MOF衍生的高选择性加氢芳香硝基化合物的石墨碳包覆镍催化剂

针对芳香硝基化合物的催化选择性加氢反应，开发可替代贵金属催化剂的低成本、高效非贵金属催化剂，对于芳香胺类化合物的绿色生产具有重要意义。利用简易、可规模化的制备方法，以镍—2,5-吡啶二羧酸金属有机框架为前驱体，热解制备了氮掺杂石墨碳包覆镍纳米催化材料（Ni@CN）。采用X射线衍射、扫描电镜、透射电镜、元素分析、N2吸脱附等检测手段对Ni@CN的物化性质进行了表征，并对其催化性能进行了评价。结果表明，Ni@CN可在温和条件下（85℃，1.0 MPa H2)高效加氢含取代官能团的芳香硝基化合物生成对应的芳香胺类化合物。对比试验表明，镍纳米颗粒是Ni@CN的加氢活性中心，而石墨碳壳的存在有利于优先吸附硝基官能团。此外，进一步考察了Ni@CN的循环使用性能以及抗硫化物中毒的特性。     

Lighting the Path: Light Delivery Strategies to Activate Photoresponsive Biomaterials In Vivo

Photoresponsive biomaterials are experiencing a transition from in vitro models to in vivo demonstrations that point toward clinical translation. Dynamic hydrogels for cell encapsulation, light-responsive carriers for controlled drug delivery, and nanomaterials containing photosensitizers for photodynamic therapy are relevant examples. Nonetheless, the step to the clinic largely depends on their combination with technologies to bring light into the body. This review highlights the challenge of photoactivation in vivo, and presents strategies for light management that can be adopted for this purpose. The authors’ focus is on technologies that are materials-driven, particularly upconversion nanoparticles that assist in “direct path” light delivery through tissue, and optical waveguides that “clear the path” between external light source and in vivo target. The authors’ intention is to assist the photoresponsive biomaterials community transition toward medical technologies by presenting light delivery concepts that can be integrated with the photoresponsive targets. The authors also aim to stimulate further innovation in materials-based light delivery platforms by highlighting needs and opportunities for in vivo photoactivation of biomaterials.     

Metabolic Profiling of VOCs Emitted by Bacteria Isolated from Pressure Ulcers and Treated with Different Concentrations of Bio-AgNPs

Considering the advent of antibiotic resistance, the study of bacterial metabolic behavior stimulated by novel antimicrobial agents becomes a relevant tool to elucidate involved adaptive pathways. Profiling of volatile metabolites was performed to monitor alterations of bacterial metabolism induced by biosynthesized silver nanoparticles (bio-AgNPs). Escherichia coli, Enterococcus faecalis, Klebsiella pneumoniae and Proteus mirabilis were isolated from pressure ulcers, and their cultures were prepared in the presence/absence of bio-AgNPs at 12.5, 25 and 50 µg mL⁻¹. Headspace solid phase microextraction associated to gas chromatography–mass spectrometry was the employed analytical platform. At the lower concentration level, the agent promoted positive modulation of products of fermentation routes and bioactive volatiles, indicating an attempt of bacteria to adapt to an ongoing suppression of cellular respiration. Augmented response of aldehydes and other possible products of lipid oxidative cleavage was noticed for increasing levels of bio-AgNPs. The greatest concentration of agent caused a reduction of 44 to 80% in the variety of compounds found in the control samples. Pathway analysis indicated overall inhibition of amino acids and fatty acids routes. The present assessment may provide a deeper understanding of molecular mechanisms of bio-AgNPs and how the metabolic response of bacteria is untangled.     

Nanoarchitectonics of CdS/ZnSnO3 heterostructures for Z-Scheme mediated directional transfer of photo-generated charges with enhanced photocatalytic performance

The construction of heterostructure is an effective strategy to synergetically couple wide-band-gap with the narrow-band-gap semiconductor with a mediate optical property and charge transfer capability. Herein, the Z-Scheme CdS/ZnSnO₃ (CdS/ZSO) heterostructures were constructed by anchoring CdS nanoparticles on the surface of double-shell hollow cubic ZnSnO₃ via the hydrothermal method. The direct recombination of excited electrons in the conduction band (CB) of ZSO and holes in the valence band (VB) of CdS via d-p conjugation at the interface greatly accelerated the internal electric field (IEF). The transfer mode follows the Z-Scheme mechanism, where CdS/ZSO synergistically facilitates the efficient charges transfer from CdS to ZnSnO₃ through the intimate interface. Here, ZnSnO₃ and CdS serve as an oxidation photocatalyst (OP) and reduction photocatalyst (RP), respectively. Thus, it can promote synergistically the oxidation half-reaction and reduction half-reaction of H₂ evolution. The density-functional theory (DFT) calculation further confirms the charges transfer from CdS to ZnSnO₃. The hydrogen evolution of 5% CdS/ZSO heterostructure reached 1167.3 μmol g^?1, which was about 8 and 3 folds high compared to pristine ZSO (141.9 μmol g^?1) and CdS (315.5 μmol g^?1), during 3 h of reaction respectively. Furthermore, the CdS/ZSO heterostructures could suppress the photo corrosion of CdS, resulting in its high stability. This work is expected to enlighten the rational design of heterostructure for OP and RP to promote the hybrid heterostructures photocatalytic H₂ evolution.     

