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.     

Vacancy Manipulation Induced Optimal Carrier Concentration,Band Convergence and Low Lattice Thermal Conductivity in Nano-Crystalline SnTe Yielding Superior Thermoelectric Performance

Synergetic optimization of electrical and thermal transport properties is achieved for SnTe-based nano-crystalline materials. Gd doping is able to suppress the Sn vacancy, which is confirmed by positron annihilation measurements and corresponding theoretical calculations. Hence, the optimal hole carrier concentration is obtained, leading to the improvement of electrical transport performance and simultaneous decrease of electronic thermal conductivity. In addition, the incremental density of states effective mass m* in SnTe is realized by the promotion of the band convergence via Gd doping, which is further confirmed by the band structure calculation. Hence, the enhancement of the Seebeck coefficient is also achieved, leading to a high power factor of 2922 µW m⁻¹ K⁻² for Sn_0.96Gd_0.04Te at 900 K. Meanwhile, substantial suppression of the lattice thermal conductivity is observed in Gd-doped SnTe, which is originated from enhanced phonon scattering by multiple processes including mass and strain fluctuations due to the Gd doping, scattering of grain boundaries, nano-pores, and secondary phases induced by Gd doping. With the decreased phonon mean free path and reduced average phonon group velocity, a rather low lattice thermal conductivity is achieved. As a result, the synergetic optimization of the electric and thermal transport properties contributes to a rather high ZT value of ≈1.5 at 900 K, leading to the superior thermoelectric performance of SnTe-based nanoscale polycrystalline materials.     

Surface Oxygen Coordination of Hydrogen Bond Chemistry for Aqueous Ammonium Ion Hybrid Supercapacitor

Aqueous ammonium ion hybrid supercapacitor (A-HSC) combines the charge storage mechanisms of surface adsorption and bulk intercalation, making it a low-cost, safe, and sustainable energy storage candidate. However, its development is hindered by the low capacity and unclear charge storage fundamentals. Here, the strategy of phosphate ion-assisted surface functionalization is used to increase the ammonium ion storage capacity of an α-MoO₃ electrode. Moreover, the understanding of charge storage mechanisms via structural characterization, electrochemical analysis, and theoretical calculation is advanced. It is shown that NH₄⁺ intercalation into layered α-MoO₃ is not dominant in the A-HSC system; rather, the charge storage mainly depends on the adsorption energy of surface “O” to NH₄⁺. It is further revealed that the hydrogen bond chemistry of the coordination between “O” of surface phosphate ion and NH₄⁺ is the reason for the capacity increase of MoO₃. This study not only advances the basic understanding of rechargeable aqueous A-HSC but also demonstrates the promising future of surface engineering strategies for energy storage devices.     

Proximity-Induced Fully Ferromagnetic Order with Eightfold Magnetic Anisotropy in Heavy Transition Metal Oxide CaRuO3

Ferromagnetic materials with a strong spin-orbit coupling (SOC) have attracted much attention in recent years because of their exotic properties and potential applications in energy-efficient spintronics. However, such materials are scarce in nature. Here, a proximity-induced paramagnetic to ferromagnetic transition for the heavy transition metal oxide CaRuO₃ in (001)-(LaMnO₃/CaRuO₃) superlattices is reported. Anomalous Hall effect is observed in the temperature range up to 180 K. Maximal anomalous Hall conductivity and anomalous Hall angle are as large as ∼15 Ω⁻¹ cm⁻¹ and ∼0.93%, respectively, by one to two orders of magnitude larger than those of the typical 3d ferromagnetic oxides such as La_0.67Sr_0.33MnO₃. Density functional theory calculations indicate the existence of avoid band crossings in the electronic band structure of the ferromagnetic CRO layer, which enhances Berry curvature thus strong anomalous Hall effects. Further evidences from polarized neutron reflectometry show that the CaRuO₃ layers are in a fully ferromagnetic state (∼0.8 μ_B/Ru), in sharp contrast to the proximity-induced canted antiferromagnetic state in 5d oxides SrIrO₃ and CaIrO₃ (∼0.1 μ_B/Ir). More than that, the magnetic anisotropy of the (001)-(LaMnO₃/CaRuO₃) superlattices is eightfold symmetric, showing potential applications in the technology of multistate data storage.     

