Organic Reactions Enabled by Mechanical Force-Induced Single Electron Transfer.

Mechanochemical reactions, achieved through milling, grinding, or other mechanical actions, have emerged as a solvent-free alternative to traditional solution-based chemistry. Mechanochemistry not only provides the opportunity to eliminate bulk solvent use, reducing waste generation, but also unveils a new reaction strategy which enables the realization of reactions previously inaccessible in solution. While the majority of organic reactions facilitated by mechanical force traditionally follow two-electron transfer pathways similar to their solution-based counterparts, the field of mechanochemically induced single-electron transfer (SET) reactions has witnessed rapid development. This review outlines examples of mechanochemical reactions facilitated by the SET process, focusing on the reagents that initiate SET, thereby positioning mechanochemistry as a burgeoning field within the realm of single-electron chemistry.

Piezoelectric Materials and Pyroelectric Materials:High Efficient Catalysts for Photoelectrochemical Water Splitting.

Directly transforming solar energy into chemical compounds via photocatalytic water splitting can continually producing hydrogen, regarded as one of the ultimate sustainable energy sources. The key point of achieving high photoelectrochemical (PEC) water splitting performance depends on the successful design and synthesis of high-efficient photocatalysts. However, the slow separation and fast recombination of photo generated charge carriers greatly limit the utilization of solar energy, resulting in low PEC water splitting efficiency. Recently, piezoelectric/pyroelectric effect assisted PEC water splitting brings new sight on improving charger separate and transfer behaviors. In this review, the recent advancements and state-of-the-art progress in piezoelectric/pyroelectric effect assisted PEC water splitting are summarized and discussed. Different types of photocatalysts are classified according to their chemical constitutions and the corresponding advantages of each type are also discussed. Furthermore, the progress of coupling piezoelectric effect and pyroelectric effect in one PEC water splitting system is also introduced. Finally, the prospects, critical challenges and promising strategies for the application of piezoelectric/pyroelectric materials in PEC water splitting are highlighted.

Ultrasonic-responsive piezoelectric stimulation enhances sonodynamic therapy for HER2-positive breast cancer.

INTRODUCTION: Breast cancer ranks second as the most common malignancy globally, after lung cancer. Among the various subtypes of breast cancer, HER2 positive breast cancer (HER2 BC)poses a particularly challenging prognosis due to its heightened invasiveness and metastatic potential. The objective of this study was to construct a composite piezoelectric nanoparticle based on poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)) for imaging and treatment of HER2 BC. METHOD: By reshaping the crystal structure of P(VDF-TrFE) piezoelectric nanoparticles, improving hydrophilicity, and incorporating imaging capabilities, we developed piezoelectric composite nanoparticles (PGd@tNBs) that integrate imaging and therapeutic functions. The in vitro characterization encompassed the assessment of piezoelectric properties, hydrophilicity, imaging performance, and therapeutic efficacy of these particles. The targeting and therapeutic effectiveness of PGd@tNBs particles were further validated in the SK-BR3 cell line and subsequently confirmed in HER2-positive tumor-bearing mice. RESULTS: The nanoparticle demonstrated excellent biocompatibility and impressive multimodal imaging performance. Magnetic resonance imaging (MRI) observations revealed significant accumulation of PGd@tNBs particles in the HER2 positive tumor, exhibiting superior contrast-enhanced ultrasound performance compared to traditional ultrasound contrast agents, and small animal in vivo imaging showed that PGd@tNBs particles were primarily excreted through respiration and urinary metabolism. Piezoforce Microscopy characterization highlighted the outstanding piezoelectric properties of PGd@tNBs particles. Upon targeted binding to HER2-BC, ultrasound stimulation influenced the cell membrane potential, leading to reversible electroporation. This, in turn, affected the balance of calcium ions inside and outside the cells and the mitochondrial membrane potential. Following ingestion by cells, PGd@tNBs, when exposed to ultrasound, triggered the generation of reactive oxygen species (ROS), resulting in the consumption of glutathione and superoxide dismutase and achieving sonodynamic therapy. Notably, repeated ultrasound stimulation, post PGd@tNBs particles binding and entry into cells, increased ROS production and elevated the apoptosis rate by approximately 45%. CONCLUSION: In conclusion, the PGd@tNBs particles developed exhibit outstanding imaging and therapeutic efficacy, holding potential for precise diagnosis and personalized treatment of HER2 BC.

Mechanochemical Synthesis of Aryl Fluorides by Using Ball Milling and a Piezoelectric Material as the Redox Catalyst.