Tailored-Made Polydopamine Nanoparticles to Induce Ferroptosis in Breast Cancer Cells in Combination with Chemotherapy

Ferroptosis is gaining followers as mechanism of selective killing cancer cells in a non-apoptotic manner, and novel nanosystems capable of inducing this iron-dependent death are being increasingly developed. Among them, polydopamine nanoparticles (PDA NPs) are arousing interest, since they have great capability of chelating iron. In this work, PDA NPs were loaded with Fe³⁺ at different pH values to assess the importance that the pH may have in determining their therapeutic activity and selectivity. In addition, doxorubicin was also loaded to the nanoparticles to achieve a synergist effect. The in vitro assays that were performed with the BT474 and HS5 cell lines showed that, when Fe³⁺ was adsorbed in PDA NPs at pH values close to which Fe(OH)₃ begins to be formed, these nanoparticles had greater antitumor activity and selectivity despite having chelated a smaller amount of Fe³⁺. Otherwise, it was demonstrated that Fe³⁺ could be released in the late endo/lysosomes thanks to their acidic pH and their Ca²⁺ content, and that when Fe³⁺ was co-transported with doxorubicin, the therapeutic activity of PDA NPs was enhanced. Thus, reported PDA NPs loaded with both Fe³⁺ and doxorubicin may constitute a good approach to target breast tumors.     

The influence of FeNi nanoparticles on the microstructures and soft magnetic properties of FeSi soft magnetic composites

In this work, a new type of FeSi/FeNi soft magnetic powder core (SMPC) was successfully fabricated by coating FeNi nanoparticles on the surface of FeSi micrometer powder. The effects of different contents of FeNi nanoparticles on the micromorphology, internal structures, and soft magnetic properties of SMPCs were studied. The results show that FeNi nanoparticles adhere to the surface of FeSi powder, which can effectively fill the air gap between FeSi powder and is beneficial to the compaction of the powder cores during the pressing process. Thus, the density of the SMPCs is increased. Compared to FeSi SMPCs, the comprehensive soft magnetic properties of FeSi/FeNi SMPCs have been greatly improved. When adding 15 wt% FeNi nanoparticles, the SMPCs exhibit excellent magnetic properties with high effective permeability (increased by 43.8 %) and low core loss (decreased by 22.1 %). The high performance FeSi/FeNi SMPCs prepared in this work are expected to be widely used in power choke coils, uninterruptible power supplies, and boosts and inverter inductors.     

Maskless Preparation of Spatially-Resolved Plasmonic Nanoparticles on Polydimethylsiloxane via In Situ Fluoride-Assisted Synthesis

Here, a fluoride-assisted route for the controlled in-situ synthesis of metal nanoparticles (NPs) (i.e., AgNPs, AuNPs) on polydimethylsiloxane (PDMS) is reported. The size and coverage of the NPs on the PDMS surface are modulated with time and over space during the synthetic process, leveraging the improved yield (10×) and faster kinetics (100×) of NP formation in the presence of F⁻ ions, compared to fluoride-free approaches. This enables the maskless preparation of both linear and step gradients and patterns of NPs in 1D and 2D on the PDMS surface. As an application in flexible plasmonics/photonics, continuous and step-wise spatial modulations of the plasmonic features of PDMS slabs with 1D and 2D AgNP gradients on the surface are demonstrated. An excellent spatially resolved tuning of key optical parameters, namely, optical density from zero to 5 and extinction ratio up to 100 dB, is achieved with AgNP gradients prepared in AgF solution for 12 minutes; the performance are comparable to those of commercial dielectric/interference filters. When used as a rejection filter in optical fluorescence microscopy, the AgNP-PDMS slabs are able to reject the excitation laser at 405 nm and retain the green fluorescence of microbeads (100 µm) used as test cases.     

Impact behavior of aminosilane functionalized nanosilica based shear thickening fluid impregnated Kevlar fabrics

In the present work, two types of shear thickening fluids have been synthesized by using neat and aminosilane functionalized silica nanoparticles and their viscosity curves have been obtained by the rheometer. Based on the values of peak viscosity of synthesized shear thickening fluids, the surface functionalized nanosilica based shear thickening fluid has been chosen as a best candidate due to the high viscosity for impregnation into the neat Kevlar of different layers viz. four (04) and eight (08) layers for velocity impact study. The experimental investigations reveal high energy absorption of shear thickening fluid impregnated Kevlar as compared to the neat Kevlar. The maximum energy absorption 62 J is achieved corresponding to the initial velocity 154 m∙s⁻¹ for 08 layers shear thickening fluid impregnated Kevlar specimen. The data have also been analytically determined and validated with the experimental data. The experimental data have good agreement with the analytical data within the accuracy of around 15 to 20%. The present findings can have significant inferences towards the fabrication of shear thickening fluids using nanomaterials for numerous applications such as soft armors, dampers, nanofinishing and so forth.     

Synthesis of a Fe3O4-rGO-ZnO-catalyzed photo-Fenton system with enhanced photocatalytic performance

In this work, we designed a magnetically-separable Fe₃O₄-rGO-ZnO ternary catalyst, ZnO anchored on the surface of reduced graphene oxide (rGO)-wrapped Fe₃O₄ magnetic nanoparticles, where rGO, as an effective interlayer, can enhance the synergistic effect between ZnO and Fe₃O₄. The effects of three operational parameters, namely irradiation time, hydrogen peroxide dosage, and the catalyst dosage, on the photo-Fenton degradation of methylene blue and methyl orange were investigated. The results showed that the Fe₃O₄-rGO-ZnO had great potential for the destruction of organic compounds from wastewater using the Fenton chemical oxidation method at neutral pH. Repeatability of the photocatalytic activity after 5 cycles showed only a tiny drop in the catalytic efficiency.