Antioxidant and Immunomodulatory Polymer Vesicles for Effective Diabetic Wound Treatment through ROS Scavenging and Immune Modulating.

Chronic diabetic wound patients usually show high glucose levels and systemic immune disorder, resulting in high reactive oxygen species (ROS) levels and immune cell dysfunction, prolonged inflammation, and delayed wound healing. Herein, we prepared an antioxidant and immunomodulatory polymer vesicle for diabetic wound treatment. This vesicle is self-assembled from poly(ε-caprolactone)36-block-poly[lysine4-stat-(lysine-mannose)22-stat-tyrosine)16] ([PCL36-b-P[Lys4-stat-(Lys-Man)22-stat-Tyr16]). Polytyrosine is an antioxidant polypeptide that can scavenge ROS. d-Mannose was introduced to afford immunomodulatory functions by promoting macrophage transformation and Treg cell activation through inhibitory cytokines. The mice treated with polymer vesicles showed 23.7% higher Treg cell levels and a 91.3% higher M2/M1 ratio than those treated with PBS. Animal tests confirmed this vesicle accelerated healing and achieved complete healing of S. aureus-infected diabetic wounds within 8 days. Overall, this is the first antioxidant and immunomodulatory vesicle for diabetic wound healing by scavenging ROS and regulating immune homeostasis, opening new avenues for effective diabetic wound healing.

A Volcano Correlation between Catalytic Activity for Sulfur Reduction Reaction and Fe Atom Count in Metal Center.

Sulfur reduction reaction (SRR) facilitates up to 16 electrons, which endows lithium-sulfur (Li-S) batteries with a high energy density that is twice that of typical Li-ion batteries. However, its sluggish reaction kinetics render batteries with only a low capacity and cycling life, thus remaining the main challenge to practical Li-S batteries, which require efficient electrocatalysts of balanced atom utilization and site-specific requirements toward highly efficient SRR, calling for an in-depth understanding of the atomic structural sensitivity for the catalytic active sites. Herein, we manipulated the number of Fe atoms in iron assemblies, ranging from single Fe atom to diatomic and triatomic Fe atom groupings, all embedded within a carbon matrix. This led to the revelation of a "volcano peak" correlation between SRR catalytic activity and the count of Fe atoms at the active sites. Utilizing operando X-ray absorption and X-ray diffraction spectroscopies, we observed that polysulfide adsorption-desorption and electrochemical conversion kinetics varied up and down with the incremental addition of even a single iron atom to the catalyst's metal center. Our results demonstrate that the metal center with exactly two iron atoms represents the optimal configuration, maximizing atom utility and adeptly handling the conversion of varied intermediate sulfur species, rendering the Li-S battery with a high areal capacity of 23.8 mAh cm-2 at a high sulfur loading of 21.8 mg cm-2. Our results illuminate the pivotal balance between atom utilization and site-specific requirements for optimal electrocatalytic performance in SRR and diverse electrocatalytic reactions.

Dual-Responsive Gradient Structured Actuator via Photopolymerization-Induced Diffusion.

Stimuli-responsive materials have recently gained significant attention in the field of soft robotics, sensors, and biomimetic devices. The most facile way for the fabrication of such materials remains to endow bilayer structures which are fabricated with the combination of active and passive layers. Although, easily fabricated, these structures suffer from the generation of stress points between connection areas. In this work we develop a method to create a thin film with controlled cross-link variation across its thickness. The cross-link gradient is achieved through polymerization induced diffusion of dithiol molecules in thiol-ene network. As a result, the film exhibits bending deformation upon illumination with light or exposure to a chemical solvent, thereby demonstrating dual responsiveness. Light actuation of the film is achieved via photothermal effects due to the incorporation of dye into the system which can absorb UV light and heat the network. While solvent induced actuation is due to anisotropic swelling. Furthermore, the straightforward fabrication procedure allows for the creation of more complex deformations by patterning the film using a photomask during photopolymerization.

Cover Feature: Dual-Responsive Gradient Structured Actuator via Photopolymerization-Induced Diffusion (Chem. Eur. J. 33/2024).