Aryl fluorides are important structural motifs in many pharmaceuticals. Although the Balz-Schiemann reaction provides an entry to aryl fluorides from aryldiazonium tetrafluoroborates, it suffers from drawbacks such as long reaction time, high temperature, toxic solvent, toxic gas release, and low functional group tolerance. Here, we describe a general method for the synthesis of aryl fluorides from aryldiazonium tetrafluoroborates using a piezoelectric material as redox catalyst under ball milling conditions in the presence of Selectfluor. This approach effectively addresses the aforementioned limitations. Furthermore, the piezoelectric material can be recycled multiple times. Mechanistic investigations indicate that this fluorination reaction may proceed via a radical pathway, and Selectfluor plays a dual role as both a source of fluorine and a terminal reductant.

Vibration Energy Conversion Power Supply Based on the Piezoelectric Thin Film Planar Array.

Vibration energy harvesting has received much attention as a new type of power solution for low-power micro/nano-devices. However, VEH (vibration energy harvester) based on PVDF (polyvinylidene fluoride) piezoelectric materials have a low output power and energy conversation efficiency due to the relatively low piezoelectric constant, coupling coefficient, and dielectric constant. For this reason, we design a vibration energy conversion power supply, which consists of a VEH with a PVDF piezoelectric thin film planar array vibration structure and an energy harvesting circuit for regulating the electric energy of multiple sources. Furthermore, our solution was validated by simulations of structural dynamics in COMSOL and equivalent circuits model in Multisim. From the circuitry simulation results, the output current and the charging period increase and decrease, doubling, respectively, for each doubling of the number of array groups of films. Moreover, the solid mechanics simulation results show that the planar array structure makes the phase and amplitude of the input vibration waves as consistent as possible so that the same theoretical enhancement effect of the circuitry model is achieved. An identical experimental test was implemented with vibration conditions of 75 Hz-2.198 g. The fabricated harvester quickly charged the 22 V-0.022 F ultracapacitor bank to 5 V in 24 min. The maximum open circuit voltage and output power, respectively, were 10.4 V and 0.304 mW. This maximum charging power was 11.69 times higher than that of a single film. This special power supply can replace batteries to power low-power electronics deployed in vibrating environments, thus reducing the maintenance costs of equipment and environmental pollution rates.

Neuron Compatibility and Antioxidant Activity of Barium Titanate and Lithium Niobate Nanoparticles.

The biocompatibility and the antioxidant activity of barium titanate (BaTiO3) and lithium niobate (LiNbO3) were investigated on a neuronal cell line, the PC12, to explore the possibility of using piezoelectric nanoparticles in the treatment of inner ear diseases, avoiding damage to neurons, the most delicate and sensitive human cells. The cytocompatibility of the compounds was verified by analysing cell viability, cell morphology, apoptotic markers, oxidative stress and neurite outgrowth. The results showed that BaTiO3 and LiNbO3 nanoparticles do not affect the viability, morphological features, cytochrome c distribution and production of reactive oxygen species (ROS) by PC12 cells, and stimulate neurite branching. These data suggest the biocompatibility of BaTiO3 and LiNbO3 nanoparticles, and that they could be suitable candidates to improve the efficiency of new implantable hearing devices without damaging the neuronal cells.

Wide Bandwidth Vibration Energy Harvester with Embedded Transverse Movable Mass.

One of the biggest challenges associated with vibration energy harvesters is their limited bandwidth, which reduces their effectiveness when utilized for Internet of Things applications. This paper presents a novel method of increasing the bandwidth of a cantilever beam by using an embedded transverse out-of-plane movable mass, which continuously changes the resonant frequency due to mass change and non-linear dynamic impact forces. The concept was investigated through experimentation of a movable mass, in the form of a solid sphere, that was embedded within a stationary proof mass with hollow cylindrical chambers. As the cantilever oscillated, it caused the movable mass to move out-of-plane, thus effectively altering the overall effective mass of the system during operation. This concept combined high bandwidth non-linear dynamics from the movable mass with the high power linear dynamics from the stationary proof mass. This paper experimentally investigated the frequency and power effects of acceleration, the amount of movable mass, the density of the mass, and the size of the movable mass. The results demonstrated that the bandwidth can be significantly increased from 1.5 Hz to >40 Hz with a transverse movable mass, while maintaining high power output. Dense movable masses are better for high acceleration, low frequency applications, whereas lower density masses are better for low acceleration applications.

Design and Analysis of an Active Reflection Controller That Can Reduce Acoustic Signal Refer to the Angle of Incidence.