Solid Solvation Assisted Electrical Doping Conserves High-Performance in 500 nm Active Layer Organic Solar Cells

Organic solar cells (OSCs) process fascinating solution-printing capability to achieve low-cost and large-scale manufacture. However, the rapid power conversion efficiency (PCE) decay with active layer thickness enlargement inhibits the implement of OSCs’ potential advantages. To overcome the bottlenecks of PCE decay in thick active layer OSCs, the electrical doping with componential selectivity in bulk heterojunction (BHJ) film is achieved by introducing a solid solvation additive. Benefiting from the higher exciton splitting efficiency together with the longer drift (L_dr) and diffusion (L_diff) lengths, an OSC with 100 nm BHJ film demonstrates a PCE increment from 16.44% to 18.24% with prolonged dark and illuminated storage stabilities. Applying the solid solvation assisted (SSA) doping method in the OSCs with 500 nm active layer, the PCE significantly increases by 31.9%, from the original value of 11.79% to 15.55%. It further improves to 15.84% in a ternary blend thick-film device, which is the record value to the best of our knowledge. Besides, the SSA doping narrows the PCE gap between the 0.04 and 1 cm² devices. All improvements demonstrate the great potential of SSA doping for OSC commercial manufacture, since it optimizes the photovoltaic performance under all practical conditions of long-term, thick-film, and large-area.     

Simultaneous CO2 and H2O Activation via Integrated Cu Single Atom and N Vacancy Dual-Site for Enhanced CO Photo-Production

Photocatalytic conversion of CO₂ into fuels using pure water as the proton source is of immense potential in simultaneously addressing the climate-change crisis and realizing a carbon-neutral economy. Single-atom photocatalysts with tunable local atomic configurations and unique electronic properties have exhibited outstanding catalytic performance in the past decade. However, given their single-site features they are usually only amenable to activations involving single molecules. For CO₂ photoreduction entailing complex activation and dissociation process, designing multiple active sites on a photocatalyst for both CO₂ reduction and H₂O dissociation simultaneously is still a daunting challenge. Herein, it is precisely construct Cu single-atom centers and two-coordinated N vacancies as dual active sites on CN (Cu₁/N_2CV-CN). Experimental and theoretical results show that Cu single-atom centers promote CO₂ chemisorption and activation via accumulating photogenerated electrons, and the N_2CV sites enhance the dissociation of H₂O, thereby facilitating the conversion from COO* to COOH*. Benefiting from the dual-functional sites, the Cu₁/N_2CV-CN exhibits a high selectivity (98.50%) and decent CO production rate of 11.12 µmol g⁻¹ h⁻¹. An ingenious atomic-level design provides a platform for precisely integrating the modified catalyst with the deterministic identification of the electronic property during CO₂ photoreduction process.     

Freely Tailorable Yolk-Shell Encapsulation: Versatile Applications in Ultralow-k Dielectric,Drug Delivery Systems,and Catalysts

Herein, a facile, controllable, and versatile method is reported to prepare monodisperse yolk-shell and yolk-multishell silica nanoparticles (NPs) with mesoporous shells by a novel selective etching strategy. The mechanism of selective etching based on fluoride-silica chemistry is investigated in detail and thus provides a fundamentally novel principle for the fabrication of yolk-shell NPs. Specifically, this unprecedented and versatile synthesis strategy can be used to encapsulate essentially any silica-based, carbon-based, metal, metal oxide, or other possible NPs. Noteworthy is that most of the yolk-shell mesoporous silica (mSiO₂) NPs are prepared for the first time. To demonstrate the major structural and compositional advantages of the designed yolk-shell NPs, their applications in the fields of ultralow-dielectric constant (k) materials, drug delivery systems, and catalysts were explored. In detail, the lowest k value of the prepared yolk-shellordered mesoporous silica@mSiO₂/fluorinated polybenzoxazole composite films is 2.02; The obtained yolk-shell mSiO₂/C@mSiO₂/C NPs possess high hydrophilicity and pH-responsive sensitivity; The conversion of the catalytic reaction of the designed magnetic yolk-shell hollow Fe₃O₄@SiO₂/Au@mSiO₂ NPs at 20 min is 97% with a high conversion rate (92%) and recyclability even after 10 reuses. This innovative work lays a solid foundation for freely tailorable yolk-shell encapsulation and will greatly stimulate more efforts devoted to relevant research and development.     

