Patterning π‐Conjugated Polymers

π‐Conjugated polymers show promise as active materials in application areas such as microelectronics, electro‐optics, opto‐electronics, and photonics. A critical feature in this emerging technology is device fabrication and the reproducible deposition of active material. This review focuses on current trends in the spatial deposition of conjugated polymers.     

Amyloid Self‐Assembly of hIAPP8‐20 via the Accumulation of Helical Oligomers, α‐Helix to β‐Sheet Transition,and Formation of β‐Barrel Intermediates

The self‐assembly of human islet amyloid polypeptide (hIAPP) into β‐sheet‐rich nanofibrils is associated with the pathogeny of type 2 diabetes. Soluble hIAPP is intrinsically disordered with N‐terminal residues 8–17 as α‐helices. To understand the contribution of the N‐terminal helix to the aggregation of full‐length hIAPP, here the oligomerization dynamics of the hIAPP fragment 8–20 (hIAPP8‐20) are investigated with combined computational and experimental approaches. hIAPP8‐20 forms cross‐β nanofibrils in silico from isolated helical monomers via the helical oligomers and α‐helices to β‐sheets transition, as confirmed by transmission electron microscopy, atomic force microscopy, circular dichroism spectroscopy, Fourier transform infrared spectroscopy, and reversed‐phase high performance liquid chromatography. The computational results also suggest that the critical nucleus of aggregation corresponds to hexamers, consistent with a recent mass‐spectroscopy study of hIAPP8‐20 aggregation. hIAPP8‐20 oligomers smaller than hexamers are helical and unstable, while the α‐to‐β transition starts from the hexamers. Converted β‐sheet‐rich oligomers first form β‐barrel structures as intermediates before aggregating into cross‐β nanofibrils. This study uncovers a complete picture of hIAPP8‐20 peptide oligomerization, aggregation nucleation via conformational conversion, formation of β‐barrel intermediates, and assembly of cross‐β protofibrils, thereby shedding light on the aggregation of full‐length hIAPP, a hallmark of pancreatic beta‐cell degeneration.     

Multilayer Amorphous‐Si‐B‐C‐N/γ‐Al2O3/α‐Al2O3 Membranes for Hydrogen Purification

The hydrogen and carbon monoxide separation is an important step in the hydrogen production process. If H₂ can be selectively removed from the product side during hydrogen production in membrane reactors, then it would be possible to achieve complete CO conversion in a single‐step under high temperature conditions. In the present work, the multilayer amorphous‐Si‐B‐C‐N/γ‐Al₂O₃/α‐Al₂O₃ membranes with gradient porosity have been realized and assessed with respect to the thermal stability, geometry of pore space and H₂/CO permeance. The α‐Al₂O₃ support has a bimodal pore‐size distribution of about 0.64 and 0.045 µm being macroporous and the intermediate γ‐Al₂O₃ layer—deposited from boehmite colloidal dispersion—has an average pore‐size of 8 nm being mesoporous. The results obtained by the N₂‐adsorption method indicate a decrease in the volume of micropores—0.35 vs. 0.75 cm³ g^?1—and a smaller pore size ?6.8 vs. 7.4 Å—in membranes with the intermediate mesoporous γ‐Al₂O₃ layer if compared to those without. The three times Si‐B‐C‐N coated multilayer membranes show higher H₂/CO permselectivities of about 10.5 and the H₂ permeance of about 1.05 × 10^?8 mol m^?2 s^?1 Pa^?1. If compared to the state of the art of microporous membranes, the multilayer Si‐B‐C‐N/γ‐Al₂O₃/α‐Al₂O₃ membranes are appeared to be interesting candidates for hydrogen separation because of their tunable nature and high‐temperature and high‐pressure stability.     

Self‐Assembled α‐Cyanostilbenes for Advanced Functional Materials

In the specific context of condensed media, the significant and increasing recent interest in the α‐cyanostilbene (CS) motif [? Ar? CH?C(CN)? Ar? ] is relevant. These compounds have shown remarkable optical features in addition to interesting electrical properties, and hence they are recognized as very suitable and versatile options for the development of functional materials. This progress report is focused on current and future use of CS structures and molecular assemblies with the aim of exploring and developing for the next generations of functional materials. A critical selection of illustrative materials that contain the CS motif, including relevant subfamilies such as the dicyanodistyrylbenzene and 2,3,3‐triphenylacrylonitrile shows how, driven by the self‐assembly of CS blocks, a variety of properties, effects, and possibilities for practical applications can be offered to the scientific community, through different rational routes for the elaboration of advanced materials. A survey is provided on the research efforts directed toward promoting the self‐assembly of the solid state (polycrystalline solids, thin films, and single crystals), liquid crystals, nanostructures, and gels with multistimuli responsiveness, and applications for sensors, organic light‐emitting diodes, organic field effect transistors, organic lasers, solar cells, or bioimaging purposes.     

