Insight into Interfacial Polarization for Enhancing Piezoelectricity in Ferroelectric Nanocomposites.

The interfacial effect is widely used to optimize the properties of ferroelectric nanocomposites, however, there is still a lack of direct evidence to understand its underlying mechanisms limited by the nano size and complex structures. Here, taking piezoelectricity, for example, the mechanism of interfacial polarization in barium titanate/poly(vinylidene fluoride-ran-trifluoroethylene) (BTO/P(VDF-TrFE)) nanocomposite is revealed at multiple scales by combining Kelvin probe force microscope (KPFM) with theoretical stimulation. The results prove that the mismatch of permittivity between matrix and filler leads to the accumulation of charges, which in turn induces local polarization in the interfacial region, and thus can promote piezoelectricity independently. Furthermore, the strategy of interfacial polarization to enhance piezoelectricity is extended and validated in other two similar nanocomposites. This work uncovers the mechanism of interfacial polarization and paves newfangled insights to boost performances in ferroelectric nanocomposites.

Piezoelectric nanogenerators for personalized healthcare.

The development of flexible piezoelectric nanogenerators has experienced rapid progress in the past decade and is serving as the technological foundation of future state-of-the-art personalized healthcare. Due to their highly efficient mechanical-to-electrical energy conversion, easy implementation, and self-powering nature, these devices permit a plethora of innovative healthcare applications in the space of active sensing, electrical stimulation therapy, as well as passive human biomechanical energy harvesting to third party power on-body devices. This article gives a comprehensive review of the piezoelectric nanogenerators for personalized healthcare. After a brief introduction to the fundamental physical science of the piezoelectric effect, material engineering strategies, device structural designs, and human-body centered energy harvesting, sensing, and therapeutics applications are also systematically discussed. In addition, the challenges and opportunities of utilizing piezoelectric nanogenerators for self-powered bioelectronics and personalized healthcare are outlined in detail.

Understanding the Potential Screening Effect through the Discretely Structured ZnO Nanorods Piezo Array.

The potential screening effect of one-dimensional ZnO nanorods from carriers has been theoretically proved to severely limit its piezoelectricity, but its exact mechanism needs to be further revealed in experiments to guide the design of piezoelectric semiconductors. Here, a discretely structured design was proposed to prevent the free carriers from tunneling among adjacent ZnO nanorods for suppressing the screening effect. Piezoresponse force microscope and finite element analysis were employed in combination to uncover the underlying mechanism in experiment. Further, the output voltage of this discretely structured device was 1.62 times higher than that of the nondesigned device, which clearly authenticates this suppression behavior. Besides, this design prompts an unexpected improvement in flexibility, where the flexural modulus of this piezo-film was reduced by 35.74%. Notably, this work opens a new way to understand the potential screening effect, as expected, and to advance the development of piezo-electronics toward better piezoelectricity and more excellent flexibility.

Manipulating Relative Permittivity for High-Performance Wearable Triboelectric Nanogenerators.

As the world marches into the era of the Internet of Things (IoT), the practice of human health care is on the cusp of a revolution, driven by an unprecedented level of personalization enabled by a variety of wearable bioelectronics. A sustainable and wearable energy solution is highly desired , but challenges still remain in its development. Here, we report a high-performance wearable electricity generation approach by manipulating the relative permittivity of a triboelectric nanogenerator (TENG). A compatible active carbon (AC)-doped polyvinylidene fluoride (AC@PVDF) composite film was invented with high relative permittivity and a specific surface area for wearable biomechanical energy harvesting. Compared with the pure PVDF, the 0.8% AC@PVDF film-based TENG obtained an enhancement in voltage, current, and power by 2.5, 3.5, and 9.8 times, respectively. This work reports a stable, cost-effective, and scalable approach to improve the performance of the triboelectric nanogenerator for wearable biomechanical energy harvesting, thus rendering a sustainable and pervasive energy solution for on-body electronics.

Copper-Catalyzed Radical 1,4-Difunctionalization of 1,3-Enynes with Alkyl Diacyl Peroxides and N-Fluorobenzenesulfonimide.

