The Role of NiO Doping in Reducing the Impact of Humidity on the Performance of SnO2‐Based Gas Sensors: Synthesis Strategies,and Phenomenological and Spectroscopic Studies

The humidity dependence of the gas‐sensing characteristics in SnO₂‐based sensors, one of the greatest obstacles in gas‐sensor applications, is reduced to a negligible level by NiO doping. In a dry atmosphere, undoped hierarchical SnO₂ nanostructures prepared by the self‐assembly of crystalline nanosheets show a high CO response and a rapid response speed. However, the gas response, response/recovery speeds, and resistance in air are deteriorated or changed significantly in a humid atmosphere. When hierarchical SnO₂ nanostructures are doped with 0.64–1.27 wt% NiO, all of the gas‐sensing characteristics remain similar, even after changing the atmosphere from a dry to wet one. According to diffuse‐reflectance Fourier transform IR measurements, it is found that the most of the water‐driven species are predominantly absorbed not by the SnO₂ but by the NiO, and thus the electrochemical interaction between the humidity and the SnO₂ sensor surface is totally blocked. NiO‐doped hierarchical SnO₂ sensors exhibit an exceptionally fast response speed (1.6 s), a fast recovery speed (2.8 s) and a superior gas response (R_a/R_g = 2.8 at 50 ppm CO (R_a: resistance in air, R_g: resistance in gas)) even in a 25% r.h. atmosphere. The doping of hierarchical SnO₂ nanostructures with NiO is a very‐promising approach to reduce the dependence of the gas‐sensing characteristics on humidity without sacrificing the high gas response, the ultrafast response and the ultrafast recovery.     

An O2 Self‐Supplementing and Reactive‐Oxygen‐Species‐Circulating Amplified Nanoplatform via H2O/H2O2 Splitting for Tumor Imaging and Photodynamic Therapy

Conventional photodynamic therapy (PDT) has limited applications in clinical cancer therapy due to the insufficient O₂ supply, inefficient reactive oxygen species (ROS) generation, and low penetration depth of light. In this work, a multifunctional nanoplatform, upconversion nanoparticles (UCNPs)@TiO₂@MnO₂ core/shell/sheet nanocomposites (UTMs), is designed and constructed to overcome these drawbacks by generating O₂ in situ, amplifying the content of singlet oxygen (¹O₂) and hydroxyl radical (?OH) via water‐splitting, and utilizing 980 nm near‐infrared (NIR) light to increase penetration depth. Once UTMs are accumulated at tumor site, intracellular H₂O₂ is catalyzed by MnO₂ nanosheets to generate O₂ for improving oxygen‐dependent PDT. Simultaneously, with the decomposition of MnO₂ nanosheets and 980 nm NIR irradiation, UCNPs can efficiently convert NIR to ultraviolet light to activate TiO₂ and generate toxic ROS for deep tumor therapy. In addition, UCNPs and decomposed Mn²⁺ can be used for further upconversion luminescence and magnetic resonance imaging in tumor site. Both in vitro and in vivo experiments demonstrate that this nanoplatform can significantly improve PDT efficiency with tumor imaging capability, which will find great potential in the fight against tumor.     

Ultrasensitive Detection of VOCs Using a High‐Resolution CuO/Cu2O/Ag Nanopattern Sensor

The p‐type semiconducting copper oxides (CuO and Cu₂O) are promising materials for gas sensors, owing to their characteristic oxygen adsorption properties and low operation temperature. In this study, the sensing performance of a CuO‐based chemiresistor is significantly enhanced by incorporating Ag nanoparticles on high‐resolution p‐type CuO/Cu₂O nanopattern channels. The high‐resolution CuO/Cu₂O/Ag nanochannel is fabricated using a unique top‐down nanolithographic approach. The gas response (ΔR/R_a) of the CuO/Cu₂O/Ag gas sensor increases by a maximum factor of 7.3 for various volatile organic compounds compared with a pristine CuO/Cu₂O gas sensor. The sensors exhibit remarkable sensitivity (ΔR/R_a = 8.04) at 125 parts per billion (ppb) for acetone analytes. As far as it is known, this is the highest sensitivity achieved for p‐type metal oxide semiconductor (MOS)‐based gas sensors compared to previous studies. Furthermore, the outstanding gas responses observed in this study are superior to the most of n‐type MOS‐based gas sensors. The high sensitivity of the sensor is attributed to i) the high resolution (≈30 nm), high aspect ratio (≈12), and ultrasmall grain boundaries (≈10 nm) of the CuO/Cu₂O nanopatterns and ii) the electronic sensitization and chemical sensitization effects induced by incorporating Ag nanoparticles on the CuO/Cu₂O channels.     

