Solvation largely accounts for the effect of N-alkylation on the properties of nickel(II/I) and chromium(III/II) cyclam complexes

The source of the effect of N-alkylation on the redox properties of Ni(II/I) and Cr(III/II) cyclam complexes has been investigated using DFT calculations. The structures of the anhydrous and hydrated complexes were optimized in the gas phase, and single point calculations were performed in a polarized continuum. The main results are the following: the decrease in outer sphere solvation upon N-alkylation is the major source of the relative stabilization of the lower oxidation state complexes by the tertiary amine ligands; tertiary amine nitrogen donors are stronger sigma-donors than the secondary amines, as predicted from the inductive effect of alkyls; steric strain elongates the metal-nitrogen bonds in the tertiary complexes and decreases the ligand strain energies; and the site of water binding to the complexes differs because of their different electronic structures (i.e., in the Ni complexes, the water molecules bind to the M[bond]N[bond]H sites, whereas in the Cr complexes they bind to the central metal cation). Outer sphere hydrogen bonding of water to the ligands in the coordination sphere lowers the ionization potentials by charge delocalization.     

基于机载光电载荷图像的无人机自主循迹导引

文章研究无人机搭载视觉传感器沿指定路径自主循迹飞行,针对如何统一确定不同形状路段的目标路径点序列的问题,提出基于无人机速度在图像中投影的矢量与无人机重心指向各候选路径点矢量的最小夹角确定目标路径点的方法。首先从采集的图像中提取出的路径区域,从图像层面提取路径的中间线,将图像栅格化并分别计算各栅格里路径中间线的中心点的坐标;然后计算图像中无人机速度矢量投影与无人机重心到各路径中心点矢量的夹角,在约束范围内选取最小夹角对应的中心点作为局部目标点。设置了包含不同形状拐角的路径,检验无人机飞行过程中采集图像的处理方法和路径引导算法结合的有效性,飞行结果表明提出的方法能够满足无人机的循迹飞行要求,轨迹偏离误差小于0.1 m。     

基于双引导滤波的红外和可见光图像融合算法

图像融合是将多幅图像中有用或互补信息整合成一幅图像的过程。本文提出了一种基于引导滤波多尺度分解的红外和可见光图像融合算法。在传统的引导滤波图像融合算法的基础之上,利用双引导滤波器代替均值滤波器将源图像分解为小尺度纹理细节、大尺度边缘和基础图像;直接利用纹理细节及边缘层图像构建显著性映射图,用其代替额外的特征提取操作,可很好地突出源图像显著性信息的同时大大降低算法复杂度;利用显著性映射图、Sigmoid函数构造权重图,将源图像中具有视觉意义的信息注入到融合图像中;利用色彩模型转换融合方式,可更好保留图像的色彩信息。定性和定量实验结果证明,相比于传统的基于引导滤波的图像融合算法,本文算法的融合效果得到进一步提升。     

Scavenging of “Dead Sulfur” and “Dead Lithium” Revealed by Integrated–Heterogeneous Catalysis for Advanced Lithium–Sulfur Batteries

The simultaneous engineering of sulfur cathode and Li anode is critical for electrolyte-starved high energy density Li–S batteries, in which slow electrochemical conversions and side chemical reactions of dead sulfur are found to be the determining factors in limiting the sulfur utilization, corresponding to the poor reversible capacity of Li–S batteries. Herein, this work challenges the conventional wisdom of heterogeneous and homogeneous catalyses in Li–S batteries and proposes the concept of integrated–heterogeneous catalysis to simultaneously scavenge the dead sulfur and dead lithium to compensate the active materials sulfur and lithium loss simply through adding a small amount of ZnI₂ into conventional electrolyte of Li–S cells. Regulated by integrated–heterogeneous catalysis, over 1300 h of cycling is realized in Li||Li symmetric cells, revealing superb compatibility of the ZnI₂-incorporated electrolyte with lithium metal. Meanwhile, the ZnI₂ shows good prospects in promoting the reutilization of dead sulfur in both theoretical calculation and experimental tests. Practically, a high initial capacity of 1170 mAh g⁻¹ with decent cycling stability is achieved in electrolyte-starved and high-loading pouch cells (5.0 µL mg⁻¹ and 5.2 mg cm⁻²).     

