Antioxidation Activity Enhancement by Intramolecular Hydrogen Bond and Non-Browning Mechanism of Active Ingredients in Rosemary: Carnosic Acid and Carnosol.

Rosemary is one of the most promising, versatile, and studied natural preservatives. Carnosic acid (CA) and carnosol (CARN), as the primary active ingredients of rosemary extracts, have little difference in structure, but their antioxidant activities vary significantly, depending on the system studied. The underlying molecular mechanisms remain unclear. By means of optical spectroscopies, stopped-flow, laser photolysis, and density functional theory (DFT) calculations, we have compared CA and CARN between their reaction dynamics of radical scavenging, metal ion chelation, and oxidation inhibition in lipid emulsion and beef, as well as between their interactions with ß-carotene (ß-Car). For reference, 3-isopropyl catechol (IC), which is structurally similar to the active groups of CA and CARN, was studied in parallel. It is found for CA that the intramolecular hydrogen bond can boost the acidity of its phenol hydroxyl and that the synergistic effect with ß-Car can substantially enhance its antioxidation activity in the model systems of lipid and meat via the CA-to-ß-Car electron transfer reaction. The substitution of A and B rings on the catechol group in both CA and CARN limits browning caused by their formation of oxidative products as antioxidants.

Thermal-Responsive Gel-Based Overheat Limiter Enabled Intelligent Photothermal Therapy.

Uncontrolled and excessive photothermal heating in photothermal therapy (PTT) inevitably causes thermal damage to surrounding normal tissues, severely limiting the universality and safety of PTT. To address this issue, an intelligent cooling thermal-responsive (ICTR) gel containing poly(N-isopropylacrylamide-co-acrylamide) (P(NIPAM-AM))microgel is applied onto the skin to realize intelligent PTT, which can avoid excessive heating and accidental injury. The high near-infrared (NIR) light transmittance (> 95%) of the ICTR gel ensures effective light delivery at low temperatures, while the refractive index of the P(NIPAM-AM) microgel increases remarkably when the temperature exceeds a predetermined threshold, resulting in progressively enhanced light scattering and weakened photothermal conversion. In animal studies, the negative feedback regulation of ICTR gel on light transmittance and photothermal heating allows the photothermal temperature in the lesion site to be stabilized within the effective therapeutic range (45 °C) while ensuring that the skin surface temperature does not exceed 35 °C. Compared with the severe skin thermal damage found in the histological staining of mice skin receiving conventional PTT, the mice skin receiving the ICTR gel-enabled intelligent PTT remains in good condition. This study establishes an intelligent and universal paradigm for PTT thermal regulation, which is of great significance for achieving safe and effective PTT.

Revealing the Mechanism of Ink Flaking from Surfaces of Palm Leaves (Corypha umbraculifera).

Palm leaves are the primary literary support in South and Southeast Asia before the widespread use of paper. However, palm leaf manuscripts face the threat of information loss due to the persistent issue of ink flaking during long-term preservation. Herein, we focus on studying the botanical structure, surface properties, and surface composition of palm leaves to gain an insightful understanding of the mechanism of ink flaking. According to the surface energy analysis, the surface of palm leaves is dominated by the dispersive component due to the presence of hydrophobic substances, resulting in the weak interaction between the handwriting and palm leaves. Moreover, the accumulation of silicon on palm leaves creates a "cuticle-silicon double layer", leading to a dense structure that hinders deep ink absorption. These two main reasons are considered to cause the ink flaking easily, which is further proven by the ink flaking test with the simulated palm leaf manuscripts. To the best of our knowledge, this is the first in-depth technical study on the adhesion performance of handwriting on plant leaves. This work also provides a theoretical basis for the study of the deterioration, adhesive repair, enhancement of flexibility, handwriting reinforcement, and beyond, which contributes to the conservation of precious palm leaf manuscripts.

Stretchable, Programmable and Magnet-Insensitive Protonic Display Based on Integrated Ionic Circuit.