Invited for the cover of this issue is the group of Danqing Liu and co-workers at the University of Eindhoven University of Technology. The image depicts two-step photopolymerization-induced diffusion for the fabrication of gradient-structured dual-responsive thiol-ene networks. Read the full text of the article at 10.1002/chem.202400515.

In vitro cytocompatibility of triclosan coated Polyglactin910 sutures.

Bioabsorbable sutures can improve the medical functions of existing non-absorbable sutures, and may produce new medical effects, and are expected to become a new generation of medical degradable materials. In this study, the cytocompatibility of triclosan coated polyglactin910 sutures (CTS-PLGA910) was analyzed and different concentrations of sutures were prepared. The effects of sutures on the cytotoxicity and cell proliferation of HUVEC were studied by CCK-8 assay. The hemolysis, total antioxidant capacity (T-AOC) activity and nitric oxide (NO) content were investigated to improve the blood compatibility of sutures. The results showed that the hemolysis rate of CTS-PLGA910 was less than 5%. After treatment on HUVEC cells for 48 and 72 h, there was no significant change in NO content in CTS-PLGA910 groups compared with the control group, while T-AOC activity and antioxidant capacity were significantly increased in medium and high dose groups. In summary, the blood compatibility and cell compatibility were significantly improved, which provided a basis for the clinical application of sutures in the future.

Dual-frequency fundamental-mode NPRO laser for low-noise microwave generation.

Monolithic nonplanar ring oscillators (NPROs) have achieved great success in industry, scientific applications and space missions due to their excellent narrow-linewidth, low-noise, high beam-quality, lightweight and compact performances. Here, we show that stable dual-frequency or multi-frequency fundamental-mode (DFFM or MFFM) laser can be stimulated directly by tunning pump divergence-angle and beam-waist injected to NPRO. The DFFM laser has a frequency deviation of one free spectral range of the resonator and thus can be utilized for pure microwave generation by common-mode-rejection. To demonstrate the purity of the microwave signal, a theoretical phase noise model is established, and the phase noise and the frequency tunability of the microwave signal are experimentally studied. Single sideband phase noise for a 5.7 GHz carrier is measured as low as -112 dBc/Hz at 10 kHz offset, and -150 dBc/Hz at 10 MHz offset in the free running condition of the laser, which outperforms its counterparts from dual-frequency Laguerre-Gaussian (LG) modes. The frequency of the microwave signal can be efficiently tunned through two channels, with frequency tunning coefficients of 15 Hz/V by piezo, and -60.5 kHz/K by temperature, respectively. We expect that such compact, tunable, low-cost and low-noise microwave sources can facilitate multiple applications including miniaturized atomic clocks, communication and radar, etc.

Unexcited Light Source Imaging for Biomedical Applications.

Optical imaging has a wide range of applications in the biomedical field, allowing the visualization of physiological processes and helping in the diagnosis and treatment of diseases. Unexcited light source imaging technologies, such as chemiluminescence imaging, bioluminescence imaging and afterglow imaging have attracted great attention in recent years because of the absence of excitation light interference in their application and the advantages of high sensitivity and high signal-to-noise ratio. In this review, the latest advances in unexcited light source imaging technology for biomedical applications are highlighted. The design strategies of unexcited light source luminescent probes in improving luminescence brightness, penetration depth, quantum yield and targeting, and their applications in inflammation imaging, tumor imaging, liver and kidney injury imaging and bacterial infection imaging are introduced in detail. The research progress and future prospects of unexcited light source imaging for medical applications are further discussed.

Research Status and Prospect of Non-Viral Vectors Based on siRNA: A Review.