A Phase Engineering Strategy of Perovskite-Type ZnSnO3:Nd for Boosting the Sonodynamic Therapy Performance

The sensitization performance of sonosensitizers plays a key role in the sonodynamic therapy (SDT) effect. Herein, ZnSnO₃:Nd nanoparticles with R3c phase/amorphous heterogeneous structure are developed by phase engineering strategy and applied as an ideal sonosensitizer. In the crystalline perovskite-type ZnSnO₃:Nd, the substitution of the Zn²⁺ with Nd³⁺ causes the O 2p non-bonded state to move toward the Fermi level, which optimizes the band structure for ultrasound sensitization by reducing bandgap. Meanwhile, the unequal charge substitution can also form electron traps and oxygen vacancies to shorten the electron migration distance, which accelerates the electron–hole separation and inhibits carrier recombination, thus improving the acoustic sensitivity. Moreover, the dangling bonds exposed on the surface of amorphous ZnSnO₃:Nd provide more active sites, and the localized states of the amorphous phase may also promote carrier separation, resulting in synergistic SDT effect. In particular, the Zn²⁺ released from ZnSnO₃:Nd in the acidic tumor microenvironment (TME) reduces the adenosine triphosphate production by inhibiting the electron transport chain , which promotes the tumor cell apoptosis through destroying the redox balance of TME. Combining the inherent second near infrared and computed tomography imaging capabilities, this ZnSnO₃:Nd nanoplatform shows a promising perspective in clinic SDT field.     

The Golden Touch by Light: A Finely Engineered Luminogen Empowering High Photoactivatable and Photodynamic Efficiency for Cancer Phototheranostics

Photoactivatable agent is a powerful tool in biomedicine studies due to high-precision spatiotemporal control of light. However, those previously reported agents generally suffer from short wavelength, fluorescence self-quenching effect, and the lack of photosensitizing property, which severely restrict their practical applications. To address these issues, molecular engineering of 1,4-dihydropyridine derivatives is conducted to obtain an optimized agent, namely TPA-DHPy-Py, which exhibits low oxidation potential, high photoactivation efficiency, and excellent type I/II combined photodynamic activity. Concurrently, its photoactivated counterpart is featured by aggregation-induced near-infrared emission and remarkable reactive oxygen species (ROS) production efficiency. Upon photoactivation, TPA-DHPy-Py is capable of precisely identifying cancer cells from co-culturing cancer cells and normal cells without the assistance of any extra targeting units, and in situ monitoring lipid droplets and endoplasmic reticulum alteration under ROS stress, as well as achieving fluorescent visualization of tumor in vivo with supremely high imaging contrast. Furthermore, the unprecedented performance on photodynamic cancer therapy is demonstrated by the significant inhibition of tumor growth. Therefore, the photoactivatable TPA-DHPy-Py with dual-organelle-targeted and excellent photodynamic activity associated with self-monitoring ability is highly promising for cancer theranostics in clinical trials.     

Ultra-Damping Composites Enhanced by Yolk–Shell Piezoelectric Damping Mechanism

High-performance damping materials are significant toward reducing vibration and maintaining stability for industrial applications. Herein, a yolk–shell piezoelectric damping mechanism is reported, which can enhance mechanical energy dissipation and improve damping capability. With the addition of yolk–shell particles and carbon nanotube (CNT) conductive network, damping properties of various resin matrices are enhanced with the energy dissipation path of mechanical to electrical to heat energy. Particularly, the peak loss factor of epoxy composites reaches 1.91 and tan δ area increases by 25.72% at 20 °C. The results prove the general applicability of yolk–shell piezoelectric damping mechanism. Besides, the novel damping materials also exhibit excellent flexibility, stretchability, and resilience, offering a promising application toward damping coating, indicating broad scope of application in transportation and sophisticated electronics, etc.     

