Domain Engineering in ReS2 by Coupling Strain during Electrochemical Exfoliation

Chemical exfoliation has been used for the fast and large‐scale production of 2D nanosheets from graphene and transition metal dichalcogenides; however, it is rarely used for domain engineering of exfoliated nanosheets. Herein, it is found that the use of large sized molecular intercalants during electrochemical intercalation induce atomic row dislocation and parallel mirror twin boundaries (MTBs) on an otherwise pristine rhenium disulfide (ReS₂) crystal, such that the exfoliated flakes possess a parallel, multi‐domain structure. These domains can be distinguished under a polarized microscope owing to the intrinsic in‐plane optical dichroic properties of ReS₂, thereby affording a way to track the number of domains introduced versus the size of the molecular intercalant during electrochemical exfoliation. Ferromagnetism is detected on the intercalated sample using large sized molecular intercalants. Density function theory suggests that these may be due to the coupled effects of lattice strain and S vacancies in the MTBs.     

Wet shells and dry tales: the evolutionary ‘Just-So’ stories behind the structure–function of biominerals

The ability of evolution to shape organic form involves the interactions of multiple systems of constraints, including fabrication, phylogeny and function. The tendency to place function above everything else has characterized some of the historical biological literature as a series of ‘Just-So’ stories that provided untested explanations for individual features of an organism. A similar tendency occurs in biomaterials research, where features for which a mechanical function can be postulated are treated as an adaptation. Moreover, functional adaptation of an entire structure is often discussed based on the local characterization of specimens kept in conditions that are far from those in which they evolved. In this work, environmental- and frequency-dependent mechanical characterization of the shells of two cephalopods, Nautilus pompilius and Argonauta argo, is used to demonstrate the importance of multi-scale environmentally controlled characterization of biogenic materials. We uncover two mechanistically independent strategies to achieve deformable, stiff, strong and tough highly mineralized structures. These results are then used to critique interpretations of adaptation in the literature. By integrating the hierarchical nature of biological structures and the environment in which they exist, biomaterials testing can be a powerful tool for generating functional hypotheses that should be informed by how these structures are fabricated and their evolutionary history.     

“Quasi‐freestanding” Graphene‐on‐Single Walled Carbon Nanotube Electrode for Applications in Organic Light‐emitting Diode

An air‐stable transparent conductive film with “quasi‐freestanding” graphene supported on horizontal single walled carbon nanotubes (SWCNTs) arrays is fabricated. The sheet resistance of graphene films stacked via layer‐by‐layer transfer (LBL) on quartz, and modified by 1‐Pyrenebutyric acid N‐hydroxysuccinimide ester (PBASE), is reduced from 273 Ω/sq to about 76 Ω/sq. The electrical properties are stable to heat treatment (up to 200 ºC) and ambient exposure. Organic light‐emitting diodes (OLEDs) constructed of this carbon anode (T ≈ 89.13% at 550 nm) exhibit ≈88% power efficiency of OLEDs fabricated on an ITO anode (low turn on voltage ≈3.1 eV, high luminance up to ≈29 490 cd/m², current efficiency ≈14.7 cd/A). Most importantly, the entire graphene‐on‐SWCNT hybrid electrodes can be transferred onto plastic (PET) forming a highly‐flexible OLED device, which continues to function without degradation in performance at bending angles >60°.     

Synthesis,characterization and biophysical evaluation of the 2D Ti2CTx MXene using 3D spheroid-type cultures

MXenes are novel 2-D materials which have been extensively investigated for use in advanced biocomposites, water purification, biosensors, bioimaging and antibacterial systems. However, the knowledge associated with the mechanism of cytotoxic response is still limited to lack of verification against 3D spheroid-type cultures. Herein, we present a report on the in vitro cytotoxicity of Ti₂CT_x MXene against cervical cancer cell lines (HeLa) in a form of 3D spheroid with comparison to 2D cell culture system. Ti₂CT_x MXenes can be characterized by their multi-layered structure that is produced by the efficient elimination of Al and appearance of the surface functional groups. The biological results with 2D and 3D HeLa indicated that the Ti₂CT_x MXene was moderately cytotoxic to cells and the cytotoxicity was dose dependent. Our results showed that the toxicity of MXenes is potentially due to direct contact of the Ti₂CT_x MXene with the cell membrane wall. The Raman spectra suggested that the Ti₂CT_x MXenes interfered with the cytoplasmic proteins’ conformation and the surrounding microenvironment. This inherently modified the biochemistry of the cell membrane and caused cell apoptosis. This paper contributes to the pool of knowledge regarding the biocompatibility and biophysical properties of Ti₂CT_x MXene.     

