Structural dependence of microwave dielectric properties in ilmenite-type Mg(Ti1-xNbx)O3 solid solutions by Rietveld refinement and Raman spectra

Mg(Ti_1-xNb_x)O₃ (x = 0–0.09) ceramics were prepared by the conventional solid-state reaction method. The phase composition, sintering characteristics, microstructure and dielectric properties of Ti⁴⁺ replacement by Nb⁵⁺ in the formed solid solution Mg(Ti_1-xNb_x)O₃ (x = 0–0.09) ceramics were systematically studied. The structural variations and influence of Nb⁵⁺ doping in Mg(Ti_1-xNb_x)O₃ were also systematically investigated by X-ray diffraction and Raman spectroscopy, respectively. X-ray diffraction and its Rietveld refinement results confirmed that Mg(Ti_1-xNb_x)O₃ (x = 0–0.09) ceramics crystallised into an ilmenite-type with R-3 (148) space group. The replacement of the low valence Ti⁴⁺ by the high valence Nb⁵⁺ can improve the dielectric properties of Mg(Ti_1-xNb_x)O₃ (x = 0–0.09). This paper also studied the different sintering temperatures for Mg(Ti_1-xNb_x)O₃ (x = 0–0.09) ceramics. The obtained results proved that 1350 °C is the best sintering temperature. The permittivity and Q × f initially increased and then decreased mainly due to the effects of porosity caused by the sintering temperature and the doping amount of Nb₂O₅, respectively. Furthermore, the increased Q × f is correlated to the increase in Ti–O bond strength as confirmed by Raman spectroscopy, and the electrons generated by the oxygen vacancies will be compensated by Nb⁵⁺ to a certain extent to suppress Ti⁴⁺ to Ti³⁺, which was confirmed by XPS. The increase in τ_f from ?47 ppm/°C to ?40.1 ppm/°C is due to the increment in cell polarisability. Another reason for the increased τ_f is the reduction in the distortion degree of the [TiO₆] octahedral, which was also confirmed by Raman spectroscopy. Mg(Ti_0.95Nb_0.05)O₃ ceramics sintered at 1350 °C for 2 h possessed excellent microwave dielectric properties of ε_r = 18.12, Q × f = 163618 GHz and τ_f = ?40.1 ppm/°C.     

Dual-phase rare-earth-zirconate high-entropy ceramics with glass-like thermal conductivity

A series of rare earth zirconates (RE₂Zr₂O₇) high-entropy ceramics with single- and dual-phase structure were prepared. Compared with La₂Zr₂O₇ and Yb₂Zr₂O₇, the smaller “rattling” ions (Yb³⁺, Er³⁺, Y³⁺) have been incorporated into pyrochlore lattice in (La_0.2Nd_0.2Y_0.2Er_0.2Yb_0.2)₂Zr₂O₇ (LNYEY) while larger ions (La³⁺, Nd³⁺, Sm³⁺, Eu³⁺) incorporated into fluorite lattice in (La_0.2Nd_0.2Sm_0.2Gd_0.2Yb_0.2)₂Zr₂O₇ (LNSGY). Due to high-entropy lattice distortion and resonant scattering derived from smaller ions Yb³⁺, Er³⁺, and Y³⁺, LNYEY shows a lower glass-like thermal conductivity (1.62-1.59 W m^-1 K^-1, 100-600℃) than LNSGY (1.74-1.75 W m^-1 K^-1, 100-600℃). Moreover, LNYEY and LNSGY exhibit enhanced Vickers’ hardness (LNYEY, H_v = 11.47 ± 0.41 GPa; LNSGY, H_v = 10.96 ± 0.26 GPa) and thermal expansion coefficients (LNYEY, 10.45 × 10^-6 K^-1, 1000℃; LNSGY, 11.02 × 10^-6 K^-1, 1000℃). These results indicate that dual-phase rare-earth-zirconate high-entropy ceramics could be desirable for thermal barrier coatings.     