Many reactions involving allenyl ion species have been studied, but reactions involving allenyl radicals are less well understood, perhaps because of the inconvenience associated with the generation of short-lived allenyl radicals. We describe here a versatile method for the generation of allenyl radicals and their previously unreported applications in the intermolecular 1,4-carbocyanation and 1,4-sulfimidocyanation of 1,3-enynes. With the assistance of the trifunctional reagents, alkyl diacyl peroxides or N-fluorobenzenesulfonimide, a range of synthetically challenging multisubstituted allenes can be prepared with high regioselectivity. These multisubstituted allenes can be easily transformed into synthetically useful structures such as fluorinated vinyl cyanides, lactones, functionalized allenyl amides, 1-aminonaphthalenes, and pyridin-2(1 H)-ones, and several novel transformations are reported. The results of radical scavenger and radical clock experiments are consistent with the proposed allenyl radical pathway. Density functional theory (DFT) and IR spectroscopy studies suggest the formation of an isocyanocopper(II) species in the ligand exchange step. On the basis of the results of IR, DFT, and diastereoselectivity studies, an isocyanocopper(II)/copper(I) catalytic cycle is proposed, which differs from the previously considered Cu(III) mechanism in cyanation reactions.

A Mussel-Inspired Conductive, Self-Adhesive, and Self-Healable Tough Hydrogel as Cell Stimulators and Implantable Bioelectronics.

A graphene oxide conductive hydrogel is reported that simultaneously possesses high toughness, self-healability, and self-adhesiveness. Inspired by the adhesion behaviors of mussels, our conductive hydrogel shows self-adhesiveness on various surfaces and soft tissues. The hydrogel can be used as self-adhesive bioelectronics, such as electrical stimulators to regulate cell activity and implantable electrodes for recording in vivo signals.

Enhanced performance of ZnO microballoon arrays for a triboelectric nanogenerator.

In recent years, triboelectric nanogenerators (TENGs), harvesting energy from the environment as a sustainable power source, have attracted great attention. Currently, many reports focus on the effect of surface modification on the electrical output performance of the TENG. In this work, we have fabricated vertically grown ZnO microballoon (ZnOMB) arrays on top of pyramid-featured PDMS patterned film, contacted with PTFE film to construct the TENG. The electrical output performances of the designed TENG are presented under external forces with different frequencies. The corresponding output open-circuit voltage with ZnOMBs could reach about 57 V the current density about 59 mA m-2 at 100 Hz, which was about 2.3 times higher than without any ZnO. The global maximum of the instantaneous peak power could reach 1.1 W m-2 when the external load resistance was about 2 MΩ. Furthermore, the electrical output of the fabricated device could light 30 commercial LED bulbs without any rectifier circuits or energy-storage elements. This clearly suggests that this kind of surface modification can dramatically enhance the output performance of the TENG. Moreover, the design of TENG demonstrated here can be applied to various energy harvesting applications.

Zebularine potentiates anti-tumor immunity by inducing tumor immunogenicity and improving antigen processing through cGAS-STING pathway.

DNA methylation is an important epigenetic mechanism involved in the anti-tumor immune response, and DNA methyltransferase inhibitors (DNMTi) have achieved impressive therapeutic outcomes in patients with certain cancer types. However, it is unclear how inhibition of DNA methylation bridges the innate and adaptive immune responses to inhibit tumor growth. Here, we report that DNMTi zebularine reconstructs tumor immunogenicity, in turn promote dendritic cell maturation, antigen-presenting cell activity, tumor cell phagocytosis by APCs, and efficient T cell priming. Further in vivo and in vitro analyses reveal that zebularine stimulates cGAS-STING-NF-κB/IFNß signaling to enhance tumor cell immunogenicity and upregulate antigen processing and presentation machinery (AgPPM), which promotes effective CD4+ and CD8+ T cell-mediated killing of tumor cells. These findings support the use of combination regimens that include DNMTi and immunotherapy for cancer treatment.

Hierarchical Piezoelectric Composites for Noninvasive Continuous Cardiovascular Monitoring.

Continuous monitoring of blood pressure (BP) and multiparametric analysis of cardiac functions are crucial for the early diagnosis and therapy of cardiovascular diseases. However, existing monitoring approaches often suffer from bulky and intrusive apparatus, cumbersome testing procedures, and challenging data processing, hampering their applications in continuous monitoring. Here, a heterogeneously hierarchical piezoelectric composite is introduced for wearable continuous BP and cardiac function monitoring, overcoming the rigidity of ceramic and the insensitivity of polymer. By optimizing the hierarchical structure and components of the composite, the developed piezoelectric sensor delivers impressive performances, ensuring continuous and accurate monitoring of BP at Grade A level. Furthermore, the hemodynamic parameters are extracted from the detected signals, such as local pulse wave velocity, cardiac output, and stroke volume, all of which are in alignment with clinical results. Finally, the all-day tracking of cardiac function parameters validates the reliability and stability of the developed sensor, highlighting its potential for personalized healthcare systems, particularly in early diagnosis and timely intervention of cardiovascular disease.

