双对苯醌的抗氧化活性分析及其固体发酵条件优化

为探索生物活性未知的双对苯醌（2,7-dihydroxy-3,6,9-trimethyl-9H-xanthene-1,4,5,8-tetraone，DTXT）的抗氧化活性，并提高其发酵产量，考察DTXT的还原力以及对超氧阴离子自由基、羟自由基、1,1-二苯基-2-三硝基苯肼（1,1-diphenyl-2-picrylhydrazyl，DPPH）自由基的清除效果，在单因素试验基础上，采用响应面法优化了DTXT产生菌瓶生顶孢霉（Acremonium cavaraeanum）CA022菌株的固体发酵培养基。结果表明：在200 μg/mL质量浓度下，DTXT的还原力与芦丁差异不显著，高于VE和2,6-二叔丁基-4甲基苯酚，对超氧阴离子自由基清除率达到67.00%，对羟自由基清除率达到78.83%，对DPPH自由基清除率达到76.53%。通过响应面试验，得到最佳培养基配方为葡萄糖0.773%、硝酸钠0.185%、H3BO3 0.032%、VB1 100 μg/100 g，在此条件下实际获得的DTXT产量为4 150.8 mg/kg，是优化前产量的（2 864.83 mg/kg）1.45 倍。     

Interfacial microstructure and mechanical properties of Ti3SiC2 ceramic and TC11 alloy joint diffusion bonded with a Cu interlayer

Reliable joints of Ti₃SiC₂ ceramic and TC11 alloy were diffusion bonded with a 50 μm thick Cu interlayer. The typical interfacial structure of the diffusion boned joint, which was dependent on the interdiffusion and chemical reactions between Al, Si and Ti atoms from the base materials and Cu interlayer, was TC11/α-Ti + β-Ti + Ti₂Cu + TiCu/Ti₅Si₄ + TiSiCu/Cu(s, s)/Ti₃SiC₂. The influence of bonding temperature and time on the interfacial structure and mechanical properties of Ti₃SiC₂/Cu/TC11 joint was analyzed. With the increase of bonding temperature and time, the joint shear strength was gradually increased due to enhanced atomic diffusion. However, the thickness of Ti₅Si₄ and TiSiCu layers with high microhardness increased for a long holding time, resulting in the reduction of bonding strength. The maximum shear strength of 251 ± 6 MPa was obtained for the joint diffusion bonded at 850 °C for 60 min, and fracture primarily occurred at the diffusion layer adjacent to the Ti₃SiC₂ substrate. This work provided an economical and convenient solution for broadening the engineering application of Ti₃SiC₂ ceramic.     

Efficient Visible-to-UV Photon Upconversion Systems Based on CdS Nanocrystals Modified with Triplet Energy Mediators

Developing high-performance visible-to-UV photon upconversion systems based on triplet–triplet annihilation photon upconversion (TTA-UC) is highly desired, as it provides a potential approach for UV light-induced photosynthesis and photocatalysis. However, the quantum yield and spectral range of visible-to-UV TTA-UC based on nanocrystals (NCs) are still far from satisfactory. Here, three different sized CdS NCs are systematically investigated with triplet energy transfer to four mediators and four annihilators, thus substantially expanding the available materials for visible-to-UV TTA-UC. By improving the quality of CdS NCs, introducing the mediator via a direct mixing fashion, and matching the energy levels, a high TTA-UC quantum yield of 10.4% (out of a 50% maximum) is achieved in one case, which represents a record performance in TTA-UC based on NCs without doping. In another case, TTA-UC photons approaching 4 eV are observed, which is on par with the highest energies observed in optimized organic systems. Importantly, the in-depth investigation reveals that the direct mixing approach to introduce the mediator is a key factor that leads to close to unity efficiencies of triplet energy transfer, which ultimately governs the performance of NC-based TTA-UC systems. These findings provide guidelines for the design of high-performance TTA-UC systems toward solar energy harvesting.     

