The integrated smart electronics for real-time monitoring and personalized therapy of disease-related analytes have been gradually gaining tremendous attention. However, human tissue barriers, including the skin barrier and brain-blood barrier, pose significant challenges for effective biomarker detection and drug delivery. Microneedle (MN) electronics present a promising solution to overcome these tissue barriers due to their semi-invasive structures, enabling effective drug delivery and target-analyte detection without compromising the tissue configuration. Furthermore, MNs can be fabricated through solution processing, facilitating large-scale manufacturing. This review provides a comprehensive summary of the recent three-year advancements in smart MNs development, categorized as follows. First, the solution-processed technology for MNs is introduced, with a focus on various printing technologies. Subsequently, smart MNs designed for sensing, drug delivery, and integrated systems combining diagnosis and treatment are separately summarized. Finally, the prospective and promising applications of next-generation MNs within mediated diagnosis and treatment systems are discussed.
The carbon generalized system of preferences (CGSP) is an innovative incentive mechanism implemented by the Chinese government, which has also become an important part of carbon emission reduction at the living end, and it is of great significance to study whether the Pilot Policy can reduce the carbon emissions of residents. This study firstly accounts for the total carbon emissions and per capita carbon emissions of the residents of 284 cities in China, and on this basis, adopts the SCM method to quantitatively study and analyze the overall and local implementation effects of CGSP in China by taking the first batch of CGSP pilots in China as an example, and further applies the mediation effect model to test the pathways of the role of CGSP. The main findings of the study are as follows: (1) During the period of 2010-2020, the total carbon emissions from urban residents' living in China showed a yearly growth trend, from 36,623.98 ×10-2Mt in 2010-85,241.20 ×10-2Mt in 2020, an increase of 8.83%. Total carbon emissions present a structural difference of "electricity consumption > central heating > private transport > gas (oil, natural gas) consumption". (2) Overall, the implementation of the CGSP had a robust positive impact on the overall carbon emission reduction in the pilot cities, with an average annual emission reduction effect value of 36.53 ×10-2Mt. Locally, the annual net policy effect values of Dongguan, Zhongshan, Heyuan, and Guangzhou are 6169.79 ×10-2, 26,600.17 ×10-2, 17,081.34 ×10-2 and 9393.36 ×10-2Mt respectively. (3) CGSP has a good carbon emission reduction effect by suppressing the impact on residents' carbon emissions through enhancing the city's innovation capacity and promoting electricity saving and consumption reduction, while the mediating effect played by the promotion of green and low-carbon travel in the pilot policy is not significant. Finally, based on the research findings, relevant suggestions are targeted.
Carbon , Cities , China , Humans , Air Pollution/prevention & control , Carbon Dioxide/analysis
The ability to control the catalytic activity of enzymes in chemical transformations is essential for the design and development of artificial catalysts. Herein, we report the synthesis and characterization of functional ligands featuring two 1,4,7,10-tetraazacyclododecane units linked by an azobenzene group and their corresponding dinuclear Zn(II) complexes. We show that the configuration switching (E/Z) of the azobenzene spacer in the ligands and their dinuclear Zn(II) complexes is reversibly controlled by irradiation with UV and visible light. The Zn(II)-metal complexes are light-responsive catalysts for the hydrolytic cleavage of nerve agent simulants, i.e., p-nitrophenyl diphenyl phosphate and methyl paraoxon. The catalytic activity of the Z-isomers of the dinuclear Zn(II) complexes outperformed that of the E-counterparts. Moreover, combining the less active E-isomers with gold nanoparticles induced an enhancement in the hydrolysis rate of p-nitrophenyl diphenyl phosphate. Kinetic analysis has shown that the catalytic site appears to involve a single metal ion. We explain our results by considering the different desolvation effects occurring in the catalyst's configurations in the solution and the catalytic systems involving gold nanoparticles.
