Two-Dimensional Supramolecular Polymerization of DNA Amphiphiles is Driven by Sequence-Dependent DNA-Chromophore Interactions

Two-dimensional (2D) assemblies of water-soluble block copolymers have been limited by a dearth of systematic studies that relate polymer structure to pathway mechanism and supramolecular morphology. Here, we employ sequence-defined triblock DNA amphiphiles for the supramolecular polymerization of free-standing DNA nanosheets in water. Our systematic modulation of amphiphile sequence shows the alkyl chain core forming a cell membrane-like structure and the distal π-stacking chromophore block folding back to interact with the hydrophilic DNA block on the nanosheet surface. This interaction is crucial to sheet formation, marked by a chiral “signature”, and sensitive to DNA sequence, where nanosheets form with a mixed sequence, but not with a homogeneous poly(thymine) sequence. This work opens the possibility of forming well-ordered, bilayer-like assemblies using a single DNA amphiphile for applications in cell sensing, nucleic acid therapeutic delivery and enzyme arrays.     

Catalyst-Controlled Divergent Generations and Transformations of α-Carbonyl Cations from Alkynes**

α-Carbonyl cations are the umpolung forms of the synthetically fundamental α-carbonyl carbanions. They are highly reactive yet rarely studied and utilized species and their precursors were rather limited. Herein, we report the catalyst-controlled divergent generations of α-carbonyl cations from single alkyne functionalities and the interception of them via Wagner–Meerwein rearrangement. Two chemodivergent catalytic systems have been established, leading to two different types of α-carbonyl cations and, eventually, two different types of products, i.e. the α,β- and β,γ-unsaturated carbonyl compounds. Broad spectrum of alkynes including aryl alkyne, ynamide, alkynyl ether, and alkynyl sulfide could be utilized and the migration priorities of different groups in the Wagner–Meerwein rearrangement step was elucidated. Density functional theory calculations further supported the intermediacy of α-carbonyl cations via the N−O bond cleavage in both the two catalytic systems. Another key feature of this methodology was the fragmentation of synthetically inert tert-butyl groups into readily transformable olefin functionalities. The synthetic potential was highlighted by the scale-up reactions and the downstream diversifications including the formal synthesis of nicotlactone B and galbacin.     

Maldistribution of Chemical Bond Strength Inducing Exceptional Anisotropy of Thermal Conductivity in Non-Layered Materials

Currently, the efforts to find materials with high κ anisotropy ratios mainly focus on layered materials, however, the limited quantity and lower workability comparing to non-layered ones boost the exploration of non-layered materials with high κ anisotropy ratios. Here, taking PbSnS₃, a typical non-layered orthorhombic compound, as an example, we propose that maldistribution of chemical bond strength can lead to large anisotropy of κ in non-layered materials. Our result reveals that the maldistribution of Pb−S bonds lead to obvious collective vibrations of dioctahedron chain units, resulting in an anisotropy ratio up to 7.1 at 200 K and 5.5 at 300 K, respectively, which is one of the highest ever reported in non-layered materials and even surpasses many classical layered materials such as Bi₂Te₃ and SnSe. Our findings can not only broaden the horizon for exploring high anisotropic κ materials but also provide new opportunities for the application of thermal management.     

A Cross-linked Polyethylene with Recyclability and Mechanical Robustness Enabled by Establishment of Multiple Hydrogen Bonds Network via Reactive Melt Blending

Physical cross-linking by hydrogen-bonds(H-bonds), providing a good combination of application properties of thermosets and processability of thermoplastics, is a potential strategy to resolve the recycling problem of traditional chemically cross-linked polyethylene.However, ureidopyrimidone(UPy), the most widely used H-bonding motif, is unfavorable for large-scale industrial application due to its poor thermal stability. In this work, H-bonds cross-linked polyethylene was successfully prepared ...     