Development of a Highly Selective,Sensitive, and Fast Response Upconversion Luminescent Platform for Hydrogen Sulfide Detection

Hydrogen sulfide (H₂S) has been recognized as one of most important gaseous signaling molecules mediated by a variety of physiological and pathological processes. Yet, its functions remain largely elusive due to the lack of potent monitoring methods. Hereby this issue is addressed with a powerful new platform—dye‐assembled upconversion nanoparticles (UCNPs). A series of chromophores with different absorption bands and fast responses towards H₂S is combined with UCNPs and results in a library of H₂S sensors with responsive emission signals ranging from the visible to the near‐infrared (NIR) region. These nanoprobes demonstrate highly selective and rapid responses to H₂S in vitro and in cells. Furthermore, H₂S levels in blood can be detected using the developed nanoprobes. Hence the reported H₂S sensing platform can serve as a powerful diagnostic tool to research H₂S functions and to investigate H₂S‐related diseases.     

Imaging‐Guided pH‐Sensitive Photodynamic Therapy Using Charge Reversible Upconversion Nanoparticles under Near‐Infrared Light

Photodynamic therapy (PDT) based on upconversion nanoparticles (UCNPs) can effectively destroy cancer cells under tissue‐penetrating near‐infrared light (NIR) light. Herein, we synthesize manganese (Mn²⁺)‐doped UCNPs with strong red light emission at ca. 660 nm under 980 nm NIR excitation to activate Chlorin e6 (Ce6), producing singlet oxygen (¹O₂) to kill cancer cells. A layer‐by‐layer (LbL) self‐assembly strategy is employed to load multiple layers of Ce6 conjugated polymers onto UCNPs via electrostatic interactions. UCNPs with two layers of Ce6 loading (UCNP@2xCe6) are found to be optimal in terms of Ce6 loading and ¹O₂ generation. By further coating UCNP@2xCe6 with an outer layer of charge‐reversible polymer containing dimethylmaleic acid (DMMA) groups and polyethylene glycol (PEG) chains, we obtain a UCNP@2xCe6‐DMMA‐PEG nanocomplex, the surface of which is negatively charged and PEG coated under pH 7.4; this could be converted to have a positively charged naked surface at pH 6.8, significantly enhancing cell internalization of nanoparticles and increasing in vitro NIR‐induced PDT efficacy. We then utilize the intrinsic optical and paramagnetic properties of Mn²⁺‐doped UCNPs for in vivo dual modal imaging, and uncover an enhanced retention of UCNP@2xCe6‐DMMA‐PEG inside the tumor after intratumoral injection, owing to the slightly acidic tumor microenvironment. Consequently, a significantly improved in vivo PDT therapeutic effect is achieved using our charge‐reversible UCNP@2xCe6‐DMMA‐PEG nanoparticles. Finally, we further demonstrate the remarkably enhanced tumor‐homing of these pH‐responsive charge‐switchable nanoparticles in comparison to a control counterpart without pH sensitivity after systemic intravenous injection. Our results suggest that UCNPs with finely designed surface coatings could serve as smart pH‐responsive PDT agents promising in cancer theranostics.     

Stretchable and Temperature‐Sensitive Polymer Optical Fibers for Wearable Health Monitoring

Stretchable physical sensors that can detect and quantify human physiological signals such as temperature, are essential to the realization of healthcare devices for biomedical monitoring and human–machine interfaces. Despite recent achievements in stretchable electronic sensors using various conductive materials and structures, the design of stretchable sensors in optics remains a considerable challenge. Here, an optical strategy for the design of stretchable temperature sensors, which can maintain stable performance even under a strain deformation up to 80%, is reported. The optical temperature sensor is fabricated by the incorporation of thermal‐sensitive upconversion nanoparticles (UCNPs) in stretchable polymer‐based optical fibers (SPOFs). The SPOFs are made from stretchable elastomers and constructed in a step‐index core/cladding structure for effective light confinements. The UCNPs, incorporated in the SPOFs, provide thermal‐sensitive upconversion emissions at dual wavelengths for ratiometric temperature sensing by near‐infrared excitation, while the SPOFs endow the sensor with skin‐like mechanical compliance and excellent light‐guiding characteristics for laser delivery and emission collection. The broad applications of the proposed sensor in real‐time monitoring of the temperature and thermal activities of the human body, providing optical alternatives for wearable health monitoring, are demonstrated.     