Understanding the structure-function relationships encoded on chiral catalysts is important for investigating the fundamental principles of catalytic enantioselectivity. Herein, the synthesis and self-assembly of naphthalene substituted bis-l/d-histidine amphiphiles (bis-l/d-NapHis) in DMF/water solution mixture is reported. The resulting supramolecular assemblies featuring well-defined P/M nanoribbons (NRs). With combination of the (P/M)-NR and metal ion catalytic centers (Mn+ = Co2+, Cu2+, Fe3+), the (P)-NR-Mn+ as chiral supramolecular catalysts show catalytic preference to 3,4-dihydroxy-S-phenylalanine (S-DOPA) oxidation while the (M)-NR-Mn+ show enantioselective bias to R-DOPA oxidation. In contrast, their monomeric counterparts bis-l/d-NapHis-Mn+ display an inverse and dramatically lower catalytic selectivity in the R/S-DOPA oxidation. Among them, the Co2+-coordinated supramolecular nanostructures show the highest catalytic efficiency and enantioselectivity (select factor up to 2.70), while the Fe3+-coordinated monomeric ones show nearly racemic products. Analysis of the kinetic results suggests that the synergistic effect between metal ions and the chiral supramolecular NRs can significantly regulate the enantioselective catalytic activity, while the metal ion-mediated monomeric bis-l/d-NapHis were less active. The studies on association constants and activation energies reveal the difference in catalytic efficiency and enantioselectivity resulting from the different energy barriers and binding affinities existed between the chiral molecular/supramolecular structures and R/S-DOPA enantiomers. This work clarifies the correlation between chiral molecular/supramolecular structures and enantioselective catalytic activity, shedding new light on the rational design of chiral catalysts with outstanding enantioselectivity.
Background: Restless legs syndrome (RLS) is a prevalent sensorimotor nervous system disorder in patients accompanied with insomnia, blood pressure fluctuation, and sympathetic dysfunction. These symptoms may disrupt cerebral hemodynamics. Dynamic cerebral autoregulation (dCA) describes the temporary response of cerebrovascular system to abrupt fluctuations in blood pressure, which keep cerebral blood flow stable and serve as a marker of cerebrovascular system ability. Objective: This research aimed to assess dCA in RLS patients. Methods: In this study, RLS patients were recruited and subsequently classified into four groups (mild, moderate, severe, and very severe) based on the International RLS Rating Scale (IRLS). Healthy controls matched for age and sex were enrolled. All participants were evaluated dCA by assessing phase difference (PD). A portion of patients with RLS was reassessed for dCA after one month of medication therapy (pramipexole [0.125 mg/day] and gabapentin [300 mg/day]). Results: There were altogether 120 patients with RLS and 30 controls completed the polysomnography and dCA assessment. PD was lower in the moderate, severe, and very severe RLS groups than that in the controls and mild RLS groups. Periodic limb movement index (PLMI), arousal index, and IRLS all showed a linear correlation with PD in RLS patients. Additionally, PD increased in RLS patients after therapy. Conclusion: The dCA was compromised in moderate, severe, and very severe RLS patients and was negatively correlated with the IRLS, arousal index, and PLMI. After 1 month of therapy, dCA improved in RLS patients.
L/D-Phenylglycine amphiphiles and metal ions with peroxidase-like activity self-assembled into chiral nanoribbons, which act as efficient chiral supramolecular nanozymes for catalyzing the 3,4-dihydroxy-L/D-phenylalanine (L/D-DOPA) oxidation reactions. The catalytic efficiency and enantioselectivity are dominated by the chirality transfer and the synergistic effect between the metal ions and chiral nanoribbons.
Innate immune response is the first line of defense for the host against virus invasion. One important response is the synthesis and secretion of type I interferon (IFN-I) in the virus-infected host cells. Here, we found that respiratory syncytial virus (RSV) infection induced high expression of TRIM25, which belongs to the tripartite motif-containing (TRIM) family of proteins. TRIM25 bound and activated retinoic acid-inducible gene I (RIG-I) by K63-linked ubiquitination. Accordingly, RIG-I mediated the production of IFN-I mainly through the nuclear factor kappa-B (NF-κB) pathway in respiratory epithelial cells. Interestingly, IFN-I, in turn, promoted a high expression of TRIM38 which downregulated the expression of IFN-I by reducing the protein level of RIG-I by K48-linked ubiquitination. More importantly, the binding site of TRIM25 to RIG-I was found in the narrow 25th-43rd amino acid (aa) region of RIG-I N-terminus. In contrast, the binding sites of TRIM38 to RIG-I were found in a much wider amino acid region, which included the binding site of TRIM25 on RIG-I. As a result, TRIM38 inhibits the production of IFN-I by competing with TRIM25 for RIG-I binding. Thus, TRIM38 negatively regulates RIG-I activation to, in turn, downregulate IFN-I expression, thus interfering with host immune response. A negative feedback loop effectively "puts the brakes" on the reaction once host immune response is overactivated and homeostasis is unbalanced. We also discovered that TRIM25 bound RIG-I by a new K63-linked ubiquitination located at K-45 of the first caspase recruitment domain (CARD). Collectively, these results confirm an antagonism between TRIM38 and TRIM25 in regulating IFN-I production by affecting RIG-I activity following RNA virus infection.