Techniques for reducing the reflection of acoustic signals have recently been actively studied. Most methods for reducing acoustic signals were studied using the normal-incidence wave reduction technique. Although the technique of canceling an object from the normal incidence wave is essential, research on reducing acoustic signals according to the angle of incidence is required for practical applications. In this study, we designed, fabricated, and experimented with an active reflection controller that can reduce acoustic signals according to the angle of incidence. The controller consists of a transmitter on one layer, a receiver sensor on two layers, and an acoustic window on three layers. To reduce the reflected signal, a combination of the time delay and phase was applied to the controller to minimize the acoustic signal by up to -23 dB at an angle of 10°. A controller array simulation was performed based on the results of a controlled experiment. In conclusion, our proposed controller can reduce acoustic signals according to the angle of incidence, which makes it suitable for many applications.

Reflected Wave Reduction Based on Time-Delay Separation for the Plane Array of Multilayer Acoustic Absorbers.

This paper presents a control technique for reducing the reflection of acoustic signals for the plane array of multilayer acoustic absorbers underwater. In order to achieve this, a plane array of multilayer acoustic absorbers is proposed to attenuate low-frequency noise, with each unit consisting of a piezoelectric transducer, two layers of polyvinylidene fluorides and three layers of the acoustic window. Time-delay separation is used to find the incident and reflected acoustic signals to achieve reflected sound reduction. Experimental comparison of the attenuation rate of the reflected acoustic signal when performing passive and active controls is considered to verify the effectiveness of the time-delay separation technique applied plane array absorbers. Experiments on the plane array of smart skin absorbers confirmed that the reduction of reflected acoustic signals makes it suitable for a wide range of underwater applications.

Photoluminescence and piezoelectric behaviour of Y2 Zr2 O7 pyrochlore-based multifunctional materials and the influence of Eu3+ and Sm3.

Y2 Zr2 O7 -doped with Eu3+ and Sm3+ phosphors were prepared for the first time as multifunctional smart materials using a solid-state reaction method at 1400o C. Thermal behaviour, crystal structure, surface morphology, and elemental analysis were characterized using thermogravimetric (TG) and differential thermal (DTA) analyses, X-ray diffraction (XRD) and scanning electron microscope equipped with energy-dispersive X-ray spectroscopy (SEM-EDX). Experimental results revealed that both phosphors have a pyrochlore structure with a cubic crystal system. Photoluminescence properties were also measured and red emission was observed from Y1.90 Eu0.10 Zr2 O7 and Y1.90 Sm0.10 Zr2 O7 phosphors. Dielectric constant, loss tangent, piezoelectric charge constant, and Curie temperature of all the samples were determined using an LCR-meter, d33 -meter, and TG/DTA. Eu doping in Y2 Zr2 O7 resulted in a high dielectric constant (9.61) and low loss tangent (1.67%) values, whereas high piezoelectric charge constant (0.68 pC/N) and high Curie temperature (820°C) could be obtained using Sm-doped Y2 Zr2 O7 .

Comparison between Resonance and Non-Resonance Type Piezoelectric Acoustic Absorbers.

In this study, piezoelectric acoustic absorbers employing two receivers and one transmitter with a feedback controller were evaluated. Based on the target and resonance frequencies of the system, resonance and non-resonance models were designed and fabricated. With a lateral size less than half the wavelength, the model had stacked structures of lossy acoustic windows, polyvinylidene difluoride, and lead zirconate titanate-5A. The structures of both models were identical, except that the resonance model had steel backing material to adjust the center frequency. Both models were analyzed in the frequency and time domains, and the effectiveness of the absorbers was compared at the target and off-target frequencies. Both models were fabricated and acoustically and electrically characterized. Their reflection reduction ratios were evaluated in the quasi-continuous-wave and time-transient modes.

Damage Quantification with Embedded Piezoelectric Aggregates Based on Wavelet Packet Energy Analysis.

Cement-based components have been widely used in civil engineering structures. However, due to wearing and deterioration, the cement-based components may have brittle failure. To provide early warning and to support predictive reinforcement, the piezoelectric materials are embedded into the cement-based components to excite and receive elastic waves. By recognizing the abnormalities in the elastic waves, hidden damage can be identified in advance. However, few research has been published regarding the damage quantification. In this paper, the wavelet packet analysis is adopted to calculate the energy of the transmitted elastic waves based on the improved piezoelectric aggregates (IPAs). Due to the growth of the damage, less elastic waves can pass through the damage zone, decreasing the energy of the acquired signals. A set of cement beams with different crack depths at the mid-span is tested in both numerical and experimental ways. A damage quantification index, namely the wavelet packet-based energy index (WPEI), is developed. Both the numerical and experimental results demonstrate that the WPEI decreases with respect to the crack depth. Based on the regression analysis, a strong linear relationship has been observed between the WPEI and the crack depth. By referring to the linear relationship, the crack depth can be estimated by the WPEI with a good accuracy. The results demonstrated that the use of the IPAs and the WPEI can fulfill the real-time quantification of the crack depth in the cement beams.