A New Single 808 nm NIR Light‐Induced Imaging‐Guided Multifunctional Cancer Therapy Platform

The NIR light‐induced imaging‐guided cancer therapy is a promising route in the targeting cancer therapy field. However, up to now, the existing single‐modality light‐induced imaging effects are not enough to meet the higher diagnosis requirement. Thus, the multifunctional cancer therapy platform with multimode light‐induced imaging effects is highly desirable. In this work, captopril stabilized‐Au nanoclusters Au₂₅(Capt)₁₈?(Au₂₅) are assembled into the mesoporous silica shell coating outside of Nd³⁺‐sensitized upconversion nanoparticles (UCNPs) for the first time. The newly formed Au₂₅ shell exhibits considerable photothermal effects, bringing about the photothermal imaging and photoacoustic imaging properties, which couple with the upconversion luminescence imaging. More importantly, the three light‐induced imaging effects can be simultaneously achieved by exciting with a single NIR light (808 nm), which is also the triggering factor for the photothermal and photodynamic cancer therapy. Besides, the nanoparticles can also present the magnetic resonance and computer tomography imaging effects due to the Gd³⁺ and Yb³⁺ ions in the UCNPs. Furthermore, due to the photodynamic and the photothermal effects, the nanoparticles possess efficient in vivo tumor growth inhibition under the single irradiation of 808 nm light. The multifunctional cancer therapy platform with multimode imaging effects realizes a true sense of light‐induced imaging‐guided cancer therapy.     

Solution‐Processable Near‐Infrared–Responsive Composite of Perovskite Nanowires and Photon‐Upconversion Nanoparticles

Organolead halide perovskites (OHPs) have shown unprecedented potentials in optoelectronics. However, the inherent large bandgap has restrained its working wavelength within 280–800 nm, while light at other regions, e.g., near‐infrared (NIR), may cause drastic thermal heating effect that goes against the duration of OHP devices, if not properly exploited. Herein, a solution processable and large‐scale synthesis of multifunctional OHP composites containing lanthanide‐doped upconversion nanoparticles (UCNPs) is reported. Upon NIR illumination, the upconverted photons from UCNPs at 520–550 nm can be efficiently absorbed by closely surrounded OHP nanowires (NWs) and photocurrent is subsequently generated. The narrow full width at half maximum of the absorption of rare earth ions (Yb³⁺ and Er³⁺) has ensured high‐selective NIR response. Lifetime characterizations have suggested that Förster resonance energy transfer with an efficiency of 28.5% should be responsible for the direct energy transfer from UCNPs to OHP NWs. The fabricated proof‐of‐concept device has showcased perfect response to NIR light at 980 and 1532 nm, which has paved new avenues for applications of such composites in remote control, distance measurement, and stealth materials.     

Near‐Infrared Photoregulated Drug Release in Living Tumor Tissue via Yolk‐Shell Upconversion Nanocages

Phototrigger‐controlled drug‐release devices (PDDs) can be conveniently manipulated by light to obtain on‐demand release patterns, thereby affording an improved therapeutic efficacy. However, no example of the PDDs has been demonstrated beyond the cellular level to date. By loading 7‐amino‐coumarin derivative caged anticancer drug chlorambucil to yolk–shell structured nanocages possessing upconversion nanophosphors (UCNPs) as moveable core and silica as mesoporous shell, a near‐infrared (NIR)‐regulated PDD is successfully created. In vitro experiments demonstrate that drug release from the PDD could be triggered by continuous‐wave 980 nm light in a controlled pattern. The PDD could be taken up by cancer cells and release the drug to kill cancer cells upon NIR irradiation. Further in vivo studies demonstrate that the PDD can effectively response the NIR stimuli in living tissue. This is the first example of successful NIR‐regulated drug release in living animal model. Such achievement resolves the problem of low tissue penetration depth for traditional PDDs by adopting UCNPs as an NIR light switcher, which gives impetus to practical applications.     