考虑双目竞争视觉现象的非对称失真立体图像质量评价方法

目的 现有方法存在特征提取时间过长、非对称失真图像预测准确性不高的问题,同时少有工作对非对称失真与对称失真立体图像的分类进行研究,为此提出了基于双目竞争的非对称失真立体图像质量评价方法。方法 依据双目竞争的视觉现象,利用非对称失真立体图像两个视点的图像质量衰减程度的不同,生成单目图像特征的融合系数,融合从左右视点图像中提取的灰度空间特征与HSV （hue-saturation-value）彩色空间特征。同时,量化两个视点图像在结构、信息量和质量衰减程度等多方面的差异,获得双目差异特征。并且将双目融合特征与双目差异特征级联为一个描述能力更强的立体图像质量感知特征向量,训练基于支持向量回归的特征—质量映射模型。此外,还利用双目差异特征训练基于支持向量分类模型的对称失真与非对称失真立体图像分类模型。结果 本文提出的质量预测模型在4个数据库上的SROCC （Spearman rank order correlation coefficient）和PLCC （Pearson linear correlation coefficient）均达到0.95以上,在3个非对称失真数据库上的均方根误差（root of mean square error,RMSE）取值均优于对比算法。在LIVE-II（LIVE 3D image quality database phase II）、IVC-I（Waterloo-IVC 3D image qualityassessment database phase I）和IVC-II （Waterloo-IVC 3D image quality assessment database phase II）这3个非对称失真立体图像测试数据库上的失真类型分类测试中,对称失真立体图像的分类准确率分别为89.91%、94.76%和98.97%,非对称失真立体图像的分类准确率分别为95.46%,92.64%和96.22%。结论 本文方法依据双目竞争的视觉现象融合左右视点图像的质量感知特征用于立体图像质量预测,能够提升非对称失真立体图像的评价准确性和鲁棒性。所提取双目差异性特征还能够用于将对称失真与非对称失真立体图像进行有效分类,分类准确性高。     

基于3D路径聚合高分辨率网络的胰腺分割

目的 胰腺的准确分割是胰腺癌识别和分析的重要前提。现有基于深度学习的主流胰腺分割网络大多是编码—解码结构,对特征图采用先降低再增加分辨率的方式,严重丢失了胰腺位置和细节信息,导致分割效果不佳。针对上述问题,提出了基于3D路径聚合高分辨率网络的胰腺分割方法。方法 首先,为了捕获更多3D特征上下文信息,将高分辨率网络中的2D运算拓展为3D运算;其次,提出全分辨特征路径聚合模块,利用连续非线性变换缩小全分辨率输入图像与分割头网络输出特征语义差异的同时,减少茎网络下采样丢失的位置和细节信息对分割结果的影响;最后,提出多尺度特征路径聚合模块,利用渐进自适应特征压缩融合方式,避免低分辨率特征通道过度压缩导致的信息内容损失。结果 在公开胰腺数据集上,提出方法在Dice系数（Dice similarity coefficient,DSC）、Jaccard系数（Jaccard index,JI）、精确率（precision）和召回率（recall）上相比3D高分辨率网络（3D high-resolution net,3DHRNet）分别提升了1.41%、2.09%、2.35%和0.49%,相比具有代表性编码—解码结构的胰腺分割方法,取得了更高的分割精度。结论 本文提出的3D路径聚合高分辨率网络（3D pathaggregation high-resolution network,3DPAHRNet）具有更强的特征位置和细节信息的保留能力,能够显著改善在腹部CT（computed tomography）图像中所占比例较小的胰腺器官的分割结果。开源代码可在https：//github.com/qiuchengjian/PAHRNet3D获得。     

Regulation of Ionic Distribution and Desolvation Activation Energy Enabled by In Situ Zinc Phosphate Protective Layer toward Highly Reversible Zinc Metal Anodes

Despite the merits of high specific capacity, low cost, and high safety, the practical application of aqueous Zn metal batteries (AZMBs) is plagued by the dendritic growth and corrosion reaction of Zn metal anodes. To solve these issues, a Zn₃(PO₄)₂·4H₂O protective layer is in-situ constructed on Zn foil (Zn@ZnPO) by a simple hydrothermal method, avoiding the traditional slurry-casting process. The insulating and conformable ZnPO layer improves the wettability of Zn@ZnPO and aqueous electrolyte via decreasing the contact angle to 11.7^o. Compared with bare Zn, the Zn@ZnPO possesses a lower desolvation activation energy of 35.25 kJ mol^-1, indicating that the ZnPO fasters the desolvation of hydrated Zn²⁺ ions and thereby ameliorates their transport dynamics. Micro-morphology and structural characterization show that there are no dendrites forming on the post-cycling Zn@ZnPO anodes, and the interfacial ZnPO layer remains almost identical before and after cycles. It can be explained that the electrochemically stable ZnPO layer acts as an ionic modulator to enable the homogeneous distribution of Zn²⁺ ions, inhibiting the growth of Zn dendrites. Benefiting from these advantages, the Zn@ZnPO based symmetric and full cells deliver highly reversible Zn plating/stripping behavior and long cycling lifespans.