As a new approach to "More than Moore", integrated ionic circuits serve as a possible alternative to traditional electronic circuits, yet the integrated ionic circuit composed of functional ionic elements and ionic connections is still challenging. Herein, a stretchable and transparent ionic display module of the integrated ionic circuit has been successfully prepared and demonstrated by pixelating a proton-responsive hydrogel. It is programmed to excite the hydrogel color change by a Faraday process occurring at the electrode at the specific pixel points, which enables the display of digital information and even color information. Importantly, the display module exhibits stable performance under strong magnetic field conditions (1.7 T). The transparent and stretchable nature of such ionic modules also allows them to be utilized in a broad range of scenarios, which paves the way for integrated ionic circuits.

Deepened Photodynamic Therapy through Skin Optical Clearing Technology in the Visible Light Window.

The trade-off that shorter wavelength light facilitates the efficient generation of reactive oxygen species (ROS) from photosensitizer (PS) while facing the drawback of limited penetration depth through skin tissue restricts the further development of photodynamic therapy (PDT). Here, we address this contradiction and achieve visible-light-tailored deep PDT combined with the skin optical clearing technology. With the help of the prepared skin optical clearing gel, the refractive index inhomogeneity between skin tissue components is greatly attenuated, and the light scattering effect within the skin tissue is remarkably reduced. As a consequence, the transmittance of visible light at 600 nm through in vitro porcine skin and in vivo mouse skin after treatment increases from approximately 10 and 40 to 70 and 70%, respectively. Furthermore, in the tumor cell eradication experiment, the local ROS generation efficiency in the experimental group is several times higher than that in the control group owing to improved visible transmittance, which is thus responsible for the complete eradication of tumor cells, even when shaded by skin tissue. The results suggest that this strategy may serve as a valuable supplement to the current deep PDT strategies.

Fast Interfacial Polymerization for Stabilizing Emulsion Droplets with Polymer Films beyond Emulsifiers.

Stabilizing emulsion droplets with amphiphilic emulsifiers are the current prevailing method, but the extensive use of such amphiphilic substances has caused widespread concerns. In this Perspective, three traditional methods for the stabilization of emulsion droplets according to the type of emulsifiers used are outlined, and the emphasis is placed on the mechanism of steric hindrance for emulsion stabilization. Then, we provide a concise introduction and discussion of the fast interfacial polymerization method as a new strategy for preparing stable emulsifier-free emulsion droplets with a polymer film, including its research background, current progress, and possible development directions. It is anticipated that this paper will promote the development of emulsifier-free emulsion production via fast interfacial polymerization and other related methods.

Uniformly Hybrid Surface Containing Adjustable Hydrophobic/Hydrophilic Components Obtained by Programmed Strain for Synergistic Anti-Icing.

Sufficient efforts have been put into the design of anti-icing materials to eliminate the icing hazard. Among the currently approved anti-icing concepts, hydrophilic/hydrophobic hybrid anti-icing materials inspired by antifreeze proteins show excellent properties in inhibiting ice nucleation, inhibiting ice crystal growth, and reducing ice adhesion. However, it is still a great challenge to accurately regulate the hydrophilic and hydrophobic hybrid components of the coating surface to clarify the synergistic mechanism. This work proposes a strain-manipulated surface modification strategy, and an anti-icing coating with adjustable hydrophilic/hydrophobic hybrid components prepared by combining chemical vapor deposition and siloxane chemistry is obtained. According to the ice resistance experiment at -15 °C, the performance of anti-icing is closely related to the proportion of hydrophilic and hydrophobic hybrids. The icing delay time and ice adhesion strength of the material with the optimal hydrophilic/hydrophobic components are 280 s and 18.6 kPa, respectively. These unique properties can be attributed to the synergistic effect of hydrophilic and hydrophobic structures on the regulation of interfacial water.

Skin Thermal Management for Subcutaneous Photoelectric Conversion Reaching 500 mW.

