) copolymer coated magnetite nanoparticles was investigated by protein adsorption, in vitro cytotoxicity and cell uptake studies. It was found that the copolymer content of magnetite nanoparticles correlates with its biocompatibility. Excellent biocompatibility could be obtained when the content of the copolymer in the composite nanoparticles reached to 54%.

Probing the adjustments of macromolecules during their surface adsorption.

Thiol-terminated polymers poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC-SH), poly(N,N-isopropylacrylamide) (PNIPAM-SH), and poly(tert-butyl acrylate) (PtBA-SH) were synthesized, and the polymers were grafted on the gold surfaces of quartz crystal microbalance with dissipation (QCM-D) and surface plasmon resonance (SPR) sensor chips to form brushes. The grafting process of the polymer brushes as well as protein adsorption onto the brush layers was monitored by in situ QCM-D and SPR techniques. By examining the changes in frequency and dissipation factor as well as the value of ∂D/∂f from QCM-D measurements, different stages of the polymer grafting and protein adsorption are distinguished. The most interesting discovery is the conformation change of BSA protein adsorption from a weakly adsorbed native state to a strongly immobilized denatured state on the polymer brushes. The corresponding change in BSA adsorption from a reversible state to an irreversible state was confirmed by SPR measurements. The adsorption of protein on the polymer brushes' surface relies largely on interaction between the protein and the polymers, and the stronger hydrophilicity of the surfaces is proved to be more effective to suppress the protein adsorption. Analysis of the D-f plot of QCM-D measurements helps to characterize different binding strength of protein and the underlying polymer surface.

Diffusion of ionic fluorescent probes atop polyelectrolyte brushes.

The lateral diffusion of ionic fluorescent molecules atop polyelectrolyte brushes was adopted to probe the distribution of counterions of the polyelectrolyte brushes. With a combination of single molecule fluorescence techniques, fluorescence correlation spectroscopy and single molecule fluorescence imaging, the lateral diffusion of the ionic probes (sulforhodamine B, rhodamine 6G) at the top of the model polyelectrolyte brushes with the opposite charges, poly([2-(methylacryloyloxyl)ethyl] trimethylammonium chloride) (PMETAC) and polystyrene sulfonate (PSS), was studied with different external salt concentrations. A huge decrease of the diffusion rate of the probes was observed at salt concentrations 2-3 orders of magnitude lower than that for any detectable change of brushes thickness could be observed. The results reflect the early collapse of the top portion of the polyelectrolyte brushes and also the penetration of the probes into the brushes due to the increase of osmotic pressure by the salt level in the solution. The diffusion of the fluorescent counterion can serve as a very sensitive probe of the structure atop the polyelectrolyte brushes.