Triplet–Triplet Annihilation‐Based Anti‐Stokes Oxygen Sensing Materials with a Very Broad Dynamic Range

A novel concept for designing optical oxygen sensing materials is reported. Oxygen‐sensitive anti‐Stokes emission is generated via triplet–triplet annihilation‐based upconversion and serves as an analytical parameter. Porous glass beads are used to incorporate the “sensing chemistry” including a sensitizer and an annihilator dissolved in a high boiling solvent. The beads are dispersed in silicone rubber or Teflon AF to produce solid state optodes. Inexpensive low power light sources (LEDs) are used for the excitation. The upconverted emission shows unmatched sensitivity both for the luminescence decay time and for the luminescence intensity. The latter features unusual quadratic Stern‐Volmer plots. Much lower sensitivity of the residual NIR luminescence of the sensitizer allows determination of pO₂ in the broad dynamic range from trace oxygen quantities to ≈40 kPa. Interrogation of the sensors in frequency domain is demonstrated. Influence of the excitation light power on the calibration, temperature effects, dynamic response to altering pO₂, and photostability of the sensing materials are also investigated.     

Low‐Temperature Growth of SnO2 Nanorod Arrays and Tunable n–p–n Sensing Response of a ZnO/SnO2 Heterojunction for Exclusive Hydrogen Sensors

Uniform SnO₂ nanorod arrays have been deposited at low temperature by plasma‐enhanced chemical vapor deposition (PECVD). ZnO surface modification is used to improve the selectivity of the SnO₂ nanorod sensor to H₂ gas. The ZnO‐modified SnO₂ nanorod sensor shows a normal n‐type response to 100 ppm CO, NH₃, and CH₄ reducing gas whereas it exhibits concentration‐dependent n–p–n transitions for its sensing response to H₂ gas. This abnormal sensing behavior can be explained by the formation of n‐ZnO/p‐Zn‐O‐Sn/n‐SnO₂ heterojunction structures. The gas sensors can be used in highly selective H₂ sensing and this study also opens up a general approach for tailoring the selectivity of gas sensors by surface modification.     

Remarkable NIR Enhancement of Multifunctional Nanoprobes for In Vivo Trimodal Bioimaging and Upconversion Optical/T2‐Weighted MRI‐Guided Small Tumor Diagnosis

Effective nanoprobes and contrast agents are urgently sought for early‐stage cancer diagnosis. Upconversion nanoparticles (UCNPs) are considerable alternatives for bioimaging, cancer diagnosis, and therapy. Yb³⁺/Tm³⁺ co‐doping brings both emission and excitation wavelengths into the near‐infrared (NIR) region, which is known as “optical transmission window” and ideally suitable for bioimaging. Here, NIR emission intensity is remarkably enhanced by 113 times with the increase of Yb³⁺ concentration from 20% to 98% in polyethylene glycol (PEG) modified NaYF₄:Yb³⁺/Tm³⁺ UCNPs. PEG‐UCNPs‐5 (98% Yb³⁺) can act as excellent nanoprobes and contrast agents for trimodal upconversion (UC) optical/CT/T₂‐weighted magnetic resonance imaging (MRI). In addition, the enhanced detection of lung in vivo long‐lasting tracking, as well as possible clearance mechanism and excretion routes of PEG‐UCNPs‐5 have been demonstrated. More significantly, a small tumor down to 4 mm is detected in vivo via intravenous injection of these nanoprobes under both UC optical and T₂‐weighted MRI modalities. PEG‐UCNPs‐5 can emerge as bioprobes for multi‐modal bioimaging, disease diagnosis, and therapy, especially the early‐stage tumor diagnosis.     

