Frustrated Lewis Pair-Type Reactivity of Intermolecular Rare-Earth Aryloxide and N-Heterocyclic Carbene/Olefin Combinations.

This work reports the cooperative reactivity of rare-earth aryloxide complexes with N-heterocyclic carbene (NHC) or N-heterocyclic olefin (NHO), showcasing their synergistic effect on the activation of H2 and diverse organic substrates. Reactions of RE(OAr)3 (RE=La, Sm, and Y; Ar=2,6-tBu2-C6H3) with unsaturated NHC ItBu (:C[N(R)CH]2, R=tBu) isolated abnormally bound RE metal NHC complexes RE/aNHC. In contrast, no metal-NHO adducts were formed when RE(OAr)3 were treated with NHO (R2C=C[N(R)C(R)]2, R=CH3). Both RE/aNHC and RE/NHO Lewis pairs enabled cooperative H2 activation. Furthermore, RE(OAr)3 were found to catalyze the hydrogenation of the exocyclic C=C double bond of NHO under mild conditions. Moreover, treatment of the La/aNHC complex with benzaldehyde produced a La/C4 1,2-addition product. The La/NHO Lewis pair could react with (trimethylsilyl)diazomethane and α, ß-conjugated imine, affording an isocyanotrimethylsilyl lanthanum amide complex and a La/C 1,4-addition product, respectively.

Double Bond Cleavage in Small Molecules Using a Geminal Sc/P Lewis Pair.

Frustrated Lewis pairs (FLPs) have proven capable of cleaving the H-H σ-bond and binding a variety of unsaturated small molecules. In contrast, examples of FLP-mediated complete rupture of double-bonded substrates remain scarce. Herein, we present a geminal Sc/P Lewis pair, i.e., (ArO)2ScN(tBu)PPh2 (Ar = 2,6-tBu2-C6H3), that exhibits typical FLP-type 1,2-addition reactivity toward CO2. Notably, it enables the complete cleavage of a series of double bonds, such as the N═N bond in azobenzene or pyridazine, the N═O bond in nitrosobenzene, and the N═S and S═O bonds in N-sulfinylaniline, to yield the corresponding metallacyclic products. Moreover, the first rare-earth metal sulfur monoxide adduct could be obtained through the bond cleavage of PhNSO, demonstrating the capability of rare-earth metal complexes to capture reactive species.

Enhancing Thermal Insulation of EPDM Ablators via Constructing Alternating Planar Architectures.

Ethylene-propylene-diene monomer (EPDM) composites were usually enhanced with ablative additives to protect solid rocket motor (SRMs) casings. However, the poor thermal insulation caused by the high thermal conductive ablative fillers can lead to rocket motor failure. Herein, the novel EPDM composites containing alternating layers of ablative EPDM (AM) and heat-insulated EPDM (HM) were prepared through layer-multiplying extrusion. Compared with conventional EPDM ablative material, the multilayer composites showed enhanced thermal insulation and mechanical properties that could be further improved by tuning the number of layers. The ablation and thermal insulation properties possessing in AM and HM layers could be combined by forced assembly during co-extrusion, and the alternating multilayer composite was capable of showing the effect of each component. In particular, compared with AM, the maximum back-face temperature with 40 alternating layers of AM/HM decreased from 96.2 °C to 75.6 °C during oxyacetylene test, while the good ablation properties were preserved in the AM component. This significant improvement was attributed to the planar orientation and densification of ablative additives, and the interruption of conductive pathways in the through-plane direction of AM/HM alternating laminate. The anisotropic EPDM composites featuring mechanical robustness, good ablative resistance and thermal insulation suggest considerable potential application in the aerospace industry.

Reaction kinetics and a physical model of the charring layer by depositing Al2O3 at ultra-high temperatures.

The thermochemical ablation of insulation material caused by slag deposition in solid rocket motors has increasingly attracted researchers' attention. Understanding the ablation mechanism and the ability to calculate reaction kinetics parameters determine the height of the thermal protection design for advanced solid rocket motors. In this work, the interaction of the Al2O3-C system is determined through static ablation experiments. Using X-ray diffraction, HSC thermodynamic software, and a thermogravimetric analyser, the carbon thermal reduction of alumina is analysed and the reaction mechanism and physical model are obtained. Isothermal experiments at 1700-1850 °C and mathematical analysis provide the kinetic parameters of the overall and step-by-step reactions. The results show that the overall reaction of the Al2O3-C system involves three steps. The overall reaction kinetics are described by the contracting area model R2 with apparent activation and frequency factors estimated as 254.5 kJ mol-1 and 5.5 × 106 min-1, respectively. The distribution reaction kinetics of steps 1 and 2 are described by the first-order chemical reaction control model (F1) and that of step 3 is described by the one-dimensional diffusion control model (D1). The corresponding activation energies are 107.9 kJ mol-1, 240.3 kJ mol-1, and 567.5 kJ mol-1, and frequency factors are 625.94 min-1, 8.3 × 105 min-1, and 1.6 × 1014 min-1, respectively.

Efficient label-free chemiluminescent immunosensor based on dual functional cupric oxide nanorods as peroxidase mimics.

Dual-functional cupric oxide nanorods (CuONRs) as peroxidase mimics are proposed for the development of a flow-through, label-free chemiluminescent (CL) immunosensor. Forming the basis of this cost-efficient, label-free immunoassay, CuONRs, synthesized using a simple hydrothermal method, were deposited onto epoxy-activated standard glass slides, followed by immobilization of biotinylated capture antibodies through a streptavidin bridge. The CuONRs possess excellent catalytic activity, along with high stability as a solid support. Antigens could then be introduced to the sensing system, forming large immunocomplexes that prevent CL substrate access to the surface, thereby reducing the CL signal in a concentration dependent fashion. Using carcinoembryonic antigen (CEA) as a model analyte, the proposed label-free immunosensor was able to rapidly determine CEA with a wide linear range of 0.1-60ngmL-1 and a low detection limit of 0.05ngmL-1. This nanozyme-based immunosensor is simple, sensitive, cost-efficient, and has the potential to be a very promising platform for fast and efficient biosensing applications.