Mass-Produced Skin-Inspired Piezoresistive Sensing Array with Interlocking Interface for Object Recognition.

E-skins, capable of responding to mechanical stimuli, hold significant potential in the field of robot haptics. However, it is a challenge to obtain e-skins with both high sensitivity and mechanical stability. Here, we present a bioinspired piezoresistive sensor with hierarchical structures based on polyaniline/polystyrene core-shell nanoparticles polymerized on air-laid paper. The combination of laser-etched reusable templates and sensitive materials that can be rapidly synthesized enables large-scale production. Benefiting from the substantially enlarged deformation of the hierarchical structure, the developed piezoresistive electronics exhibit a decent sensitivity of 21.67 kPa-1 and a subtle detection limit of 3.4 Pa. Moreover, an isolation layer is introduced to enhance the interface stability of the e-skin, with a fracture limit of 66.34 N/m. Furthermore, the e-skin can be seamlessly integrated onto gloves without any detachment issues. With the assistance of deep learning, it achieves a 98% accuracy rate in object recognition. We anticipate that this strategy will render e-skin with more robust interfaces and heightened sensing capabilities, offering a favorable pathway for large-scale production.

Glycolysis inhibition for synergistic phototherapy of triple-negative breast cancer.

Phototherapy is a local and precise therapeutic technique for tumor treatment. However, the therapeutic effects of photothermal and photodynamic therapies are inevitably encountered by hypoxia of the tumor microenvironment and heat shock protein induced by hyperthermia, respectively. Herein, we found that mannose, a glucose analog, could reverse tumor hypoxia by inhibiting glycolysis of cancer cells and suppressing the expression of heat shock protein through inhibiting cellular adenosine triphosphate (ATP) generation. Next, we used lipid nanoparticles simultaneously loaded with indocyanine green (ICG) and mannose molecules, named imLipo, for tumor therapy. Both in vitro and in vivo experiments evidenced that the imLipo nanoplatform has significant therapeutic efficacy through synergistic phototherapy under single near-infrared laser irradiation. This work shows that glycolysis inhibition can overcome the challenges of phototherapy. In addition, all three parts (mannose, ICG, and lipid) of imLipo are clinically approved and our designed nanoplatforms have great potential for future tumor treatment.

Carrier concentration-dependent interface engineering for high-performance zinc oxide piezoelectric device.

Piezoelectric semiconductor zinc oxide (ZnO) shows promising applications in many fields, however, its excellent piezoelectric performance is limited by the intrinsic screening effect. Forming p-n junction through interface engineering is an effective strategy to enhance its piezoelectric output, but the unclear regulation mechanism is a bottleneck in developing high-performance devices. In this work, the enhancement mechanism of interface engineering on the piezoelectric performance of ZnO nanorods (NRs) based devices is revealed from the perspective of carrier concentration. Both the theoretical and experimental results show that the piezoelectric output is significantly correlated with the carrier concentration, which is mainly attributed to the suppression of screening effect and the modulation of the device capacitance. After a reasonable matching design of carrier concentration, the piezoelectric potential of the ZnO NRs-based device is greatly enhanced by about 12 times. Apparently, these findings provide a fresh insight to further understand the enhancement mechanism of interface engineering on the electrical output of piezoelectric semiconductor devices, and provide effective support for the design of p-n junction piezoelectric devices.

Modulating piezoelectricity and mechanical strength via three-dimensional gradient structure for piezoelectric composites.

Advanced flexible electronic devices make urgent demand for wearing comfort and data accuracy. Piezoelectric composites exhibit great potential, but mutually constrained mechanical strength and electrical output limit their further applications. Here, we design a gradient PMN-PT/PVDF nanocomposite via a non-equilibrium process integrated with a modified electrospinning and hot-pressing process to modulate the piezoelectric output and mechanical strength. The enhanced piezoelectric output together with the mechanical strength of the gradient structure are verified from both the experimental and simulation results. Ascribed to a unique three-dimensional gradient distribution, the prepared PMN-PT/PVDF nanocomposite exhibits an excellent mechanical strength (830 MPa) and piezoelectric performance (1.08 V), which are substantially higher than those of a randomly dispersed nanocomposite. The enhancement mechanism is revealed in terms of polarization, stress and crystallinity. These results of the gradient structure offer new opportunities to understand the structure-related mechanical and electrical behaviors of a nanocomposite, and support the design of a nanocomposite with overall performance.