Superior Low-Temperature Reversible Adhesion Based on Bio-Inspired Microfibrillar Adhesives Fabricated by Phenyl Containing Polydimethylsiloxane Elastomers

Gecko-inspired microfibrillar adhesives have achieved great progress in microstructure design and adhesion improvement over the past two decades. Space applications nowadays show great interest in this material for the characteristics of reversible adhesion and universal van der Waals interactions. However, the impact of harsh environment of space on the performance of microfibrillar adhesives, especially the extreme low temperature, is rarely addressed. Herein, microfibrillar adhesives fabricated by phenyl containing polydimethylsiloxane (p-PDMS) elastomers with superior low-temperature reversible adhesion is proposed. p-PDMS elastomers are synthesized through one-pot anionic ring-opening copolymerization, and the resulting elastomers become non-crystallizable with excellent low-temperature elasticity. Low-temperature adhesion tests demonstrate that the adhesion strength of microfibrillar adhesives fabricated by p-PDMS elastomers can be well maintained to as low as −120 °C. In contrast, the adhesion strength of pure PDMS microfibrillar adhesive reduces more than 50% below its crystallization temperature. The low-temperature cyclic adhesion tests further demonstrate that p-PDMS microfibrillar adhesives exhibit superior reversible adhesion compared to that of PDMS microfibrillar adhesives, owing to the sustainable conformal contact and even distribution of loads over repeated cycles. This study provides a new fabrication strategy for microfibrillar adhesives, and is beneficial for the practical application of microfibrillar adhesives.     

Fabrication and upconversion luminescence properties of Er:SrF2 transparent ceramics compared with Er:CaF2

SrF₂ transparent ceramic is a promising upconversion material due to the low phonon energy. The effect of different sintering temperatures on Er:SrF₂ transparent ceramics was investigated. The suitable sintering temperature for Er:SrF₂ transparent ceramics was 900 °C by hot-pressed sintering in this study. High quality of Er:SrF₂ transparent ceramics with different doping concentrations were obtained. The upconversion luminescence spectra and decay behavior were compared between Er:SrF₂ and Er:CaF₂ transparent ceramics with different Er³⁺ doping concentration. The green emission of 5 at.% Er:SrF₂ ceramic was much stronger than that of 5 at.% Er:CaF₂ ceramic, while the red emission of Er:SrF₂ ceramic was almost the same as that of Er:CaF₂ ceramic. The upconversion luminescence lifetime of Er:SrF₂ transparent ceramics was longer than that of Er:CaF₂.All the results indicated Er:SrF₂ transparent ceramics was a candidate for green fluorescent upconversion materials.     

Nanovaccine-Mediated Cell Selective Delivery of Neoantigens Potentiating Adoptive Dendritic Cell Transfer for Personalized Immunization

Neoantigen vaccines and adoptive dendritic cell (DC) transfer are major clinical approaches to initiate personalized immunity in cancer patients. However, the immunization efficacy is largely limited by the in vivo trajectory including neoantigens’ access to resident DCs and DCs’ access to lymph nodes (LNs). Herein, an innovative strategy is proposed to improve personalized immunization through neoantigen-loaded nanovaccines synergized with adoptive DC transfer. It is found that it enables selective delivery of neoantigens to resident DCs and macrophages by coating cancer cell membranes onto neoantigen-loaded nanoparticles. In addition, the nanovaccines promote the secretion of chemokine C-C motif ligand 2 (CCL2), CCL3, and C-X-C motif ligand 10 from macrophages, thus potentiating the access of transferred DCs to LNs. This immunization strategy enables coordinated delivery of identified neoantigens and autologous tumor lysate-derived undefined antigens, leading to initiation of antitumor T cell immunity in a personalized manner. It significantly inhibits tumor growth in prophylactic and established mouse tumor models. The findings provide a new vision for potentiating adoptive cell transfer by nanovaccines, which may open the door to a transformative possibility for improving personalized immunization.     