A NIR-II AIEgen-Based Supramolecular Nanodot for Peroxynitrite-Potentiated Mild-Temperature Photothermal Therapy of Hepatocellular Carcinoma

Compared to conventional photothermal therapy (PTT) which requires hyperthermia higher than 50 °C, mild-temperature PTT is a more promising antitumor strategy with much lower phototoxicity to neighboring normal tissues. However, the therapeutic efficacy of mild-temperature PTT is always restricted by the thermoresistance of cancer cells. To address this issue, a supramolecular drug nanocarrier is fabricated to co-deliver nitric oxide (NO) and photothermal agent DCTBT with NIR-II aggregation-induced emission (AIE) characteristic for mild-temperature PTT. NO can be effectively released from the nanocarriers in intracellular reductive environment and DCTBT is capable of simultaneously producing reactive oxygen species (ROS) and hyperthermia upon 808 nm laser irradiation. The generated ROS can further react with NO to produce peroxynitrite (ONOOˉ) bearing strong oxidization and nitration capability. ONOOˉ can inhibit the expression of heat shock proteins (HSP) to reduce the thermoresistance of cancer cells, which is necessary to achieve excellent therapeutic efficacy of DCTBT-based PTT at mild temperature (<50 °C). The antitumor performance of ONOOˉ-potentiated mild-temperature PTT is validated on subcutaneous and orthotopic hepatocellular carcinoma (HCC) models. This research puts forward an innovative strategy to overcome thermoresistance for mild-temperature PTT, which provides new inspirations to explore ONOOˉ-sensitized tumor therapy strategies.     

An Intrinsically Nonflammable Electrolyte for Prominent-Safety Lithium Metal Batteries with High Energy Density and Cycling Stability

Nex-generation high-energy-density storage battery, assembled with lithium (Li)-metal anode and nickel-rich cathode, puts forward urgent demand for advanced electrolytes that simultaneously possess high security, wide electrochemical window, and good compatibility with electrode materials. Herein an intrinsically nonflammable electrolyte is designed by using 1 M lithium difluoro(oxalato)borate (LiDFOB) in triethyl phosphate (TEP) and N-methyl-N-propyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide [Pyr₁₃][TFSI] ionic liquid (IL) solvents. The introduction of IL can bring plentiful organic cations and anions, which provides a cation shielding effect and regulates the Li⁺ solvation structure with plentiful Li⁺-DFOB⁻ and Li⁺-TFSI⁻ complexes. The unique Li⁺ solvation structure can induce stable anion-derived electrolyte/electrode interphases, which effectively inhibit Li dendrite growth and suppress side reactions between TEP and electrodes. Therefore, the LiNi_0.9Co_0.05Mn_0.05O₂ (NCM90)/Li coin cell with this electrolyte can deliver stable cycling even under 4.5 V and 60 °C. Moreover, a Li-metal battery with thick NCM90 cathode (≈ 15 mg cm⁻²) and thin Li-metal anode (≈ 50 µm) (N/P ≈ 3), also reveals stable cycling performance under 4.4 V. And a 2.2 Ah NCM90/Li pouch cell can simultaneously possess prominent safety with stably passing the nail penetration test, and high gravimetric energy density of 470 Wh kg⁻¹ at 4.4 V.     

Vapor Phase Growth of Centimeter-Sized Band Gap Engineered Cesium Lead Halide Perovskite Single-Crystal Thin Films with Color-tunable Stimulated Emission

Single crystal metal halide perovskites thin films are considered to be a promising optical, optoelectronic materials with extraordinary performance due to their low defect densities. However, it is still difficult to achieve large-scale perovskite single-crystal thin films (SCTFs) with tunable bandgap by vapor-phase deposition method. Herein, the synthesis of CsPbCl_3(1–x)Br_3x SCTFs with centimeter size (1 cm × 1 cm) via vapor-phase deposition is reported. The Br composition of CsPbCl_3(1–x)Br_3x SCTFs can be gradually tuned from x = 0 to x = 1, leading the corresponding bandgap to change from 2.29 to 2.91 eV. Additionally, an low-threshold (≈23.9 µJ cm⁻²) amplified spontaneous emission is achieved based on CsPbCl_3(1–x)Br_3x SCTFs at room temperature, and the wavelength is tuned from 432 to 547 nm by varying the Cl/Br ratio. Importantly, the high-quality CsPbCl_3(1–x)Br_3x SCTFs are ideal optical gain medium with high gain up to 1369.8 ± 101.2 cm⁻¹. This study not only provides a versatile method to fabricate high quality CsPbCl_3(1–x)Br_3x SCTFs with different Cl/Br ratio, but also paves the way for further research of color-tunable perovskite lasing.