Flexible Lead-Free Piezoelectric Ba0.94Sr0.06Sn0.09Ti0.91O3/PDMS Composite for Self-Powered Human Motion Monitoring.

Piezoelectric wearable electronics, which can sense external pressure, have attracted widespread attention. However, the enhancement of electromechanical coupling performance remains a great challenge. Here, a new solid solution of Ba1-xSrxSn0.09Ti0.91O3 (x = 0.00~0.08) is prepared to explore potential high-performance, lead-free piezoelectric ceramics. The coexistence of the rhombohedral phase, orthorhombic phase and tetragonal phase is determined in a ceramic with x = 0.06, showing enhanced electrical performance with a piezoelectric coefficient of d33~650 pC/N. Furthermore, Ba0.94Sr0.06Sn0.09Ti0.91O3 (BSST) is co-blended with PDMS to prepare flexible piezoelectric nanogenerators (PENGs) and their performance is explored. The effects of inorganic particle concentration and distribution on the piezoelectric output of the composite are systematically analyzed by experimental tests and computational simulations. As a result, the optimal VOC and ISC of the PENG (40 wt%) can reach 3.05 V and 44.5 nA, respectively, at 138.89 kPa, and the optimal sensitivity of the device is up to 21.09 mV/kPa. Due to the flexibility of the device, the prepared PENG can be attached to the surface of human skin as a sensor to monitor vital movements of the neck, fingers, elbows, spine, knees and feet of people, thus warning of dangerous behavior or incorrect posture and providing support for sports rehabilitation.

Multichannel Gradient Piezoelectric Transducer Assisted with Deep Learning for Broadband Acoustic Sensing.

As an important part of human-machine interfaces, piezoelectric voice recognition has received extensive attention due to its unique self-powered nature. However, conventional voice recognition devices exhibit a limited response frequency band due to the intrinsic hardness and brittleness of piezoelectric ceramics or the flexibility of piezoelectric fibers. Here, we propose a cochlear-inspired multichannel piezoelectric acoustic sensor (MAS) based on gradient PVDF piezoelectric nanofibers for broadband voice recognition by a programmable electrospinning technique. Compared with the common electrospun PVDF membrane-based acoustic sensor, the developed MAS demonstrates the greatly 300%-broadened frequency band and the substantially 334.6%-enhanced piezoelectric output. More importantly, this MAS can serve as a high-fidelity auditory platform for music recording and human voice recognition, in which the classification accuracy rate can reach up to 100% in coordination with deep learning. The programmable bionic gradient piezoelectric nanofiber may provide a universal strategy for the development of intelligent bioelectronics.

Binding of ankaflavin with bovine serum albumin (BSA) in the presence of carrageenan and protective effects of Monascus yellow pigments against oxidative damage to BSA after forming a complex with carrageenan.

Ankaflavin (AK) is a typical yellow pigment extracted from Monascus-fermented rice with several biological effects; however, its solubility is poor. Thus, research studies of the delivery systems of AK, especially those constructed from protein-polysaccharide complexes, have attracted considerable attention. However, the interactions that exist in the system have rarely been investigated. This work focused on the interactions between AK and bovine serum albumin (BSA) as well as the influence of carrageenan (Car) on the binding of AK to BSA. Results revealed that the quenching of BSA by AK involved the static quenching mechanism. The formed BSA-AK complexes were mainly maintained by hydrophobic forces and AK was located within the hydrophobic cavity of BSA. Compared to free AK or AK only complexed with BSA, a higher absorption intensity of AK was observed for the formed BSA-AK-Car complexes, indicating changes in the microenvironment of AK. This was confirmed by the increase in the α-helix content of BSA after the formation of BSA-AK-Car complexes. Hydrogen bond, van der Waals, and electrostatic interactions were verified to be the primary forces preserving the BSA-AK-Car complexes. Moreover, the antioxidant potential of Monascus-fermented products rich in AK (denoted as Mps), namely BSA-Mps and BSA-Mps-Car was evaluated. The antioxidant activity of Mps was negatively impacted by BSA, while the addition of Car could enhance the antioxidant capacity of BSA-Mps-Car complexes. Meanwhile, Mps showed a protective effect against free radical-induced oxidation damage to BSA, and Car could further improve this effect.

