The artificial TDHs had unique kinetic parameters, distinct from one another. Structural analysis indicates that consensus mutations are mainly introduced in the secondary or outer shell. The functional diversity of the artificial TDHs is due to the accumulation of mutations that affect their physicochemical properties. Taken together, our findings indicate that our proposed approach can help generate artificial enzymes with unique enzymatic properties.We report on a family of five new 4f- and 4d-doped sandwich-type germanotungstates with the general formula [(n-C4H9)4N]l/mH2[(M(H2O)3)(γ-GeW10O35)2]·3(CH3)2CO [M(H 2 O) 3 (GeW 10 ) 2 ] (M = CeIII, NdIII, GdIII, ErIII, l = 7; ZrIV, m = 6), which have been synthesized at room temperature in an acetone-water mixture. Among the compound series, [Zr(H 2 O) 3 (GeW 10 ) 2 ] 8 -, which has been obtained in the presence of 30% H2O2, represents the first example of a 4d-substituted germanotungstate incorporating the intact dilacunary [γ-GeIVW10O36]8- building block. All compounds were characterized thoroughly in the solid state by single-crystal and powder X-ray diffraction (XRD), IR spectroscopy, thermogravimetric analysis (TGA), and elemental analysis and in solution by NMR and UV-vis spectroscopy. The phosphoesterase activity of [Ce(H 2 O) 3 (GeW 10 ) 2 ] 9- and [Zr(H 2 O) 3 (GeW 10 ) 2 ] 8- toward the model substrates 4-nitrophenyl phosphate (NPP) and O,O-dimethyl O-(4-nitrophenyl) phosphate (DMNP) was monitored with 1H- and 31P-NMR spectroscopy revealing an acceleration of the hydrolytic reaction by an order of magnitude (kcorr = 3.44 (±0.30) × 10-4 min-1 for [Ce(H 2 O) 3 (GeW 10 ) 2 ] 9- and kcorr = 5.36 (±0.05) × 10-4 min-1 for [Zr(H 2 O) 3 (GeW 10 ) 2 ] 8- ) as compared to the uncatalyzed reaction (kuncat = 2.60 (±0.10) × 10-5 min-1). [Ce(H 2 O) 3 (GeW 10 ) 2 ] 9- demonstrated improved antibacterial activity toward Moraxella catarrhalis (MIC 32 μg/mL), compared to the unsubstituted [GeW 10 O 36 ] 8- POM (MIC 64 μg/mL).Establishing ultimate spin current efficiency in graphene over industry-standard substrates can facilitate research and development exploration of spin current functions and spin sensing. At the same time, it can resolve core issues in spin relaxation physics while addressing the skepticism of graphene’s practicality for planar spintronic applications. In this work, we reveal an exceptionally long spin communication capability of 45 μm and highest to date spin diffusion length of 13.6 μm in graphene on SiO2/Si at room temperature. Employing commercial chemical vapor deposited (CVD) graphene, we show how contact-induced surface charge transfer doping and device doping contributions, as well as spin relaxation, can be quenched in extremely long spin channels and thereby enable unexpectedly long spin diffusion lengths in polycrystalline CVD graphene. Brimarafenib Extensive experiments show enhanced spin transport and precession in multiple longest channels (36 and 45 μm) that reveal the highest spin lifetime of ∼2.5-3.5 ns in graphene over SiO2/Si, even under ambient conditions. Such performance, made possible due to our devices approaching the intrinsic spin-orbit coupling of ∼20 μeV in graphene, reveals the role of the D’yakonov-Perel’ spin relaxation mechanism in graphene channels as well as contact regions. Our record demonstration, fresh device engineering, and spin relaxation insights unlock the ultimate spin current capabilities of graphene on SiO2/Si, while the robust high performance of commercial CVD graphene can proliferate research and development of innovative spin sensors and spin computing circuits.The hexagonal 4H phase gold nanostructures shows great potential for catalysis, optical, and biomedical fields. However, its phase stability remains largely unclear. Here, we report the 4H-to-face-centered cubic (fcc) phase transformation of gold induced by CO gas interactions and an electron beam observed through in-situ transmission electron microscopy (in-situ TEM). The atomic scale transformation mechanism is revealed experimentally and supported by first-principle calculations. Density functional theory calculations show that the 4H-to-fcc phase transformation processes via the transition of layer sliding with expanded layer spacing, which can be facilitated by both the adsorbed CO molecules and the extra electron provided by the electron beam. The transformation first takes place at the edges of the nanorods with the collective assistance of both CO and extra electrons, and then the inner portion of the bulk crystal follows with extra electrons as the lubricant. These results promote the understanding of the toxic effect of CO gas and shining light on the structural conversion and atomic migration of noble metal catalysts when they interact with CO molecules.Cancer vaccines have opened a new paradigm for safe and effective antitumor therapy, but they still suffer from shortcomings such as insufficient immunogenicity and immune tolerance, which seldom makes them the first choice in clinic. In fact, similar to providing a high-end product, a robust antitumor effect depends on the inherent supply chain, which attains, processes, and presents tumor-associated antigens via antigen presenting cells to T cells, which then leads to lysis of the cancer cells to release more antigens to complete the supply chain. Under these circumstances, the failure of cancer vaccines can be treated as a blockade or chain rupture. Thus, for effective tumor treatment, the key is to rationally design logistic systems to restore the supply chain.Under these circumstances, this Account summarizes our recent attempts to exploit the immunogenic trait of synthetic particles to enhance the distribution, presentation, and immune activations of the whole priming process in cancer vaccines (1) Raw blockade to reinforce the antitumor efficacy. Collectively, this Account aims to illustrate the potential of the particulate cancer vaccines to recapitalize the inherent host immune responses for the maximum antitumor effect. And by integrating the antitumor supply chain, optimized synthetic particles may shed light on the development of safe and effective particulate cancer vaccines.