Flexible Piezoelectric Sensor-Based Gait Recognition.

Most motion recognition research has required tight-fitting suits for precise sensing. However, tight-suit systems have difficulty adapting to real applications, because people normally wear loose clothes. In this paper, we propose a gait recognition system with flexible piezoelectric sensors in loose clothing. The gait recognition system does not directly sense lower-body angles. It does, however, detect the transition between standing and walking. Specifically, we use the signals from the flexible sensors attached to the knee and hip parts on loose pants. We detect the periodic motion component using the discrete time Fourier series from the signal during walking. We adapt the gait detection method to a real-time patient motion and posture monitoring system. In the monitoring system, the gait recognition operates well. Finally, we test the gait recognition system with 10 subjects, for which the proposed system successfully detects walking with a success rate over 93 %.

Patient Posture Monitoring System Based on Flexible Sensors.

Monitoring patients using vision cameras can cause privacy intrusion problems. In this paper, we propose a patient position monitoring system based on a patient cloth with unobtrusive sensors. We use flexible sensors based on polyvinylidene fluoride, which is a flexible piezoelectric material. Theflexiblesensorsareinsertedintopartsclosetothekneeandhipoftheloosepatientcloth. We measure electrical signals from the sensors caused by the piezoelectric effect when the knee and hip in the cloth are bent. The measured sensor outputs are transferred to a computer via Bluetooth. We use a custom-made program to detect the position of the patient through a rule-based algorithm and the sensor outputs. The detectable postures are based on six human motions in and around a bed. The proposed system can detect the patient positions with a success rate over 88 percent for three patients.

Flexible Piezoelectric Energy Harvesting from Mouse Click Motions.

In this paper, we study energy harvesting from the mouse click motions of a robot finger and a human index finger using a piezoelectric material. The feasibility of energy harvesting from mouse click motions is experimentally and theoretically assessed. The fingers wear a glove with a pocket for including the piezoelectric material. We model the energy harvesting system through the inverse kinematic framework of parallel joints in a finger and the electromechanical coupling equations of the piezoelectric material. The model is validated through energy harvesting experiments in the robot and human fingers with the systematically varying load resistance. We find that energy harvesting is maximized at the matched load resistance to the impedance of the piezoelectric material, and the harvested energy level is tens of nJ.

Broadening bandgaps in a multi-resonant piezoelectric metamaterial plate via bandgap merging phenomena.

Locally resonant metamaterials usually have narrow bandgaps, which significantly limits their applications in realistic engineering environments. In this paper, an optimization method based on the genetic algorithm is proposed to broaden bandgaps in multi-resonant piezoelectric metamaterial through the merging of multiple separated bandgaps. Using the effective medium theory, the equivalent bending stiffness and dispersion relationship of a metamaterial plate are first obtained. Then, the criteria for determining the bandgap ranges for the two cases with and without damping are provided and analyzed. Furthermore, based on the bandgap merging phenomena, an optimization method for widening the bandgap is proposed based on the genetic algorithm. By investigating the bandgap widening effects in cases without and with damping, it is found that, when there is no damping, the bandgap can only be slightly widened; while after introducing damping into the transfer functions, the bandgap can be significantly widened by more than 200%. The bandgap widening effects are verified by comparing with finite element simulation results.

Sea Cucumber-Inspired Microneedle Nerve Guidance Conduit for Synergistically Inhibiting Muscle Atrophy and Promoting Nerve Regeneration.

Muscle atrophy resulting from peripheral nerve injury (PNI) poses a threat to a patient's mobility and sensitivity. However, an effective method to inhibit muscle atrophy following PNI remains elusive. Drawing inspiration from the sea cucumber, we have integrated microneedles (MNs) and microchannel technology into nerve guidance conduits (NGCs) to develop bionic microneedle NGCs (MNGCs) that emulate the structure and piezoelectric function of sea cucumbers. Morphologically, MNGCs feature an outer surface with outward-pointing needle tips capable of applying electrical stimulation to denervated muscles. Simultaneously, the interior contains microchannels designed to guide the migration of Schwann cells (SCs). Physiologically, the incorporation of conductive reduced graphene oxide and piezoelectric zinc oxide nanoparticles into the polycaprolactone scaffold enhances conductivity and piezoelectric properties, facilitating SCs' migration, myelin regeneration, axon growth, and the restoration of neuromuscular function. These combined effects ultimately lead to the inhibition of muscle atrophy and the restoration of nerve function. Consequently, the concept of the synergistic effect of inhibiting muscle atrophy and promoting nerve regeneration has the capacity to transform the traditional approach to PNI repair and find broad applications in PNI repair.

