Binary solid-solution alloys generally adopt one of three principal crystal lattices—body-centred cubic (bcc), hexagonal close-packed (hcp) or face-centred cubic (fcc) structures—in which the structure is dominated by constituent elements and compositions. Therefore, it is a significant challenge to selectively control the crystal structure in alloys with a certain composition. Here, we propose an approach for the selective control of the crystal structure in solid-solution alloys by using a chemical reduction method. By precisely tuning the reduction speed of the metal precursors, we selectively control the crystal structure of alloy nanoparticles, and are able to selectively synthesize fcc and hcp AuRu3 alloy nanoparticles at ambient conditions. This approach enables us to design alloy nanomaterials with the desired crystal structures to create innovative chemical and physical properties.
The
crystal structure significantly affects the physical and chemical
properties of solids. However, the crystal structure-dependent properties
of alloys are rarely studied because controlling the crystal structure
of an alloy at the same composition is extremely difficult. Here,
for the first time, we successfully demonstrate the synthesis of binary
Ru–Pt (Ru/Pt = 7:3) and Ru–Ir (Ru/Ir = 7:3) and ternary
Ru–Ir–Pt (Ru/Ir/Pt = 7:1.5:1.5) solid-solution alloy
nanoparticles (NPs) with well-controlled hexagonal close-packed (hcp)
and face-centered cubic (fcc) phases, through the chemical reduction
method. The crystal structure control is realized by precisely tunning
the reduction speeds of the metal precursors. The effect of the crystal
structure on the catalytic performance of solid-solution alloy NPs
is systematically investigated. Impressively, all the hcp alloy NPs
show superior electrocatalytic activities for the hydrogen evolution
reaction in alkaline solution compared with the fcc alloy NPs. In
particular, hcp-RuIrPt exhibits extremely high intrinsic (mass) activity,
which is 3.1 (3.2) and 6.7 (6.9) times enhanced compared to that of
fcc-RuIrPt and commercial Pt/C.
The semisynthesis of arglabin, an anticancer drug in clinical application, is developed from abundant natural product parthenolide via three steps. Each step in this sequence is highly stereoselective, and the substrate-dependent stereoselectivity in the epoxidation step can be explained by computational calculations. The success of chemical semisynthesis of arglabin suggests that the biosynthesis of arglabin might proceed in a similar pathway.
Rakicidin A is a cyclic depsipeptide that has exhibited unique growth inhibitory activity against chronic myelogenous leukemia stem cells. Furthermore, rakicidin A has five chiral centers with unknown stereochemical assignment, and thus, can be represented by one of 32 possible stereoisomers. To predict the most probable stereochemistry of rakicidin A, calculations and structural comparison with natural cyclic depsipeptides were applied. A total synthesis of the proposed structure was subsequently completed and highlighted by the creation of a sterically hindered ester bond (C1-C15) through trans-acylation from an easily established isomer (C1-C13). The analytic data of the synthetic target were consistent with that of natural rakicidin A, and then the absolute configuration of rakicidin A was assigned as 2S, 3S, 14S, 15S, 16R. This work suggests strategies for the determination of unknown chiral centers in other cyclic depsipeptides, such as rakicidin B, C, D, BE-43547, and vinylamycin, and facilitates the investigations of rakicidin A as an anticancer stem cell agent.
Quasi‐zero‐stiffness (QZS) isolators of high‐static‐low‐dynamic stiffness play an important role in ultra‐low frequency vibration mitigation. While the current designs of QZS mainly exploit the combination of negative‐stiffness corrector and positive‐stiffness element, and only have a single QZS working range, here a class of tailored mechanical metamaterials with programmable QZS features is proposed. These programmed structures contain curved beams with geometries that are specifically designed to enable the prescribed QZS characteristics. When these metamaterials are compressed, the curved beams reach the prescribed QZS working range in sequence, thus enabling tailored stair‐stepping force‐displacement curves with multiple QZS working ranges. Compression tests demonstrate that a vast design space is achieved to program the QZS features of the metamaterials. Further vibration tests confirm the ultra‐low frequency vibration isolation capability of the proposed mechanical metamaterials. The mechanism of QZS stems solely from the structural geometry of the curved beams and is therefore materials‐independent. This design strategy opens a new avenue for innovating compact and scalable QZS isolators with multiple working ranges.
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