A Smart Hyperthermia Nanofiber-Platform-Enabled Sustained Release of Doxorubicin and 17AAG for Synergistic Cancer Therapy

This study demonstrates the rational fabrication of a magnetic composite nanofiber mesh that can achieve mutual synergy of hyperthermia, chemotherapy, and thermo-molecularly targeted therapy for highly potent therapeutic effects. The nanofiber is composed of biodegradable poly(ε-caprolactone) with doxorubicin, magnetic nanoparticles, and 17-allylamino-17-demethoxygeldanamycin. The nanofiber exhibits distinct hyperthermia, owing to the presence of magnetic nanoparticles upon exposure of the mesh to an alternating magnetic field, which causes heat-induced cell killing as well as enhanced chemotherapeutic efficiency of doxorubicin. The effectiveness of hyperthermia is further enhanced through the inhibition of heat shock protein activity after hyperthermia by releasing the inhibitor 17-allylamino-17-demethoxygeldanamycin. These findings represent a smart nanofiber system for potent cancer therapy and may provide a new approach for the development of localized medication delivery.     

Spatiotemporal Magnetocaloric Microenvironment for Guiding the Fate of Biodegradable Polymer Implants

The degradation behavior of implants is significantly important for bone repair. However, it is still unprocurable to spatiotemporally regulate the degradation of the implants to match bone ingrowth. In this paper, a magneto-controlled biodegradation model is established to explore the degradation behavior of magnetic scaffolds in a magnetothermal microenvironment generated by an alternating magnetic field (AMF). The results demonstrate that the scaffolds can be heated by magnetic nanoparticles (NPs) under AMF, which dramatically accelerated scaffold degradation. Especially, magnetic NPs modified by oleic acid with a better interface compatibility exhibit a greater heating efficiency to further facilitate the degradation. Furthermore, the molecular dynamics simulations reveal that the enhanced motion correlation between magnetic NPs and polymer matrix can accelerate the energy transfer. As a proof-of-concept, the feasibility of magneto-controlled degradation for implants is demonstrated, and an optimizing strategy for better heating efficiency of nanomaterials is provided, which may have great instructive significance for clinical medicine.     

超支化镍系催化剂构效关系及催化乙烯齐聚机理

采用1.0G超支化大分子（1.0G）、3-取代水杨醛和NiCl₂·6H₂O为原料，依次经席夫碱反应和络合反应合成了3种新型具有不同取代基位阻的超支化水杨醛亚胺配体及其镍系催化剂，利用红外光谱（FTIR）、核磁共振氢谱（¹H NMR）、紫外光谱（UV-vis）、电喷雾质谱（ESI-MS）及电感耦合等离子体质谱（ICP-MS）等方法对合成出产物的结构进行表征。考察了配体空间位阻、溶剂种类、助催化剂种类及反应条件对催化乙烯齐聚性能的影响。研究结果表明，配体空间位阻对催化乙烯齐聚性能有较大的影响，当以甲苯为溶剂、甲基铝氧烷（MAO）为助催化剂，在最佳反应条件下，超支化邻苯基水杨醛亚胺镍系催化剂催化乙烯齐聚的活性为2.81×10⁵g/(mol Ni·h)，对高碳烯烃（C₁₀₊）的选择性为34.28%。此外，在超支化水杨醛亚胺镍系催化剂催化性能评价的基础上，对其催化乙烯齐聚的机理进行研究。     

重力注水过程流动不稳定现象关键影响因素研究

重力驱动注水过程中由于流量较小以及蒸汽的积聚可能导致流动不稳定现象的发生，对核反应堆安全运行具有重要的影响。通过实验研究的方法，搭建了重力注水模拟实验装置，研究了不同蒸汽出口形阻、高位储水箱水位和加热棒初始温度下流动不稳定现象的变化规律。结果表明，重力驱动注水过程流动不稳定现象包含冷却水初次注入阶段、注入水逐出阶段和冷却水再注入阶段等。在一定冷却水初始温度、冷却水入口形阻以及系统压力下，蒸汽排出速度以及实验本体内筒顶部的聚集情况取决于蒸汽出口形阻，减小蒸汽出口形阻可加快蒸汽排放速度，压力峰峰值降低、振荡周期变长，有利于系统稳定；提高高位储水箱水位加快了冷却水注入速率，增加了加热棒被淹没率，降低了流动不稳定现象的发生次数和持续时间；随加热棒初始温度的升高，冷却水流量出现了波动向停滞的转变，流动不稳定现象发生的次数增加且持续时间加长。