Gene therapy has attracted much attention because of its unique mechanism of action, non-toxicity, and good tolerance, which can kill cancer cells without damaging healthy tissues. siRNA-based gene therapy can downregulate, enhance, or correct gene expression by introducing some nucleic acid into patient tissues. Routine treatment of hemophilia requires frequent intravenous injections of missing clotting protein. The high cost of combined therapy causes most patients to lack the best treatment resources. siRNA therapy has the potential of lasting treatment and even curing diseases. Compared with traditional surgery and chemotherapy, siRNA has fewer side effects and less damage to normal cells. The available therapies for degenerative diseases can only alleviate the symptoms of patients, while siRNA therapy drugs can upregulate gene expression, modify epigenetic changes, and stop the disease. In addition, siRNA also plays an important role in cardiovascular diseases, gastrointestinal diseases, and hepatitis B. However, free siRNA is easily degraded by nuclease and has a short half-life in the blood. Research has found that siRNA can be delivered to specific cells through appropriate vector selection and design to improve the therapeutic effect. The application of viral vectors is limited because of their high immunogenicity and low capacity, while non-viral vectors are widely used because of their low immunogenicity, low production cost, and high safety. This paper reviews the common non-viral vectors in recent years and introduces their advantages and disadvantages, as well as the latest application examples.

Phototriggered Complex Motion by Programmable Construction of Light-Driven Molecular Motors in Liquid Crystal Networks.

Recent developments in artificial molecular machines have enabled precisely controlled molecular motion, which allows several distinct mechanical operations at the nanoscale. However, harnessing and amplifying molecular motion along multiple length scales to induce macroscopic motion are still major challenges and comprise an important next step toward future actuators and soft robotics. The key to addressing this challenge relies on effective integration of synthetic molecular machines in a hierarchically aligned structure so numerous individual molecular motions can be collected in a cooperative way and amplified to higher length scales and eventually lead to macroscopic motion. Here, we report the complex motion of liquid crystal networks embedded with molecular motors triggered by single-wavelength illumination. By design, both racemic and enantiomerically pure molecular motors are programmably integrated into liquid crystal networks with a defined orientation. The motors have multiple functions acting as cross-linkers, actuators, and chiral dopants inside the network. The collective rotary motion of motors resulted in multiple types of motion of the polymeric film, including bending, wavy motion, fast unidirectional movement on surfaces, and synchronized helical motion with different handedness, paving the way for the future design of responsive materials with enhanced complex functions.

Self-regulating electrical rhythms with liquid crystal oligomer networks in hybrid circuitry.

Self-regulation is an essential aspect in the practicality of electronic systems, ranging from household heaters to robots for industrial manufacturing. In such devices, self-regulation is conventionally achieved through separate sensors working in tandem with control modules. In this paper, we harness the reversible actuating properties of liquid crystal oligomer network (LCON) polymers to design a self-regulated oscillator. A dynamic equilibrium is achieved by applying a thermally-responsive and electrically-functionalized LCON film as a dual-action component, namely as a combined electrical switch and composite actuating sensor, within a circuit. This hybrid circuit configuration, consisting of both inorganic and organic material, generates a self-regulated feedback loop which cycles regularly and indefinitely. The feedback loop cycle frequency is tunable between approximately 0.08 and 0.87 Hz by altering multiple factors, such as supplied power or LCON chemistry. Our research aims to drive the material-to-device transition of stimuli-responsive LCONs, striving towards applications in electronic soft robotics.

Covalent Organic Frameworks for Chemical and Biological Sensing.

Covalent organic frameworks (COFs) are a class of crystalline porous organic polymers with polygonal porosity and highly ordered structures. The most prominent feature of the COFs is their excellent crystallinity and highly ordered modifiable one-dimensional pores. Since the first report of them in 2005, COFs with various structures were successfully synthesized and their applications in a wide range of fields including gas storage, pollution removal, catalysis, and optoelectronics explored. In the meantime, COFs also exhibited good performance in chemical and biological sensing, because their highly ordered modifiable pores allowed the selective adsorption of the analytes, and the interaction between the analytes and the COFs' skeletons may lead to a detectable change in the optical or electrical properties of the COFs. In this review, we firstly demonstrate the basic principles of COFs-based chemical and biological sensing, then briefly summarize the applications of COFs in sensing some substances of practical value, including some gases, ions, organic compounds, and biomolecules. Finally, we discuss the trends and the challenges of COFs-based chemical and biological sensing.

Light- and Field-Controlled Diffusion, Ejection, Flow and Collection of Liquid at a Nanoporous Liquid Crystal Membrane.