Despite possessing higher tissue transmittance and maximum permissible exposure power density for skin relative to other electromagnetic waves, second near-infrared light (1000-1350 nm) is scarcely applicable to subcutaneous photoelectric conversion, owing to the companion photothermal effect. Here, skin thermal management is conceived to utmostly utilize the photothermal effect of a photovoltaic cell, which not only improves the photoelectric conversion efficiency but also eliminates skin hyperthermia. In vivo, the output power can be higher than 500 mW with a photoelectric conversion efficiency of 9.4%. This output power is promising to recharge all the clinically applied implantable devices via wireless power transmission, that is, clinical pacemakers (6-200 µW), drug pumps (0.5-2 mW), cochlear (5-40 mW), and wireless endo-photo cameras (≈100 mW).

Caffeic acid phenethyl ester suppresses EGFR/FAK/Akt signaling, migration, and tumor growth of prostate cancer cells.

BACKGROUND: Epidermal growth factor receptor (EGFR) is upregulated in prostate cancer (PCa). However, suppression of EGFR did not improve the patient outcome, possibly due to the activation of PI3K/Akt signaling in PCa. Compounds able to suppress both PI3K/Akt and EGFR signaling may be effective for treating advanced PCa. PURPOSE: We examined if caffeic acid phenethyl ester (CAPE) simultaneously suppresses the EGFR and Akt signaling, migration and tumor growth in PCa cells. METHODS: Wound healing assay, transwell migration assay and xenograft mice model were used to determine the effects of CAPE on migration and proliferation of PCa cells. Western blot, immunoprecipitation, and immunohistochemistry staining were performed to determine the effects of CAPE on EGFR and Akt signaling. RESULTS: CAPE treatment decreased the gene expression of HRAS, RAF1, AKT2, GSK3A, and EGF and the protein expression of phospho-EGFR (Y845, Y1069, Y1148, Y1173), phospho-FAK, Akt, and ERK1/2 in PCa cells. CAPE treatment inhibited the EGF-induced migration of PCa cells. Combined treatment of CAPE with EGFR inhibitor gefitinib showed additive inhibition on migration and proliferation of PCa cells. Injection of CAPE (15 mg/kg/3 days) for 14 days suppressed the tumor growth of prostate xenografts in nude mice as well as suppressed the levels of Ki67, phospho-EGFR Y845, MMP-9, phospho-Akt S473, phospho-Akt T308, Ras, and Raf-1 in prostate xenografts. CONCLUSIONS: Our study suggested that CAPE can simultaneously suppress the EGFR and Akt signaling in PCa cells and is a potential therapeutic agent for advanced PCa.

A Programmable Actuator as Synthetic Earthworm.

Natural earthworm with the ability to loosen soils that favors sustainable agriculture has inspired worldwide interest in the design of intelligent actuators. Given the inability to carry heavy loads and uncontrolled deformation, the vast majority of actuators can only perform simple tasks by bending, contraction, or elongation. Herein, a degradable actuator with the ability to deform in desired ways is presented, which successfully mimics the burrowing activities of earthworms to loosen soils with increased soil porosity by digging, grabbing, and lifting the soil when it receives rains. Such a scarifying actuator is made of degradable cellulose acetate and uncrosslinked polyacrylamide via the swelling-photopolymerizing method. The water absorption of polyacrylamide in moisture conditions causes rapid and remarkable bending. Such mechanical bending can be controlled in specific areas of the cellulose acetate film if polyacrylamide is polymerized in a patterned way, so as to generate complicated deformations of the whole cellulose acetate. Patterning polyacrylamide within cellulose acetate is achieved based on reversible surface protection by means of pen writing, rather than the traditional masking techniques. The water-induced deformation of programmable cellulose-based actuators is well preserved in soil, which is appropriate for promoting rain diffusion as well as root breath.