A Multi‐Functional Highly Efficient Upconversion Luminescent Film with an Array of Dielectric Microbeads Decorated with Metal Nanoparticles

Upconversion nanoparticles (UCNPs) have been integrated with photonic platforms to overcome the intrinsically low quantum efficiency limit of upconversion luminescence (UCL). However, platforms based on thin films lack transferability and flexibility, which hinders their broader and more practical application. A plasmonic structure is developed that works as a multi‐functional platform for flexible, transparent, and washable near‐infrared (NIR)‐to‐visible UCL films with ultra‐strong UCL intensity. The platform consists of dielectric microbeads decorated with plasmonic metal nanoparticles on an insulator/metal substrate. Distinct improvements in NIR confinement, visible light extraction, and boosted plasmonic effects for upconversion are observed. With weak NIR excitation, the UCL intensity is higher by three orders of magnitude relative to the reference platform. When the microbeads are organized in a square lattice array, the functionality of the platform can be expanded to wearable and washable UCL films. The platform can be transferred to transparent, flexible, and foldable films and still emit strong UCL with a wide viewing angle.     

A Self-Powered,Rechargeable, and Wearable Hydrogel Patch for Wireless Gas Detection with Extraordinary Performance

Flexible gas sensors play an indispensable role in diverse applications spanning from environmental monitoring to portable medical electronics. Full wearable gas monitoring system requires the collaborative support of high-performance sensors and miniaturized circuit module, whereas the realization of low power consumption and sustainable measurement is challenging. Here, a self-powered and reusable all-in-one NO₂ sensor is proposed by structurally and functionally coupling the sensor to the battery, with ultrahigh sensitivity (1.92%/ppb), linearity (R² = 0.999), ultralow theoretical detection limit (0.1 ppb), and humidity immunity. This can be attributed to the regulation of the gas reaction route at the molecular level. The addition of amphiphilic zinc trifluoromethanesulfonate (Zn(OTf)₂) enables the H₂O-poor inner Helmholtz layer to be constructed at the electrode–gel interface, thereby facilitating the direct charge transfer process of NO₂ here. The device is then combined with a well-designed miniaturized low-power circuit module with signal conditioning, processing and wireless transmission functions, which can be used as wearable electronics to realize early and remote warning of gas leakage. This study demonstrates a promising way to design a self-powered, sustainable, and flexible gas sensor with high performance and its corresponding wireless sensing system, providing new insight into the all-in-one system of gas detection.     

基于石墨烯的NO2和NH3气体传感器研究进展

室温下石墨烯具有较大的分子吸附比表面积、低噪声、高载流子迁移率等优异电学性能,是一种性能极佳的传感材料。与传统无机氧化物气体传感器相比,石墨烯气体传感器具有工作温度低、能耗小、恢复性高的优点。文章对两种石墨烯气体传感器的研究进展进行了综述。首先根据气体选择性不同,研究了NO₂和NH₃两种石墨烯气体传感器。然后对它们的灵敏度、气体响应灵敏度、响应时间等特性进行了分析对比。该项分析研究工作对气体传感器的实际应用与推广具有一定参考价值。     

Atomic‐Level Passivation of Individual Upconversion Nanocrystal for Single Particle Microscopic Imaging

Lanthanide‐doped upconversion nanoparticles (UCNPs) have significant applications for single‐molecule probes and high‐resolution display. However, one of their major hurdles is the weak luminescence, and this remains a grand challenge to achieve at the single‐particle level. Here, 484‐fold luminescence enhancement in LuF₃:Yb³⁺, Er³⁺ rhombic flake UCNPs is achieved, thanks to the Yb³⁺‐mediated local photothermal effect, and their original morphology, size, and good dispersibility are well preserved. These data show that the surface atomic structure of UCNPs as well as transfer from amorphous to ordered crystal structure is modulated by making use of the local photothermal conversion that is generated by the directional absorption of 980 nm light by Yb³⁺ ions. The confocal luminescence images obtained by super‐resolution stimulated emission depletion also show the great enhancement of individual LuF₃:Yb³⁺, Er³⁺ nanoparticles; the high signal‐to‐noise ratio images indicate that the laser treatment technology opens the door for single particle imaging and practical application.     