Polymerizable C70 derivatives with acrylate functionality for efficient and stable solar cells

Fullerene-based organic solar cells are generally suffering from severe microstructure evolution occurring in their bulk heterojunction active layers and thus are extremely stable. To address it, four polymerizable C₇₀ fullerene derivatives, [6,6]-phenyl-C₇₁-ethyl acrylate (PC₇₁EA), [6,6]-phenyl-C₇₁-propyl acrylate (PC₇₁PrA), [6,6]-phenyl-C₇₁-butyl acrylate (PC₇₁BA), and [6,6]-phenyl-C₇₁-pentyl acrylate (PC₇₁PeA), have been designed, synthesized, and investigated. These fullerene compounds have a molecular structure, shape and size very like the conventional C₇₀ fullerene acceptor, [6,6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM), and have been found no different in their light absorption, redox potentials, and frontier orbital energy levels. Using these fullerene acrylates individually as acceptor and poly(3-hexylthiophene) as donor, organic solar cells have been fabricated and gave optimal efficiencies ranging from 3.32% to 4.16%, comparable to PC₇₁BM-based reference cells (4.06%). Owing to their acrylate functionality, these fullerene derivatives can turn into insoluble upon heating, and thus endow their solar cell devices much better thermostability than PC₇₁BM-based reference cells. The best one, coming from PC₇₁PeA devices, reported an optimal efficiency of 4.16%, and maintained 91.7% efficiency after heat treatment at 150 °C for 35 h. As a sharp contrast, the PC₇₁BM reference cell dropped its optimal efficiency from 4.06% to 0.48% only after 5 h heat treatment. X-ray diffraction, optical and atomic force microscopy, and space-charge-limited current method have been carried out to understand active layer structure, morphology, and charge mobility change during heat treatment.     

Bulk metallic glasses based on ytterbium and calcium

We report the formation of a family of bulk metallic glasses (BMGs) based on rare earth element of ytterbium and alkaline earth element of calcium. The glass-forming ability, atomic packing density and corrosion behaviors of the BMGs show an extremum around the eutectic point with the change of the concentration of Yb and Ca.     

An Optical Sensing Platform for Beta-Glucosidase Activity Using Protein-Inorganic Hybrid Nanoflowers

In this work, a convenient and dual-signal readout optical sensing platform for the sensitively and selectively determination of beta-glucosidase (β-Glu) activity was reported using protein-inorganic hybrid nanoflowers [BSA-Cu₃(PO₄)₂·3H₂O] possessing peroxidase-mimicking activity. The nanoflowers (NFs) were facilely synthesized through a self-assembled synthesis strategy at room temperature. The as-prepared NFs could catalytically convert the colorless and non-fluorescent Amplex Red into colored and highly fluorescent resorufin in the presence of hydrogen peroxide via electron transfer process. β-Glu could hydrolyze cyanogenic glycoside, using amygdalin (Amy) as a model, into cyanide ions (CN^?), which can subsequently efficiently suppress the catalytic activity of NFs, accompanied with the fluorescence decrease and the color fading. The concentration of CN^? was controlled by β-Glu-triggered enzymatic reaction of Amy. Thus, a sensing system was established for fluorescent and visual determination of β-Glu activity. Under the optimum conditions, the present fluorescent and visual bimodal sensing platform exhibited good sensitivity for β-Glu activity assay with a detection limit of 0.33 U·L^?1. The sensing platform was further applied to determinate β-Glu in real samples and satisfactory results were attained. Additionally, the optical sensing system can potentially be a promising candidate for β-Glu inhibitors screening.

     

Lithium metal batteries for high energy density: Fundamental electrochemistry and challenges

The dependence on portable devices and electrical vehicles has triggered the awareness on the energy storage systems with ever-growing energy density.Lithium me...     

Sustainable recycling of titanium from TiO2 in spent SCR denitration catalyst via molten salt electrolysis

Spent catalyst used for denitration by selective catalytic reduction (spent SCR denitration catalysts) is one of the important urban mines due to the high conte...     

制备工艺条件对SiO2薄膜非均质特性的影响

薄膜材料的生长过程随镀膜机尺寸的增大而呈现新的规律,为制备膜层均匀性好、材料均质的大尺寸光学元件,分别在不同离子源能量、沉积压强、基板加热温度及基板转速条件下,采用离子辅助电子束蒸发方法制备了不同单层SiO2薄膜样品;利用分光光度计及椭偏仪分别对样品的透过率及椭偏参数进行测量,并对测量结果进行拟合得到不同样品的折射率及非均质特性。实验结果表明,工件架转速是使大尺寸SiO2薄膜材料产生非均质特性的主要影响因素,离子源能量、基板温度、沉积压强通过影响材料生长过程对材料的非均质特性产生调控;对于大尺寸薄膜光学元件,工件架转速存在限制的条件下,优化其他工艺参数可以获得均质SiO2薄膜材料,该结果对于制备具有优良性能的大尺寸薄膜光学元件具有借鉴意义。