Liquid crystal elastomers (LCEs) blended with photothermal nanofillers can reversibly and rapidly deform their shapes under external optical stimuli. However, nanointerfacial slipping inevitably occurs between the LCE molecules and the nanofillers due to their weak physical interactions, eventually resulting in cyclic instability. This work presents a versatile strategy to fabricate nanointerfacial-slipping-restricted photoactuation elastomers by chemically bonding the nanofillers into a thermally actuatable liquid crystal network. We experimentally and theoretically investigated three types of metal-based nanofillers, including zero-dimensional (0D) nanoparticles, one-dimensional (1D) nanowires, and two-dimensional (2D) nanosheets. The toughly crosslinked nanointerface allows for remarkably promoted interfacial thermal conductivity and stress transfer. Therefore, the resultant actuators enable the realization of long-term-cyclic-stability 4D-printed flexible intelligent systems such as the optical gripper, crawling robot, light-powered self-sustained windmill, butterflies with fluttering wings, and intelligent solar energy collection system.
With the development of wearable devices and hafnium-based ferroelectrics (FE), there is an increasing demand for high-performance flexible ferroelectric memories. However, developing ferroelectric memories that simultaneously exhibit good flexibility and significant performance has proven challenging. Here, we developed a high-performance flexible field-effect transistor (FeFET) device with a thermal budget of less than 400 °C by integrating Zr-doped HfO2 (HZO) and ultra-thin indium tin oxide (ITO). The proposed FeFET has a large memory window (MW) of 2.78 V, a high current on/off ratio (ION/IOFF) of over 108, and high endurance up to 2×107 cycles. In addition, the FeFETs under different bending conditions exhibit excellent neuromorphic properties. The device exhibits excellent bending reliability over 5×105 pulse cycles at a bending radius of 5 mm. The efficient integration of hafnium-based ferroelectric materials with promising ultrathin channel materials (ITO) offers unique opportunities to enable high-performance back-end-of-line (BEOL) compatible wearable FeFETs for edge intelligence applications.
Realization of dendric signal processing in the human brain is of great significance for spatiotemporal neuromorphic engineering. Here, we proposed an ionic dendrite device with multichannel communication, which could realize synaptic behaviors even under an ultralow action potential of 80 mV. The device not only could simulate one-to-one information transfer of axons but also achieve a many-to-one modulation mode of dendrites. By the adjustment of two presynapses, Pavlov's dog conditioning experiment was learned successfully. Furthermore, the device also could emulate the biological synaptic competition and synaptic cooperation phenomenon through the comodulation of three presynapses, which are crucial for artificial neural network (ANN) implementation. Finally, an ANN was further constructed to realize highly efficient and anti-interference recognition of fashion patterns. By introducing the cooperative device, synaptic weight updates could be improved for higher linearity and larger dynamic regulation range in neuromorphic computing, resulting in higher recognition accuracy and efficiency. Such an artificial dendric device has great application prospects in the processing of more complex information and the construction of an ANN system with more functions.