Antifreezing, Adhesive, and Ultra-Stretchable Ionogel for AI-Enabled Motion Tracking and Recognition in Winter Sports.

Motion tracking and recognition are gaining increasing attention in athletes' training for winter sports due to their importance in posture correction and injury prevention. Electronic skin serves as a better candidate compared to vision-based methods. However, the challenges of its application include sensing materials with good stretchability, softness, anti-freeze, non-volatility, and adhesion, and data processing techniques of high intelligence and efficiency. Here, we propose an antifreezing, adhesive, and ultra-stretchable organic ionogel (OIG). Maximum elongation of over 6500% has been obtained for the OIG of the double network, and the mechanical stretchability is retained at temperatures ranging from -50 to 50 °C. Importantly, the multi-sensor system could realize motion "recognition" rather than "perception" with the help of a convolutional neural network.

Stabilizing Liquid in Precise Nonequilibrium Shapes via Fast Interfacial Polymerization.

Due to the minimization of interface area caused by surface tension, the stabilization of liquid in complex and precise nonequilibrium shapes is challenging. In this work, a simple, surfactant-free, and covalent strategy to stabilize liquid in precise nonequilibrium shapes via fast interfacial polymerization (FIP) of highly reactive n-butyl cyanoacrylate (BCA) monomer triggered by water-soluble nucleophiles is described. Full interfacial coverage can be achieved instantly, and the resultant polyBCA film anchored at the interface can support the unequal interface stress, which allows the production of non-spherical droplets with complex shapes. Notably, the formulation of internal aqueous phase is nearly unaffected since no specific additive is required. Moreover, considering the excellent biocompatibility of BCA and polyBCA, the produced droplets can be used as micro-bioreactor for enzyme catalysis and even bacterial culture, which well mimic the morphology of cells and bacteria to achieve the biochemical reaction in non-spherical droplets. The present work not only opens a new sight for the stabilization of liquid in nonequilibrium shapes, but may also promote the development of synthetic biology based on non-spherical droplets, and tremendous potential applications are anticipated.

Administration of a new nano delivery system coated with Tirofiban to prevent early thrombosis of vein graft.

OBJECTIVE: To verify the administration of a new nano delivery system coated with Tirofiban on preventing early thrombosis in vein graft. METHODS: Forty New Zealand white rabbits were randomly divided into five groups with eight rabbits in each group. The rabbits of all groups underwent jugular vein transplantation, except group I with only neck opening and closing operation. Vein grafts of group II were preprocessed by intravenous injection of normal saline; group III were preprocessed by tirofiban alone; group IV were preprocessed by unloaded nanoparticles of PLGA-PEG; group V were preprocessed by PLGA-PEG coated with tirofiban. Coagulation and platelet function of peripheral and vein graft blood were detected at 1, 2, 4, 12 h and 1, 3, 7, 10, 14 days after operation. Patency rate of vein graft and blood flow index were measured by vascular ultrasound at third, seventh, 10th, and 14th days after operation; two rabbits in each group were randomly sacrificed at the corresponding time of detection. Pathological differences of vein grafts were observed by HE stainin. RESULTS: The patency rate of vein grafts in group V was significantly higher than that in group II to IV. The platelet and platelet aggregation rate in group V were inhibited in vein graft blood significantly. The post-operative PT and APTT in vein graft blood in group V were increased obviously while the FBG, D-dimer and FDP were significantly inhibited. Except group I, the lumen loss rate of vein grafts in group V was significantly lower than that in other groups, and vein graft blood in group V had a significant lower expression of platelet P-selectin and GP IIb/IIIa receptor than that in other groups. CONCLUSION: This study proves that PEG-PLGA coated with tirofiban can effectively prevent early vein graft stenosis from thrombosis by inhibition of platelet function, coagulation function.

Double Asymmetric Core Optimizes Crystal Packing to Enable Selenophene-based Acceptor with Over 18 % Efficiency in Binary Organic Solar Cells.