A piezoelectric micromachined ultrasound transducer combined with recording electrodes for acute brain preparations in vitro.

BACKGROUND: Ultrasound stimulation is used to noninvasively stimulate the local and deep areas of the brain. However, the detailed cellular mechanisms of neural activation are still unclear because studies on micro-stimulation at the cellular level are lacking. NEW METHOD: To modulate neural activity at the cellular level, we developed a piezoelectric micromachined ultrasound transducer (PMUT), having circular diaphragms for application on acute brain slice preparations. To monitor neural activities, additionally, we fabricated recording microelectrodes onto the same PMUT device for closed-loop application. RESULTS: To examine the PMUT-driven cellular responses of a brain slice, intracellular calcium signals in individual cells were measured using two calcium indicators. We successfully observed the intracellular responses triggered by the ultrasound of our novel PMUT. In addition, we performed recordings of local field potentials in a brain slice, demonstrating its usefulness as a simultaneous recording interface. COMPARISON WITH EXISTING METHOD(S): Conventional ultrasound stimulators are open-loop systems that risk inducing excessive neural activity because of the absence of neural activity monitoring. In contrast, our PMUT is packaged in a single device with both stimulation and sensor interface for neuromodulation. Further, there are no published reports on in vitro microdevices that can be used for ultrasound stimulation in rodent cortical slices that are several hundred micrometers thick, which maintain the cortical laminar structure and intrinsic neural networks. CONCLUSIONS: Our findings suggest that this novel PMUT device has the potential for being a powerful tool for in vitro brain slice applications and effective closed loop ultrasound stimulation.

Multifunctional nanoplatform based on tetragonal BaTiO3-Au@polydopamine for computed tomography imaging-guided photothermal synergistic and enhanced piezocatalytic cancer therapy.

Non-centrosymmetric tetragonal barium titanate nanocrystals have the potential to serve as piezoelectric catalysts in cancer therapy. When exposed to ultrasound irradiation, BaTiO3 can generate reactive oxygen species with a noninvasive and deep tissue-penetrating approach. However, the application of BaTiO3 in cancer nanomedicine is limited by their biosafety, biocompatibility, and dosage efficiency. To explore the potential application of BaTiO3 in nanomedical cancer treatment, we introduced ultra-small Au nanoparticles onto the surface of BaTiO3 to enhance the piezoelectric catalytic performance. Additionally, we also coated the BaTiO3 with polydopamine to improve their biosafety and biocompatibility. This led to the preparation of a novel multifunctional BaTiO3-based nanoplatform called BTAPs. In vitro and in vivo experiments demonstrated that the incorporation of Au dopants and polydopamine coating successfully improved the piezoelectric catalysis properties and biocompatibility of BaTiO3. Compared with unmodified BaTiO3, BTAPs achieved a similar piezoelectric catalytic effect at a low dose (0.3 mg ml-1 in vitro and 10 mg kg-1 in vivo). Moreover, BTAPs also exhibited enhanced properties in computed tomography imaging and photothermal effects in vivo. Therefore, BTAPs offer valuable insights into the advantages and limitations of piezoelectric catalytic nanomedicine in cancer treatment.

Orally Ingested Self-Powered Stimulators for Targeted Gut-Brain Axis Electrostimulation to Treat Obesity and Metabolic Disorders.

Obesity is a significant health concern that often leads to metabolic dysfunction and chronic diseases. This study introduces a novel approach to combat obesity using orally ingested self-powered electrostimulators. These electrostimulators consist of piezoelectric BaTiO3 (BTO) particles conjugated with capsaicin (Cap) and aim to activate the vagus nerve. Upon ingestion by diet-induced obese (DIO) mice, the BTO@Cap particles specifically target and bind to Cap-sensitive sensory nerve endings in the gastric mucosa. In response to stomach peristalsis, these particles generate electrical signals. The signals travel via the gut-brain axis, ultimately influencing the hypothalamus. By enhancing satiety signals in the brain, this neuromodulatory intervention reduces food intake, promotes energy metabolism, and demonstrates minimal toxicity. Over a 3-week period of daily treatments, DIO mice treated with BTO@Cap particles show a significant reduction in body weight compared to control mice, while maintaining their general locomotor activity. Furthermore, this BTO@Cap particle-based treatment mitigates various metabolic alterations associated with obesity. Importantly, this noninvasive and easy-to-administer intervention holds potential for addressing other intracerebral neurological diseases.