DWL-4-140: A allene small molecule targeting STING that alleviates lupus-like phenotype in Trex1-/- mice.

The innate immune system plays a critical role in the host response against pathogenic microbial infection. However, aberrant activation of the innate immune pathways is a characteristic feature of various diseases. Thus, targeted drugs must be developed based on the understanding of the innate immune signaling pathways. This study demonstrated that an allene small molecule (DWL-4-140) can efficiently and selectively exert regulatory effects on the stimulator of interferon genes (STING), resulting in the downregulation of DNA-induced interferon responses. Mechanistically, DWL-4-140 targeted the cyclized nucleotide-binding domain (CBD) of STING, inhibiting the assembly of the STING multimeric complex and the recruitment of downstream signaling mediators. In addition to downregulating the 10-carboxymethyl-9-acridanone-induced production of inflammatory factors, DWL-4-140 alleviated the pathological features of Trex1 deletion-induced lupus in mice. Thus, this study demonstrated that DWL-4-140 pharmacologically inhibits STING with potential therapeutic applications in auto-inflammatory diseases.

Understanding the Enhancement Mechanism of ZnO Nanorod-based Piezoelectric Devices through Surface Engineering.

ZnO is a typical piezoelectric semiconductor, and enhancing the piezoelectric output of ZnO-based devices is essential for their efficient applications. Surface engineering is an effective strategy to improve the piezoelectric output of ZnO-based devices, but its unclear regulation mechanism leads to a lack of reasonable guidance for device design. In this work, the regulation effect of the barrier layer in ZnO-based piezoelectric devices is systematically investigated from the carrier perspective through surface engineering, resulting in a significant improvement (nearly 10-fold) in the output performance of piezoelectric devices. The regulation mechanism of the ZnO-Cu2O p-n heterojunction devices on piezoelectric output is revealed in terms of built-in electric field, depletion layer width, and junction capacitance. These findings facilitate further insight into the enhancement mechanism of the piezoelectric output of ZnO-based devices and provide reasonable ideas for efficient device design.

Ambulatory Cardiovascular Monitoring Via a Machine-Learning-Assisted Textile Triboelectric Sensor.

Wearable bioelectronics for continuous and reliable pulse wave monitoring against body motion and perspiration remains a great challenge and highly desired. Here, a low-cost, lightweight, and mechanically durable textile triboelectric sensor that can convert subtle skin deformation caused by arterial pulsatility into electricity for high-fidelity and continuous pulse waveform monitoring in an ambulatory and sweaty setting is developed. The sensor holds a signal-to-noise ratio of 23.3 dB, a response time of 40 ms, and a sensitivity of 0.21 µA kPa-1 . With the assistance of machine learning algorithms, the textile triboelectric sensor can continuously and precisely measure systolic and diastolic pressure, and the accuracy is validated via a commercial blood pressure cuff at the hospital. Additionally, a customized cellphone application (APP) based on built-in algorithm is developed for one-click health data sharing and data-driven cardiovascular diagnosis. The textile triboelectric sensor enabled wireless biomonitoring system is expected to offer a practical paradigm for continuous and personalized cardiovascular system characterization in the era of the Internet of Things.

Hierarchically Microstructure-Bioinspired Flexible Piezoresistive Bioelectronics.

The naturally microstructure-bioinspired piezoresistive sensor for human-machine interaction and human health monitoring represents an attractive opportunity for wearable bioelectronics. However, due to the trade-off between sensitivity and linear detection range, obtaining piezoresistive sensors with both a wide pressure monitoring range and a high sensitivity is still a great challenge. Herein, we design a hierarchically microstructure-bioinspired flexible piezoresistive sensor consisting of a hierarchical polyaniline/polyvinylidene fluoride nanofiber (HPPNF) film sandwiched between two interlocking electrodes with microdome structure. Ascribed to the substantially enlarged 3D deformation rates, these bioelectronics exhibit an ultrahigh sensitivity of 53 kPa-1, a pressure detection range from 58.4 to 960 Pa, a fast response time of 38 ms, and excellent cycle stability over 50 000 cycles. Furthermore, this conformally skin-adhered sensor successfully demonstrates the monitoring of human physiological signals and movement states, such as wrist pulse, throat activity, spinal posture, and gait recognition. Evidently, this hierarchically microstructure-bioinspired and amplified sensitivity piezoresistive sensor provides a promising strategy for the rapid development of next-generation wearable bioelectronics.