A nonparametric method for fitting a straight line to a noisy image

In fitting a straight line to a noisy image, the least-squares method becomes highly unreliable either when the noise distribution is nonnormal or when it is contaminated by outliers. The authors propose a nonparametric method, the median of the intercepts, to overcome these difficulties. This method is free of assumptions about the noise distribution and insensitive to outliers, and it does not require quantization of the parameter space. Thus, unlike the Hough transform, its outcome does not depend on the bin size. The method is efficient and its implementation does not involve practical difficulties such as local minima or poor convergence of iterative procedures     

Oscillatory structure–property correlation in azelate polyols and thermoplastic polyurethanes

Azelate polyols of 2000 g mol^?1 have been successfully prepared via esterification of renewable azelaic acid with linear diols containing different number of CH₂ repeating units. Structure–property correlation of the azelate polyols had been evaluated in thermoplastic polyurethanes (TPUs). TPUs based on azelate polyols of longer chained linear diols with >4 CH₂ repeat units retained higher degrees of crystallinity associated with the polyol soft segment. The ratio of hydrogen bonded urethane in the hard segment to free urethane phase mixed with the soft segment in the TPUs showed a complex oscillating dependence with increased number of CH₂ repeating unit in the linear diols of azelate polyols. Correspondingly, static and dynamic properties of TPUs also showed the oscillatory dependence, whereby dynamic properties maximized with odd number of CH₂ repeating unit and material strength maximized with even number of CH₂ repeating unit. The results therefore can be used as guide to select appropriate azelate polyols to target specific TPU performance. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46258.     

Highly Stable Two‐Dimensional Tin(II) Iodide Hybrid Organic–Inorganic Perovskite Based on Stilbene Derivative

Hybrid organic–inorganic perovskites have recently emerged as potential disruptive photovoltaic technology. However, the toxicity of lead used in state‐of‐the‐art hybrid perovskites solar cell prevents large‐scale commercialization, which calls for lead‐free alternatives. Sn‐based perovskites have been considered as alternatives but they are limited by rapid oxidation and decomposition in ambient air. Here, an Sn‐based two‐dimensional hybrid organic–inorganic perovskites [A₂B_(n‐1)Sn_nI_(3n+1)] (n = 1 and 2) are reported with improved air stability, using bulky stilbene derivatives as the organic cations (2‐(4‐(3‐fluoro)stilbenyl)ethanammonium iodide (FSAI)). The moisture stability of the [(FSA)₂SnI₄] perovskites is attributed to the hydrophobic properties of fluorine‐functionalized organic chains (FSA), as well as the strong cohesive bonding in the organic chains provided by H bonds, CH···X type H bonds, weak interlayer F···F interaction, and weak face‐to‐face type π‐π interactions. The photodetector device fabricated on exfoliated single crystal flake of [(FSA)₂SnI₄] exhibits fast and stable photoconductor response.     

Cobalt Single-Atom-Intercalated Molybdenum Disulfide for Sulfide Oxidation with Exceptional Chemoselectivity

The identification of chemoselective oxidation process en route to fine chemicals and specialty chemicals is a long-standing pursuit in chemical synthesis. A vertically structured, cobalt single atom-intercalated molybdenum disulfide catalyst (Co₁-in-MoS₂) is developed for the chemoselective transformation of sulfides to sulfone derivatives. The single-atom encapsulation alters the electron structure of catalyst owing to confinement effect and strong metal–substrate interaction, thus enhancing adsorption of sulfides and chemoselective oxidation at the edge sites of MoS₂ to achieve excellent yields of up to 99% for 34 examples. The synthetic scopes can be extended to sulfide-bearing alkenes, alkynes, aldehydes, ketones, boronic esters, and amines derivatives as a toolbox for the synthesis of high-value, multifunctional sulfones and late-stage functionalization of pharmaceuticals, e.g., Tamiflu. The synthetic utility of cobalt single atom-intercalated MoS₂, together with its reusability, scalability, and simplified purification process, renders it promising for industrial productions.     

Multiferroic nanocomposite fabrication via liquid phase using anodic alumina template

We report a novel and inexpensive fabrication process of multiferroic nanocomposite via liquid phase using an anodic alumina template. The sol-gel spin-coating technique was used to coat the template with ferrimagnetic CoFe₂O₄. By dissolving the template with NaOH aqueous solution, a unique nanotube array structure of CoFe₂O₄ was obtained. The CoFe₂O₄ nanotube arrays were filled with, and sandwiched in, ferroelectric BaTiO₃ layers by a sol-gel spin-coating method to obtain the composite. Its multiferroicity was confirmed by measuring the magnetic and dielectric hysteresis loops.