Encapsulation of Semiconductor Gas Sensors with Gas Barrier Films for USN Application

Sensor nodes in ubiquitous sensor networks require autonomous replacement of deteriorated gas sensors with reserved sensors, which has led us to develop an encapsulation technique to avoid poisoning the reserved sensors and an autonomous activation technique to replace a deteriorated sensor with a reserved sensor. Encapsulations of In₂O₃ nanoparticles with poly(ethylene‐co‐vinyl alcohol) (EVOH) or polyvinylidene difluoride (PVDF) as gas barrier layers are reported. The EVOH or PVDF films are used for an encapsulation of In2O3 as a sensing material and are effective in blocking In2O3 from contacting formaldehyde (HCHO) gas. The activation process of In2O3 by removing the EVOH through heating is effective. However, the thermal decomposition of the PVDF affects the property of the In₂O₃ in terms of the gas reactivity. The response of the sensor to HCHO gas after removing the EVOH is 26%, which is not significantly different with the response of 28% in a reference sample that was not treated at all. We believe that the selection of gas barrier materials for the encapsulation and activation of In2O3 should be considered because of the ill effect the byproduct of thermal decomposition has on the sensing materials and other thermal properties of the barrier materials.     

A General Solution to Mitigate Water Poisoning of Oxide Chemiresistors: Bilayer Sensors with Tb4O7 Overlayer

Water poisoning, the dependence of gas-sensing characteristics on moisture, in oxide chemiresistors remains a long-standing challenge. Various approaches are explored to mitigate water poisoning but they are often accompanied by significant deterioration of sensing capabilities such as gas response deterioration, gas selectivity alteration, and sensor resistance increase up to unmeasurable levels. Herein, a novel sensor design with a moisture-blocking Tb₄O₇ overlayer is suggested as a facile and universal strategy to remove moisture poisoning without sacrificing intrinsic sensing properties. A submicrometer-thick coating of Tb₄O₇ overlayer on In₂O₃ sensors effectively eliminates the humidity dependence of the gas-sensing characteristics without significantly altering the gas response, selectivity, and sensor resistance. Furthermore, the general validity of the water-blocking effect using the Tb₄O₇ overlayer is confirmed in diverse gas sensors using SnO₂, ZnO, and Pd/SnO₂. The negligible moisture interference of the bilayer sensor is explained in terms of the hydrophobic nature of the Tb₄O₇ overlayer and the prevention of formation of the  OH radical by the interaction between Tb₄O₇ and In₂O₃. A universal solution to design diverse humidity-independent gas sensors with different gas selectivities can open up new pathways toward building accurate and robust gas sensors with new functionalities and high-performance artificial olfaction.     

Single Ho3+‐Doped Upconversion Nanoparticles for High‐Performance T2‐Weighted Brain Tumor Diagnosis and MR/UCL/CT Multimodal Imaging

Multimodal bio‐imaging has attracted great attention for early and accurate diagnosis of tumors, which, however, suffers from the intractable issues such as complicated multi‐step syntheses for composite nanostructures and interferences among different modalities like fluorescence quenching by MRI contrast agents (e.g., magnetic iron oxide NPs). Herein, the first example of T₂‐weighted MR imaging of Ho³⁺‐doped upconversion nanoparticles (UCNPs) is presented, which, very attractively, could also be simultaneously used for upconversion luminesence (UCL) and CT imaging, thus enabling high performance multi‐modal MRI/UCL/CT imagings in single UCNPs. The new finding of T₂‐MRI contrast enhancement by integrated sensitizer (Yb³⁺) and activator (Ho³⁺) in UCNPs favors accurate MR diagnosis of brain tumor and provides a new strategy for acquiring T₂‐MRI/optical imaging without fluorescence quenching. Unlike other multi‐phased composite nanostructures for multimodality imaging, this Ho³⁺‐doped UCNPs are featured with simplicity of synthesis and highly efficient multimodal MRI/UCL/CT imaging without fluorescence quenching, thus simplify nanostructure and probe preparation and enable win–win multimodality imaging.     

Effect of silver additive on electrical conductivity and methane sensitivity of SnO2

A composite powder of tin oxide (SnO₂) and silver (Ag) clusters was prepared by a simple and cost effective method of reducing their aqueous mixture with sodium borohydride (NaBH₄). Gas sensors based on the composite were made by powder pressing procedure and characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The electrical conductivity and gas sensing behavior of the sensors for methane (CH₄) gas were studied as a function of Ag concentration (0.3, 0.5, 0.8 and 1.5 wt%). The Ag additive is found to improve sensor response and widen its working temperature range with notable sensor response. The best sensor response was achieved by the sensor with 0.5 wt% Ag. The enhanced response was proved to be due to both electrical and chemical mechanisms.