Axons , Brain , Humans , Animals , Dogs , Action Potentials , Diffusion , Engineering , Ions
In a global context, the production of urban solid waste significantly varies with changes in living standards. This trend exhibits diversity across different countries and regions, reflecting shifts in lifestyles as well as varying needs and challenges in waste management strategies. However, current standards of waste recycling are too complex for the general public to follow. In this study, we propose a model called DSYOLO-Trash to identify solid waste by integrating the dual attention mechanisms convolutional block attention module (CBAM) and Contextual Transformer Networks(CotNet), which significantly enhance its ability to mine channel-related and spatial attention features while optimizing the learning process. We apply the deep simple online and realtime tracking (DeepSORT) object tracking algorithm to solid waste detection for the first time in the literature to enable the real-time identification and tracking of waste. We also develop a multi-label dataset of mixed solid waste, called MMTrash, to realistically simulate actual scenarios of waste classification. Our proposed DSYOLO-Trash delivered superior performance to classical detection algorithms on both the MMTrash and the TrashNet datasets. Our system combines the improved you only look once(YOLO) algorithm with DeepSORT technology by using industrial cameras and PLC-controlled robotic arms to intelligently sort waste. The work here constitutes an important contribution to intelligent waste management and the sustainable development of cities.
Garbage , Solid Waste , Algorithms , Cities , Electric Power Supplies
In recent years, memristors have successfully demonstrated their significant potential in artificial neural networks (ANNs) and neuromorphic computing. Nonetheless, ANNs constructed by crossbar arrays suffer from cross-talk issues and low integration densities. Here, we propose an eight-layer three-dimensional (3D) vertical crossbar memristor with an ultrahigh rectify ratio (RR > 107) and an ultrahigh nonlinearity (>105) to overcome these limitations, which enables it to reach a >1 Tb array size without reading failure. Furthermore, the proposed 3D RRAM shows advanced endurance (>1010 cycles), retention (>104 s), and uniformity. In addition, several synaptic functions observed in the human brain were mimicked. On the basis of the advanced performance, we constructed a novel 3D ANN, whose learning efficiency and recognition accuracy were enhanced significantly compared with those of conventional single-layer ANNs. These findings hold promise for the development of highly efficient, precise, integrated, and stable VLSI neuromorphic computing systems.
The development of highly efficient active integrated photonic circuits is crucial for advancing information and computing science. Lead halide perovskite semiconductors, with their exceptional optoelectronic properties, offer a promising platform for such devices. In this study, active micro multifunctional photonic devices were fabricated on monocrystalline CsPbBr3 perovskite thin films using a top-down etching technique with focused ion beams. The etched microwire exhibited a high-quality micro laser that could serve as a light source for integrated devices, facilitating angle-dependent effective propagation between coupled perovskite-microwire waveguides. Employing this strategy, multiple perovskite-based active integrated photonic devices were realized for the first time. These devices included a micro beam splitter that coherently separated lasing signals, an X-coupler performing transfer matrix functions with two distinguishable light sources, and a Mach-Zehnder interferometer manipulating the splitting and coalescence of coherent light beams. These results provide a proof-of-concept for active integrated functionalized photonic devices based on perovskite semiconductors, representing a promising avenue for practical applications in integrated optical chips.
The oxidation characteristics and spontaneous combustion (SC) tendency of raw long-flame coal (RC), water-soaked 200-day coal (S200), pre-oxidized water-soaked coal at 200 °C (O200S200), and pre-oxidized soaked coal at 300 °C (O300S200) in an oxygen-poor environment were investigated using a programmed warming system. The results show that pre-oxidation water-soaked treatment (PWT) promotes the coal-oxygen complex reaction and increases the rate of coal oxygen consumption (OCR) and the rate of carbon and oxygen compound production. The rate of CO and CO2 production of the water-soaked (WS) coal increased by 0.329 mol·(cm3·s)-1 and 0.922 mol·(cm3·s)-1, respectively, compared with that of the original coal sample. PWT reduces the activation energy of coal in the low-temperature oxidation stage (the maximum difference can be up to 110.99 kJ/mol) and enhances the oxidizing and heat-releasing capacity. There was a synergistic effect between the pre-oxidation (PO) and WS treatment, and the lowest comprehensive determination index of the SC propensity of coal in O200S200 samples was 831.92 which was 4.72 lower than that of RC samples, presenting a more SC tendency. Low oxygen concentration has an inhibitory effect on the oxidation characteristic parameters of coal, and the apparent activation energy of the low-temperature oxidation stage of pre-oxidized water-soaked coal (PWC) increased to 206.418 kJ/mol at 3% oxygen concentration. The lower the oxygen concentration of the anoxic environment, the lower the risk of SC of the coal samples. The results of the study can provide theoretical guidance for the identification and prevention of SC disasters in coal seams with shallow burial and close spacing.
