Most photocrosslinkable hydrogels have inadequacy in either mechanical performance or biodegradability. This issue is addressed by adopting a novel hydrogel design by introducing two different chitosan chains (catecholmodified methacryloyl chitosan, CMC; methacryloyl chitosan, MC) via the simultaneous crosslinking of carbon-carbon double bonds and catechol-Fe 3+ chelation. This leads to an interpenetrating network of two chitosan chains with high crosslinking-network density, which enhances mechanical performance including high compressive modulus and high ductility. The chitosan polymers not only endow the hydrogels with good biodegradability and biocompatibility, they also offer intrinsic antibacterial capability. The quinone groups formed by Fe 3+ oxidation and protonated amino groups of chitosan polymer further enhance antibacterial property of the hydrogels. Serving as one of the two types of crosslinking mechanisms, the catechol-Fe 3+ chelation can covalently link with amino, thiol, and imidazole groups, which substantially enhance the hydrogel's adhesion to biological tissues. The hydrogel's adhesion to porcine skin shows a lap shear strength of 18.1 kPa, which is 6-time that of the clinically established Fibrin Glue's adhesion. The hydrogel also has a good hemostatic performance due to the superior tissue adhesion as demonstrated with a hemorrhaging liver model. Furthermore, the hydrogel can remarkably promote healing of bacteria-infected wound.
Sonoporation is the membrane disruption generated by ultrasound and has been exploited as a non-viral strategy for drug and gene delivery. Acoustic cavitation of microbubbles has been recognized to play an important role in sonoporation. However, due to the lack of adequate techniques for precise control of cavitation activities and real-time assessment of the resulting sub-micron process of sonoporation, limited knowledge has been available regarding the detail processes and correlation of cavitation with membrane disruption at the single cell level. In the current study, we developed a combined approach including optical, acoustic, and electrophysiological techniques to enable synchronized manipulation, imaging, and measurement of cavitation of single bubbles and the resulting cell membrane disruption in real-time. Using a self-focused femtosecond laser and high frequency (7.44 MHz) pulses, a single microbubble was generated and positioned at a desired distance from the membrane of a Xenopus oocyte. Cavitation of the bubble was achieved by applying a low frequency (1.5 MHz) ultrasound pulse (duration 13.3 or 40 µs) to induce bubble collapse. Disruption of the cell membrane was assessed by the increase in the transmembrane current (TMC) of the cell under voltage clamp. Simultaneous high-speed bright field imaging of cavitation and measurements of the TMC were obtained to correlate the ultrasound-generated bubble activities with the cell membrane poration. The change in membrane permeability was directly associated with the formation of a sub-micrometer pore from a local membrane rupture generated by bubble collapse or bubble compression depending on ultrasound amplitude and duration. The impact of the bubble collapse on membrane permeation decreased rapidly with increasing distance (D) between the bubble (diameter d) and the cell membrane. The effective range of cavitation impact on membrane poration was determined to be D/d = 0.75. The maximum mean radius of the pores was estimated from the measured TMC to be 0.106 ± 0.032 µm (n = 70) for acoustic pressure of 1.5 MPa (duration 13.3 µs), and increased to 0.171 ± 0.030 µm (n = 125) for acoustic pressure of 1.7 MPa and to 0.182 ± 0.052 µm (n=112) for a pulse duration of 40 µs (1.5 MPa). These results from controlled cell membrane permeation by cavitation of single bubbles revealed insights and key factors affecting sonoporation at the single cell level.
Biological production of silver nanoparticles by lixivium of sundried Cinnamomum camphora leaf in continuous-flow tubular microreactors was investigated. Properties of silver nanoparticles were examined by transmission electron microscopy (TEM), UV-vis spectroscopy, X-ray diffraction (XRD), and energy dispersive X-ray (EDX). The concentration of residual silver ions after reaction was measured by atomic absorption spectophotometry (AAS) spectroscopy. Fourier transform infrared (FTIR) spectra of C. camphora leaf lixivium were analyzed and temperature profiles along the tubes were calculated to explore formation mechanism of silver nanoparticles. Comparison of FTIR spectra of C. camphora leaf lixivium before and after reaction demonstrated the polyols in the lixivium may be mainly responsible for reduction of silver ions. According to the temperature profiles, at the inlet of the microreactors at 90 °C, the soar of the fluid temperature induced the burst of silver nuclei by homogeneous nucleation. Subsequently, the nuclei grew gradually along the reactors into silver nanoparticles from 5 to 40 nm. Polydisperse particles were formed by combination of heterogeneous nucleation and Ostwald ripening along the tubes at 60 °C.
We have successfully controlled the shape of gold nanocrystals through a simple and low‐cost hydrothermal method based on a modified polyol process. Well‐defined gold nanocrystals of icosahedral shape were synthesized in high yields by the rapid reduction of gold precursors with ethylene glycol (EG) in the presence of poly(vinyl pyrrolidone) (PVP) under hydrothermal conditions for 1 h. Truncated icosahedra (football‐shaped) have been prepared for the first time by prolonging the reaction time to 4 h. Both nanocrystal shapes were obtained quantitatively. Addition of citric acid inhibits the shape‐change process (from icosahedron to truncated icosahedron) by blocking oxidative etching, while addition of Fe(III) facilitates the shape‐change process by enhancing oxidative etching. We propose that growth of truncated icosahedra can be induced and maintained through interplay of the following processes: generation of multiple twinned seeds, shape‐ and size‐focusing by Ostwald ripening, and oxidative etching and preferential growth on the {100} face.
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