Liquid manipulation at solid surfaces has attracted plenty of interest yet most of them are limited to one or two direction(s), while transport in three dimensions is largely unexplored. Here, we demonstrate three-dimensionally steered dynamic liquid mobility at nanoporous liquid crystal polymer coatings. To this end, we orchestrate liquid motion via sequential triggers of light and/or electric field. Upon a primary flood exposure to UV light, liquid is ejected globally over the entire coating surfaces. We further reallocate the secreted liquid by applying a secondary electric field stimulus. By doing so, the liquid is transported and collected at pre-set positions as determined by the electrode positions. We further monitor this process in real-time and perform precise analysis. Interestingly, when applying those two triggers simultaneously, we discover a UV-gated liquid-release effect, which decreases threshold voltage as well as threshold frequency.

Programmed topographical features generated on command in confined electroactive films.

This work describes a method to create dynamic pre-programmed surface textures by an alternating electric field on coatings that consist of a silicon oxide reinforced viscoelastic siloxane network. The finite element method is developed to predict the complex deformation figures and time-resolved experimental topographical surface analysis is used to confirm them.

Photo-responsive Helical Motion by Light-Driven Molecular Motors in a Liquid-Crystal Network.

Controlling sophisticated motion by molecular motors is a major goal on the road to future actuators and soft robotics. Taking inspiration from biological motility and mechanical functions common to artificial machines, responsive small molecules have been used to achieve macroscopic effects, however, translating molecular movement along length scales to precisely defined linear, twisting and rotary motions remain particularly challenging. Here, we present the design, synthesis and functioning of liquid-crystal network (LCN) materials with intrinsic rotary motors that allow the conversion of light energy into reversible helical motion. In this responsive system the photochemical-driven molecular motor has a dual function operating both as chiral dopant and unidirectional rotor amplifying molecular motion into a controlled and reversible left- or right-handed macroscopic twisting movement. By exploiting the dynamic chirality, directionality of motion and shape change of a single motor embedded in an LC-network, complex mechanical motions including bending, walking and helical motion, in soft polymer materials are achieved which offers fascinating opportunities toward inherently photo-responsive materials.

Plasmonic Enhanced Reactive Oxygen Species Activation on Low-Work-Function Tungsten Nitride for Direct Near-Infrared Driven Photocatalysis.

Realizing near-infrared (NIR) driven photocatalytic reaction is one of the promising strategies to promote the solar energy utilization and photocatalytic efficiencies. However, effective reactive oxygen species (ROS) activation under NIR irradiation remains to be great challenge for nearly all previously reported photocatalysts. Herein, the cubic-phase tungsten nitride (WN) with strong plasmonic NIR absorption and low-work function (≈3.59 eV) is proved to be able to mediate direct ROS activation by both of experimental observation and theoretical simulation. The cubic WN nanocubes (NCs) are synthesized via the hydrothermal-ammonia nitridation process and its NIR-driven photocatalytic properties, including photocatalytic degradation, hydroxylation, and de-esterification, are reported for the first time in this work. The 3D finite element simulation results demonstrate the size dependent and wavelength tuned plasmonic NIR absorption of the WN NCs. The NIR-driven photocatalytic mechanism of WN NCs is proposed based on density functional theory (DFT) calculated electronic structure and facet dependent O2 (or H2 O) molecular activation, radicals scavenging test, spin trapped electron paramagnetic resonance measurements, and ultraviolet photoelectronic spectrum (UPS). Overall, the results in this work pave a way for the application of low-work-function materials as highly reactive NIR photocatalyst.

Electrochemiluminescent detection of Escherichia coli O157:H7 based on Ru(bpy)3 2+/ZnO nanorod arrays.

Foodborne pathogens are perpetual threats to human and animal health. Detection of pathogens requires accurate, sensitive, rapid and point-of-care diagnostic assays. In this study, we described a simple and sensitive electrochemiluminescent (ECL) assay to detect the deadly bacteria Escherichia coli O157:H7 by [Formula: see text]-coated ZnO nanorods arrays (NAs). The [Formula: see text]-coated ZnO NAs were fabricated by immobilizing [Formula: see text] on ZnO NAs with a large specific surface area and good conductivity. An [Formula: see text]-2-(dibutylamino)-ethanol (DBAE) system coated on ZnO NAs exhibits high ECL intensity, rapid response and good stability. This system was further developed as an ECL immunosensor used in the detection of E. coli O157:H7. The proposed ECL immunosensor exhibits a broad detection range within the scope of 200-100 000 CFU ml-1 and quite a low detection limit of 143 CFU ml-1. The high specificity, remarkable reproducibility and good stability offer a sensitive, selective, and convenient pathway for detecting E. coli O157:H7 in the field of food safety and clinical diagnosis.