Coal , Oxygen , Oxygen/analysis , Spontaneous Combustion , Water , Hot Temperature
Researching optoelectronic memristors capable of integrating sensory and processing functions is essential for advancing the development of efficient neuromorphic vision. Here, we experimentally demonstrated an all-optical controlled and self-rectifying optoelectronic memristor (OEM) crossbar array with the function of multilevel storage under light stimuli. The NiO/TiO2 device exhibits an ultrahigh (>104) rectifying ratio (RR) thus overcoming the presence of sneak current. The reversible conductance modulation without electric signal involvement provides a novel way to realize ultrafast information processing. The proposed OEM array realized synaptic functions observed in the human brain, including long-term potentiation (LTP), long-term depression (LTD), paired-pulse facilitation (PPF), the transition from short-term memory (STM) to long-term memory (LTM), and learning experience behaviors successfully. The authors present a novel OEM crossbar that possesses complete light-modulation capabilities, potentially advancing the future development of efficient neuromorphic vision.
BACKGROUND: The global coronavirus disease 2019 (COVID-19) pandemic seriously affected people's lives. We evaluated anxiety and depression among patients with insomnia in northeast China during the first wave and release of COVID-19, providing a basis for the clinical diagnosis and treatment of insomnia. METHODS: We enrolled 4211 patients with insomnia from January 2016 to February 2020, August 2020 to February 2022, August 2022 to December 2022, and January 2023 to February 2023, from our institution. Sleep quality was evaluated using the Athens Insomnia Scale, Insomnia Severity Index (ISI), and Pittsburgh sleep quality index (PSQI), while mood disorder and fatigue were evaluated using the Hhospital anxiety and depression scale (HAD), Patient Health Questionnaire-9 (PHQ-9), Generalized Anxiety Disorder (GAD-7), and Fatigue Scale-14 (FS-14). RESULTS: Insomnia with depression increased in prevalence after COVID-19 compared with before (12.8 % vs. 15.3 %, P < 0.05), while the age of patients decreased [(50.2 ± 15.2) vs. (47.5 ± 16.8), P < 0.05]. The number of patients with insomnia and severe depression increased compared with before COVID-19 (20.3 % vs. 25.3 %, P < 0.05). A higher proportion of patients with insomnia for >2 years had depression (P < 0.05). As the epidemic subsided, insomnia increased among young and male patients (young patients: 55.2 % vs. 37.0 %; male patients: 41 % vs. 27.4 %, respectively; P < 0.05). The proportion of patients with insomnia with anxiety and depression increased (53.8 % vs. 51.8 %ï¼P < 0.05), the proportion with moderate to severe anxiety increased (7.6 % vs. 13.5 %, P < 0.05), and moderate and severe depression decreased (moderate: 25.6 % vs. 19.1 %, severe: 25.8 % vs. 20.3 %, P < 0.05, respectively). Middle-aged and elderly patients had higher PQSI scores in sleep latency, habitual sleep efficiency, subjective sleep quality, and use of sleep medications than young patients (P < 0.05). The PSQI score was positively correlated with the PHQ-9 score (r = 0.526), GAD-7 score (r = 0.563), and FS-14 score (r = 0.316) (P < 0.05). LIMITATIONS: The study was single-center, the sample size was small, and assessment data were lacking from early in the epidemic. The scale is subjective, which may affect the accuracy. CONCLUSION: Insomnia with depression increased during COVID-19. The patients were younger than before the epidemic, and a higher proportion with insomnia for >2 years had depression. The proportion of patients with insomnia with anxiety and depression was higher after the epidemic period, and the degree worsened. The proportion of insomnia with depression decreased after the epidemic period, and the degree alleviated. The proportion of young male patients with insomnia increased. Middle aged and elderly patients with insomnia had poor sleep quality, which was positively correlated with anxiety, depression, and fatigue.