Side-chain tailoring is a promising method to optimize the performance of organic solar cells (OSCs). However, asymmetric alkyl chain-based small molecular acceptors (SMAs) are still difficult to afford. Herein, we adopted a novel asymmetric n-nonyl/undecyl substitution strategy and synthesized two A-D1 A'D2 -A double asymmetric isomeric SMAs with asymmetric selenophene-based central core for OSCs. Crystallographic analysis indicates that AYT9Se11-Cl forms a more compact and order intermolecular packing compared to AYT11Se9-Cl, which contributed to higher electron mobility in neat AYT9Se11-Cl film. Moreover, the PM6 : AYT9Se11-Cl blend film shows a better morphology with appropriate phase separation and distinct face-on orientation than PM6 : AYT11Se9-Cl. The OSCs with PM6 : AYT9Se11-Cl obtain a superior PCE of 18.12 % compared to PM6 : AYT11Se9-Cl (17.52 %), which is the best efficiency for the selenium-incorporated SMAs in binary BHJ OSCs. Our findings elucidate that the promising double asymmetric strategy with isomeric alkyl chains precisely modulates the crystal packing and enhances the photovoltaic efficiency of selenophene-incorporated SMAs.

Early Braking of Overwarmed Lithium-Ion Batteries by Shape-Memorized Current Collectors.

In the context of the constant impending energy crisis, the lithium-ion battery as a burgeoning energy storage means is showing extraordinary talents in many energy relevant investigations. However, fire and explosion would probably occur when the battery is encountered with overheating, at which the shrinking of the separator routinely causes an internal short circuit. Herein, we develop a kind of novel shape-memorized current collector (SMCC), which can successfully brake battery thermal runaway at the battery internal overheating status. Unlike traditional current collectors made of commercial copper foils, SMCC is made of a micropatterned shape memory micron-sized film with copper deposition. SMCC displays ideal conductivity at normal temperatures and turns to be insulative at overheating temperatures. Following this principle, the battery consisting of an SMCC can run normally at temperatures lower than 90 °C, while it quickly achieves self-shutdown before the occurrence of battery combustion and explosion.

Subcutaneous power supply by NIR-II light.

Implantable medical devices are wished to be recharged via contactless power transfer technologies without interventional operations. Superior to subcutaneous power supply by visible light or electromagnetic wave, second near-infrared (NIR-II) light is predicted to possess 60 times subcutaneous power transmission but hard to be utilized. Here we report a photo-thermal-electric converter via the combination of photothermal conversion and thermoelectric conversion. It is able to generate an output power as high as 195 mW under the coverage of excised tissues, presenting advantages of non-invasion, high output power, negligible biological damage, and deep tissue penetration. As an in vivo demonstration, the output power of a packaged converter in the abdominal cavity of a rabbit reaches 20 mW under NIR-II light irradiation through the rabbit skin with a thickness of 8.5 mm. This value is high enough to recharge an implanted high-power-consumption wireless camera and transfer video signal out of body in real-time.

A Novel Ionic Conductive Polyurethane Based on Deep Eutectic Solvent Continuing Traditional Merits.

Artificial intelligence (AI) has become increasingly popular along with the development of the bionic neural system. Ionic conductors play an important role in the AI system due to the ability of bionic sensing and signal transporting. Traditional low-polarity elastomers possess outstanding mechanical strength and stability, such as polyurethane, which is difficult to be directly endowed with ionic conductivity without impairing its properties. Herein, we have first put forward a new approach to synthesize a liquid-free ionic conductive polyurethane (CPU) through one-step copolymerization between a green deep eutectic solvent (DES) and a prepolymer of polyurethane. The as-prepared CPU can retain the native properties of the traditional polyurethane (PU) such as the homogeneous phase, ease of molding, high transparency (about 93.3%), and excellent mechanical properties. By introducing the DES as the covalent cross-linking agent and ionic conductor at the same time, the CPU also has fine ionic conductivity (3.78 × 10-5 S cm-1), environmental resistance like anti-freezing (-20 °C), and solvent resistance. Based on the excellent conductivity and mechanical strength, the flexible CPU can be applied as a sensing element in pressure sensors. The CPU-based sensor has presented long-term stability, high sensitivity, and wide-ranging response (0.17-3.28 MPa) to the applied pressure, which will be suitable for the industrial demands for practical applications.