Preparation and antifouling performance of thin inorganic ultrafiltration membrane via assisted sol-gel method with different composition of dual additives

A novel TiO₂ thin film was prepared on the ceramic hollow fiber by the sol-gel method using poly(vinylpyrrolidone) (PVP) and polyvinyl alcohol (PVA) as additives. SEM images verified the formation of TiO₂ layer with various thickness using different composition of titania sols. The effect of the PVP and PVA contents on the TiO₂ sol properties, the separation and the antifouling performance of the ultrafiltration membranes were investigated thoroughly. When the contents of PVP and PVA were 1.0 wt% and 0.8 wt%, respectively, the resultant membrane showed a thickness of 0.55 μm with a pure water flux of 255 L m^?2 h^?1. In addition, the adherent foulant bovine serum albumin was applied to evaluate the antifouling performance. During the three fouling-recovery cycles, the flux recovery ratio and the flux decay ratio maintained about 99% and 30%. The BSA flux and rejection were still 169 L m^?2 h^?1 and 96.9% after the cycles, indicating a superior antifouling property.     

Mechanism in chlorine-enhanced Pd catalyst for H2O2 in situ synthesis in electro-Fenton system

Palladium-based catalysts have been widely employed in the electro-Fenton process for in situ generation of H₂O₂. However, the process is still far from being practical on a large scale. In this work, a series of Cl_xFePd/γ-Al₂O₃/Al catalysts were prepared by a three-step-impregnation method. They exhibited excellent activity in H₂O₂ in situ synthesis and high efficiency in phenol degradation. The characterization results showed that Cl could assist in increasing the content of Pd⁰ and reducing the isoelectric point of catalysts, which led to the drastic promotion in the synthesis of H₂O₂. Theoretical calculations further demonstrated that Cl doping could facilitate the main reaction in H₂O₂ synthesis, as well as inhibit side reactions such as dissociation of the O O bond. Furthermore, kinetic models were proposed and fitted. A plausible reaction mechanism as well as degradation pathways were elaborated based on electron spin resonance and gas chromatography–mass spectrometry results. These findings illustrate the value of palladium-based Cl_xFePd/γ-Al₂O₃/Al catalysts for their application in the electro-Fenton process.     

大鲵肝茶叶水提液脱腥过程中挥发性有机物的动态变化

目的：探讨茶叶水提液对大鲵肝的脱腥效果。方法：采用感官腥味值结合气相—离子迁移色谱(GC-IMS)分析经茶叶水提液处理不同时间(0，5，10，15，20 min)大鲵肝中挥发性成分的变化。结果：与未脱腥组相比，经茶叶水提液脱腥处理5 min后大鲵肝脏腥味值显著下降(P＜0.05)，处理10 min后腥味值基本稳定。不同脱腥时间下大鲵肝样品中共鉴定出32种挥发性有机物，包括10种醇类、8种醛类、5种酯类、5种酮类、3种烯烃类和1种醚类。经脱腥处理后，大鲵肝中醇、烯烃、醚、酯类物质相对含量下降，酮类和醛类物质相对含量增加。通过正交偏最小二乘法判别分析(OPLS-DA)结合变量投影重要性(VIP)筛选出10种潜在特征标志物(VIP＞1)，包括4种酮类、2种醇类、2种醛类、1种烯类和1种醚类。随着脱腥时间的延长，蘑菇醇、2-丁酮二聚体、异戊醇单体、2-丁酮单体相对含量呈降低趋势，而正己醛单体、异戊醛单体、丙酮相对含量呈增加趋势。结论：茶叶水提液处理5~10 min能够明显降低大鲵肝腥味，通过GC-IMS技术结合多元统计分析可以对脱腥过程中大鲵肝挥发性有机物进行区分。     

基于禁忌搜索的晶体位置谱分割与校准方法

为满足不同规格晶体探测器对分割校准晶体条响应事件位置数据的需求，开发了一种以禁忌搜索算法为核心，结合UDP数据帧、二维高斯模型及光导折射率的位置信息分割校准方法。实验结果表明，本方法在溢出率为5%时，峰谷比可达1218，空间分辨率达17 mm，晶体条响应位置识别准确度高达99%，滤除了引发伪峰的噪声，避免了过分割问题。在面对多种规格晶体阵列的位置谱时，本方法能依照阵列规格将晶体条区域的响应自动校准编号并输出晶体位置查找表，实现响应事件的精确校准。