COVID-19 , Sleep Initiation and Maintenance Disorders , Middle Aged , Aged , Humans , Male , COVID-19/epidemiology , Sleep Initiation and Maintenance Disorders/epidemiology , Cross-Sectional Studies , Depression/epidemiology , Depression/diagnosis , SARS-CoV-2 , Surveys and Questionnaires , Anxiety/epidemiology , Anxiety/diagnosis , Anxiety Disorders/epidemiology , Pandemics , China/epidemiology
Due to the limitation of inherent ultra-high electron concentration, the electrical properties of In2O3 resemble those of conductors rather than semiconductors prior to special treatment. In this study, the effect of various annealing treatments on the microstructure, optical properties, and oxygen vacancies of the films and transistors is systematically investigated. Our finding reveals a progressive crystallization trend in the films with increasing annealing temperature. In addition, a higher annealing temperature is also associated with the reduction in the concentration of oxygen vacancies, as well as an elevation in both optical transmittance and optical bandgap. Furthermore, with the implementation of annealing process, the devices gradually transform from no pronounced gate control to exhibit with excellent gate control and electrical performances. The atomic layer deposited Hf-doped In2O3 thin film transistor annealed at 250 °C exhibits optimal electrical properties, with a field-effect mobility of 18.65 cm2 V-1 s-1, a subthreshold swing of 0.18 V/dec, and an Ion/Ioff ratio of 2.76 × 106. The results indicate that the impact of varying annealing temperatures can be attributed to the modulation of oxygen vacancies within the films. This work serves as a complementary study for the existing post-treatment of oxide films and provides a reliable reference for utilization of the annealing process in practical applications.
Emulating the human nervous system to build next-generation computing architectures is considered a promising way to solve the von Neumann bottleneck. Transistors based on ferroelectric layers are strong contenders for the basic unit of artificial neural systems due to their advantages of high speed and low power consumption. In this work, the potential of Fe-TFTs integrating the HfLaO ferroelectric film and ultra-thin ITO channel for artificial synaptic devices is demonstrated for the first time. The Fe-TFTs can respond significantly to pulses as low as 14 ns with an energy consumption of 93.1 aJ, which is at the leading level for similar devices. In addition, Fe-TFTs exhibit essential synaptic functions and achieve a recognition rate of 93.2% for handwritten digits. Notably, a novel reconfigurable approach involving the combination of two types of electrical pulses to realize Boolean logic operations ("AND", "OR") within a single Fe-TFT has been introduced for the first time. The simulations of array-level operations further demonstrated the potential for parallel computing. These multifunctional Fe-TFTs reveal new hardware options for neuromorphic computing chips.
The development of chiral nanostructures-based supramolecular catalysts with satisfied enantioselectivity remains a significantly more challenging task. Herein, the synthesis and self-assembly of various amino acid amphiphiles as chiral supramolecular catalysts after metal ion coordination is reported and systematically investigate their enantioselectivity in asymmetric Diels-Alder reactions. In particular, the self-assembly of l/d-phenylglycine-based amphiphiles (l/d-PhgC16) and Cu(II) into chiral supramolecular catalysts in the methanol/water solution mixture is described, which features the interesting M/P nanohelices (diameter ≈8 nm) and mostly well-aligned M/P nanoribbons (NRs). The M/P supramolecular catalysts show both high but inverse enantioselectivity (>90% ee) in Diels-Alder reactions, while their monomeric counterparts display nearly racemic products. Analysis of the catalytic results suggests the outstanding enantioselectivities are closely related to the specific stereochemical microenvironment provided by the arrangement of the amphiphiles in the supramolecular assembly. Based on the experimental evidence of chirality transfer from supramolecular nanohelices to coordinated Cu(II) and substrate aza-chalcone and the molecular dynamics simulations, the enantioselective catalytic mechanisms are proposed. Moreover, the relationships between molecular structures of amino acid amphiphiles (the hydrophilic head group and hydrophobic alkyl chain length) in supramolecular catalysts and enantioselectivity in Diels-Alder reactions are elaborated.
Chemical double mutant cycles were used to measure the interaction of a N-methyl pyridinium cation with a π-box in a calix[4]pyrrole receptor. Although the cation-π interaction is attractive (-11 kJ mol-1), it is 7 kJ mol-1 less favourable than the corresponding aromatic interaction with the isosteric but uncharged tolyl group.
