Histidine Ligated Iron-Sulfur Peptides

Iron-sulfur clusters are thought to be ancient cofactors that could have played a role in early protometabolic systems. Thus far, redox active, prebiotically plausible iron-sulfur clusters have always contained cysteine ligands to the cluster. However, extant iron-sulfur proteins can be found to exploit other modes of binding, including ligation by histidine residues, as seen with [2Fe-2S] Rieske and MitoNEET proteins. Here, we investigated the ability of cysteine- and histidine-containing peptides to coordinate a mononuclear Fe²⁺ center and a [2Fe-2S] cluster and compare their properties with purified iron-sulfur proteins. The iron-sulfur peptides were characterized by UV-vis, circular dichroism, and paramagnetic NMR spectroscopies and cyclic voltammetry. Small (≤6 amino acids) peptides can coordinate [2Fe-2S] clusters through a combination of cysteine and histidine residues with similar reduction potentials as their corresponding proteins. Such complexes may have been important for early cell-like systems.     

Highly efficient subnanometer Ru-based catalyst for ammonia synthesis via an associative mechanism

The industrial manufacture of ammonia (NH₃) using Fe-based catalyst works under rigorous conditions. For the goal of carbon-neutrality, it is highly desired to develop advanced catalyst for NH₃ synthesis at mild conditions to reduce energy consumption and CO₂ emissions. However, the main challenge of NH₃ synthesis at mild conditions lies in the dissociation of steady NN triple bond. In this work, we report the design of subnanometer Ru clusters (0.8 nm) anchored on the hollow N-doped carbon spheres catalyst (Ru-SNCs), which effectively promotes the NH₃ synthesis at mild conditions via an associative route. The NH₃ synthesis rate over Ru-SNCs (0.49% (mass) Ru) reaches up to 11.7 mmol NH₃·(g cat)^-1·h^-1 at 400 ℃ and 3 MPa, which is superior to that of 8.3 mmol NH₃·(g cat)^-1·h^-1 over Ru nanoparticle catalyst (1.20% (mass) Ru). Various characterizations show that the N₂H₄ species are the main intermediates for NH₃ synthesis on Ru-SNCs catalyst. It demonstrates that Ru-SNCs catalyst can follow an associative route for N₂ activation, which circumvents the direct dissociation of N₂ and results in highly efficient NH₃ synthesis at mild conditions.     

Preparation of O′-Sialon-based ceramics by two-stage liquid phase sintering and study on the toughening mechanism of ultrafine-grained sintered clusters

Ultrafine-grained O′-Sialon-based ceramics were prepared by two-stage sintering at 1250 °C, with large particle GH4169 superalloy powder and nano Al₂O₃–Y₂O₃ as composite sintering aids. The effects of these aids on the densification, microstructure, and mechanical properties of O′-Sialon-based ceramics during two-stage sintering were also studied. Studies have shown that the densification process of O′-Sialon-based ceramics promoted by composite sintering additives, presents with the characteristics of two-stage liquid-phase sintering. In the first stage, GH4169 formed ultrafine-grained sintered clusters in the sintered material through liquid phase diffusion. In the second stage, the uniformly dispersed nano Al₂O₃–Y₂O₃ realized the uniform sintering of the material. In the fracture process, the ultrafine-grained sintered clusters hindered the crack propagation and promoted multiple deflections of the crack around the edge of the clusters, achieving the effect of crack deflection toughening. This effect, dominated by ultrafine-grained sintered clusters, significantly improved the fracture toughness of O′-Sialon-based ceramics up to 8.52 MPa m^1/2.     

Morphology development of ZnO produced by sonothermal process

Wurtzite ZnO (hcp) was produced by the 80 °C sonothermal reactions of 1:5, 1:10, and 1:20 molar ratios of Zn(NO₃)₂·6H₂O:NaOH in water, containing 2 g, 5 g, 10 g, and 20 g of polyethylene glycol (PEG) with the molecular weights (MWs) of 6000, 10000, and 20000 for 1 h, 3 h, and 5 h. ZnO phase with different morphologies was detected. When the amount of NaOH, both MW and the amount of PEG, and the experimental time were increased, the products still retain their single phase, but their morphologies were changed from nanoplates in clusters to nanospears with sharp tips gathering together in the shape of flowers, and long nanorods with oval tips in clusters. In the present work, formation mechanism of these products was also discussed.     