Thermal Nociception of Ionic Skin: TRPV1 Ion Channel-Inspired Heat-Activated Dynamic Ionic Liquid.

The artificial reproduction of the tactile sensory function of natural skin is crucial for intelligent sensing, human-computer interaction, and medical health. Thermal nociception is an essential human tactile function to avoid noxious thermal stimuli, which depends on the specific heat-activation of the TRPV1 ion channel. Inspired by the TRPV1, a dynamic ionic liquid with heat-activation characteristics is designed and prepared, which can be activated at 45 °C, which is near the physiological noxious temperature, accompanied by a steep rise in electrical response signals. Its electrical behavior can be deemed to be the extreme version of temperature sensation similar to the natural thermal nociceptor. The heat-activation mechanism is confirmed as a feasible strategy to regulate the thermal response behavior of ions, and this reported dynamic ionic liquid has an unprecedented intrinsic temperature response sensitivity of up to 156.79%/°C. In consideration of the similarity between the heat-activated dynamic ionic liquid and the TRPV1 ion channel in terms of heat-activation characteristics, electrical output signal, and ultrathermal sensitivity, an all-liquid ionic skin with the ability of thermal nociception is further fabricated, which shows considerable potential to assist patients with tactile desensitization to avoid noxious thermal stimuli.

Ultradeep Photothermal Therapy Strategies.

Photothermal therapy (PTT) mediated by the second near-infrared light (NIR-II) is considered as the most promising PTT in deep tissues due to the superior penetrability of NIR-II through biological tissues. However, the effective therapeutic depth of NIR-II mediated PTT is limited to only several millimeters beneath the skin tissues. So far, deep PTT still cannot satisfy the depth requirement for most common cancers, including but not limited to lung, pancreatic, colorectal, and stomach cancers. Therefore, it is highly desirable to develop ultradeep PTT strategies to enhance the therapeutic depth with clinical availability. This Perspective highlights the latest research progress in regard to ultradeep PTT strategies, including larger laser spot PTT, skin tissue optical clearing technology enhanced PTT, and optical fiber assisted PTT, followed with pertinent evaluations and expectations. In addition, challenges and perspectives in this fast-growing area of ultradeep PTT are discussed.

Iodine-Oxidized Diene-Based Rubbers as Anti-icing and Deicing Polymer Coatings.

In an effort to prevent or minimize icing hazards, techniques and materials for icing inhibition and deicing have always been highly favored throughout human history. This work discovers the integrated anti-icing and deicing effects of poly(styrene-b-butadiene-b-styrene) triblock rubber (SBS) after its easy oxidation in iodine vapor. Iodine oxidation happens on the block of polybutadiene, featured by the conversion of SBS from hydrophobic to amphiphilic and the improved capability of photothermal conversion. The oxidized SBS can serve as a polymer coating, which possesses intriguing abilities to delay the kinetics of icing on its surface and repel the ice under light illumination. According to characterizations of surface chemistry and mechanical performance, iodine oxidation is assumed to involve the processes of iodine coordination to unsaturated bonds, the formation of radical cations as a result of the redox reaction between iodine and unsaturated carbon-carbon bonds, improved light absorption owing to the formation of polyiodide anions, and intermolecular coupling of radical cations. The appearance of polar moieties/species within the oxidized SBS is attributed to the delayed ice nucleation. The significant photothermal capacity in visible and near-infrared windows enables the iodine-oxidized SBS coating to remove the adhered ice by melting under light illumination when the icing process is inevitable, even at an extremely low temperature (-25 °C).