Single-operator cholangioscopy for the treatment of concomitant gallbladder stones and secondary common bile duct stones.

BACKGROUND AND AIM: This study aims to assess the clinical validity and safety of single-operator cholangioscopy system (SOCS) for the treatment of concomitant gallbladder stones and secondary common bile duct (CBD) stones. METHODS: This retrospective study included 10 consecutive patients who had small-sized stones (< 1 cm) in both the gallbladder and CBD; the patients underwent SOCS treatment from June 2016 to December 2016. The clinical validity of this minimally invasive surgery was determined by the operation success rate, stone removal rate, postoperative hospital stay, hospitalization cost, and contrast images before and after the operation. The clinical safety was evaluated by perioperative complications and outcomes, gallbladder stone recurrence, and gallbladder contractility function. RESULTS: Both the technique success rate and the stone removal rate when using SOCS was 100%. There were no serious complications that occurred during the operation; three patients developed acute cholecystitis, and four patients underwent hyperamylasemia after the surgery. The average postoperative hospital stay was 5.8 ± 1.32 days, and the average hospitalization cost was 7466 ± 566.1 dollars. In the follow-up period, which ranged from 3 to 8 months, there was no stone residuals or recurrences in the gallbladder and CBD, and no patient showed a recurrence of biliary colic. In addition, the gallbladder contractility function was proven to be normal within 3 to 6 months after the operation. CONCLUSIONS: SOCS could successfully manage concomitant gallbladder stones and secondary CBD stones and precisely protect normal biliary function.

Signal-On Electrochemiluminescence of Self-Ordered Molybdenum Oxynitride Nanotube Arrays for Label-Free Cytosensing.

In this paper, a signal-on electrochemiluminescence (ECL) cytosensing platform was developed based on nitrogen doped molybdenum oxynitride nanotube arrays (MoO xN y NTs) for the first time. The MoO xN y NTs exhibited excellent cathodic ECL behavior with 2-(dibutylamino)-ethanol (DBAE) as a coreactant. Owing to the surface plasmon resonance (SPR) of Au triggered by the ECL emission, the generation of "hot electrons" on AuNPs hampered DBAE to give off electrons and leads to the ECL quenching. This process could be hindered via adding "barriers" on the surface of AuNPs, such as antibody molecules and cells, to achieve the signal recovery. Based on the quenching-recovering mechanism, a facile label-free ECL cytosensor was constructed. The linear response of HepG2 cells was in the range of 50-13800 cells mL-1 with a low detection limit of 47 cells mL-1 (S/N = 3). Moreover, the proposed ECL cytosensor exhibits a satisfying performance in the practical application. Due to the anodic formation from a Mo metal substrate, the valuable feature is that the MoO xN y NTs-based ECL cytosensor can be used directly, thereby providing a stable and simplified ECL cytosensing platform for future clinical applications.

Liquid crystal polymers with motile surfaces.

In analogy with developments in soft robotics it is anticipated that soft robotic functions at surfaces of objects may have a large impact on human life with respect to comfort, health, medical care and energy. In this review, we demonstrate the possibilities and versatilities of liquid crystal networks and elastomers being explored for soft robotics, with an emphasis on motile surface properties, such as topographical dynamics. Typically the surfaces reversibly transfer from a flat state to a pre-designed corrugated state under various stimuli. But also reversible conversion between different corrugated states is feasible. Generally, the driving triggers are heat, light, electricity or contact with pH changing media. Also, the macroscopic effects of those dynamic topographies, such as altering the friction, wettability and/or performing work are illustrated. The review concludes with the existing challenges as well as outlook opportunities.