Co9S8@CNFs复合材料的制备及其在锂离子电池的应用

静电纺丝是一种使聚合物在高压静电场作用下进行拉伸纺丝的纤维制造工艺。静电纺丝制备方法简单,成本低且易纺出微纳米级的纤维,在材料化学领域被广泛应用。采用硫杂杯芳烃构筑的多硫高核笼簇化合物（Co₄₈）为负载物,以聚丙烯腈（PAN）和聚甲基丙烯酸甲酯（PMMA）共混物（PAN/PMMA）为纺丝载体,通过静电纺丝技术,制备了负载Co₉S₈纳米颗粒的碳纳米纤维（Co₉S₈@CNFs）。分别以PAN和PMMA质量比为10∶0、7∶3和5∶5的纺丝载体制备复合物纳米纤维,将其热处理后得到的碳纳米纤维复合材料作为电极材料用于锂离子电池材料的研究。与Co₄₈晶体煅烧的产物相比,PAN和PMMA的加入对最终产物的电化学有促进作用。由PAN和PMMA混合物制备的复合物材料兼具较高比容量、良好循环稳定性以及倍率性能。     

Friction force microscopy investigation of nanostructured carbon films

Frictional properties of nanostructured carbon-based films, obtained by deposition of supersonic carbon clusters, have been investigated by friction force microscopy under ambient conditions. The experiment was performed at low loads to avoid plastic deformation and wear of materials. By analysing the load-dependent measurements acquired on samples with different composition, we deduced that the Hertzian-plus-offset model can take into account the frictional behaviour of these materials. A strong dependence of adhesive forces on the specific surface location was observed. A quantitative comparison among these films and atom-assembled carbon compounds is finally presented.     

Structures and stabilities of C36-rings

C₃₆-rings with D_nh symmetries have been investigated using the semi-empirical molecular orbital method (AM1). The ring structures are beneficial to the stability of the C₃₆ systems. An analysis of several factors, such as the change in strain energies due to the distortion of C₃₆ cages, the type of the bonded carbon atoms, the size of retained aromatic domains and the shared pentagon-pentagon double bonds, is given for their contributions to stabilities of the C₃₆-rings. The electronic properties are also discussed and compared with those of C₆₀-rings.     

Oxidation,Redox Disproportionation and Chain Termination Reactions Catalysed by the Pd‐561 Giant Cluster

Redox disproportionation of benzyl alcohol to benzaldehyde and toluene catalysed by the Pd₅₆₁phen₆₀(OAc)₁₈₀ (phen=1,10‐phenanthroline) giant cluster 1 under anaerobic conditions was found, whereas in an O₂ atmosphere cluster 1 catalyses the oxidation of benzyl alcohol to benzaldehyde and inhibits further oxidation of the latter. A study of the AIBN‐initiated and non‐initiated oxidation of benzyl alcohol, sec‐butyl alcohol and styrene in the presence of cluster 1 revealed that cluster 1 performs three functions in the oxidation reactions: 1) catalysis of polar oxidation of the substrates with O₂, 2) termination of the chains of radical oxidation, and 3) catalysis of redox disproportionation.     

Preparation of Benzylamine by Highly Selective Reductive Amination of Benzaldehyde Over Ru on an Acidic Activated Carbon Support as the Catalyst

Platinum particles (<1.5 nm) have been shown to behave as bases in their interaction with -alumina. FTIR spectra of adsorbed pyridine probe molecules showed that the acid strength of the -alumina was decreased by the presence of (<1.5 nm) Pt particles. Ammonium chloride treatment converts the primary Pt clusters to H _x Pt _y Cl _z intermediates that de-anchor from the support. Consequently, agglomeration to 8 nm Pt particles was observed following treatment in hydrogen at a relatively mild temperature. For the treated catalyst the IR data of absorbed pyridine show a 3 cm^-1 increase relative to the original Pt/-Al₂O₃ catalyst, indicating a strengthening of the acidity. Changes in the Pt particle size were confirmed by FTIR spectroscopy of CO absorbed onto the Pt particles before and after treatment. Consecutive CO and pyridine probe adsorption demonstrated the electronic interplay between the Pt particles and the support. Pyridine adsorption onto the -alumina support of a Pt/Al₂O₃ catalyst pre-dosed with CO produces a nearly 40 cm^-1 lowering of the CO peak position, indicative of CO bond weakening. In the case of CO adsorbed onto a catalyst pre-dosed with pyridine, a shift in the pyridine IR spectrum was only observed from the original highly dispersed catalyst.     

New Preparation Method of CdS Clusters Encapsulated in Y-Type Zeolites

CdS clusters encapsulated in Y-type zeolite were prepared by a novel technique with non-aqueous systems. The mechanical mixture of CdCl₂· 2.5H₂O crystal with Y-type zeolite was heated at 773 K, followed by the H₂S treatment at 373 K, resulting in the formation of CdS clusters with the size <2.3 nm.