H+‐Insertion Boosted α‐MnO2 for an Aqueous Zn‐Ion Battery

Rechargeable Zn/MnO₂ batteries using mild aqueous electrolytes are attracting extensive attention due to their low cost, high safety, and environmental friendliness. However, the charge‐storage mechanism involved remains a topic of controversy so far. Also, the practical energy density and cycling stability are still major issues for their applications. Herein, a free‐standing α‐MnO₂ cathode for aqueous zinc‐ion batteries (ZIBs) is directly constructed with ultralong nanowires, leading to a rather high energy density of 384 mWh g^?1 for the entire electrode. Greatly, the H⁺/Zn²⁺ coinsertion mechanism of α‐MnO₂ cathode for aqueous ZIBs is confirmed by a combined analysis of in situ X‐ray diffractometry, ex situ transmission electron microscopy, and electrochemical methods. More interestingly, the Zn²⁺‐insertion is found to be less reversible than H⁺‐insertion in view of the dramatic capacity fading occurring in the Zn²⁺‐insertion step, which is further evidenced by the discovery of an irreversible ZnMn₂O₄ layer at the surface of α‐MnO₂. Hence, the H⁺‐insertion process actually plays a crucial role in maintaining the cycling performance of the aqueous Zn/α‐MnO₂ battery. This work is believed to provide an insight into the charge‐storage mechanism of α‐MnO₂ in aqueous systems and paves the way for designing aqueous ZIBs with high energy density and long‐term cycling ability.     

Nitrogen Doped γ‐Graphyne: A Novel Anode for High‐Capacity Rechargeable Alkali‐Ion Batteries

High energy density is the major demand for next‐generation rechargeable batteries, while the intrinsic low alkali metal adsorption of traditional carbon–based electrode remains the main challenge. Here, the mechanochemical route is proposed to prepare nitrogen doped γ‐graphyne (NGY) and its high capacity is demonstrated in lithium (LIBs)/sodium (SIBs) ion batteries. The sample delivers large reversible Li (1037 mAh g^?1) and Na (570.4 mAh g^?1) storage capacities at 100 mA g^?1 and presents excellent rate capabilities (526 mAh g^?1 for LIBs and 180.2 mAh g^?1 for SIBs) at 5 A g^?1. The superior Li/Na storage mechanisms of NGY are revealed by its 2D morphology evolution, quantitative kinetics, and theoretical calculations. The effects on the diffusion barriers (E_b) and adsorption energies (E_ad) of Li/Na atoms in NGY are also studied and imine‐N is demonstrated to be the ideal doping format to enhance the Li/Na storage performance. Besides, the Li/Na adsorption routes in NGY are optimized according to the experimental and the first‐principles calculation results. This work provides a facile way to fabricate high capacity electrodes in LIBs/SIBs, which is also instructive for the design of other heteroatomic doped electrodes.     

Dipolar‐Distribution Cavity γ‐Fe2O3@C@α‐MnO2 Nanospindle with Broadened Microwave Absorption Bandwidth by Chemically Etching

Developing microwave absorption materials with ultrawide bandwidth and low density still remains a challenge, which restricts their actual application in electromagnetic signal anticontamination and defense stealth technology. Here a series of olive‐like γ‐Fe₂O₃@C core–shell spindles with different shell thickness and γ‐Fe₂O₃@C@α‐MnO₂ spindles with different volumes of dipolar‐distribution cavities were successfully prepared. Both series of absorbers exhibit excellent absorption properties. The γ‐Fe₂O₃@C@α‐MnO₂ spindle with controllable cavity volume exhibits an effective absorption (2O₃@C spindle reaches as high as ?45 dB because of the optimized electromagnetic impedance balance between polymer shell and γ‐Fe₂O₃ core. Intrinsic ferromagnetism of the anisotropy spindle is confirmed by electron holography. Strong coupling of magnetic flux stray lines between spindles is directly imaged. This unique morphology and facile etching technique might facilitate the study of core–shell type microwave absorbers.     

Oxidation protective coatings for γ‐TiAl – recent trends

Engine designers show continued interest in γ‐TiAl based titanium aluminides as light–weight structural materials to be used at moderately elevated temperatures. Although alloy development has made significant progress in terms of mechanical properties and environmental resistance, protective coatings have been developed that help to extend the lifetime of these alloys significantly. The major challenge of coating development is to prevent the formation of fast growing titania. Furthermore, changes of coating chemistries at high temperatures have to be considered in order to avoid rapid degradation of the coatings due to interdiffusion between substrate and coating. The paper describes recent work of the authors on different coatings produced by means of magnetron sputter technique. Thin ceramic Ti‐Al‐Cr‐Y‐N layers tested at 900 °C exhibited poor oxidation resistance. In contrast, intermetallic Ti‐Al‐Cr, Si‐based and aluminum rich Ti‐Al coatings were tested at exposure temperatures up to 950 °C for 1000h resulting in reasonable and partially excellent oxidation behaviour.     

Coaggregation of κ‐Casein and β‐Lactoglobulin Produces Morphologically Distinct Amyloid Fibrils

The unfolding, misfolding, and aggregation of proteins lead to a variety of structural species. One form is the amyloid fibril, a highly aligned, stable, nanofibrillar structure composed of β‐sheets running perpendicular to the fibril axis. β‐Lactoglobulin (β‐Lg) and κ‐casein (κ‐CN) are two milk proteins that not only individually form amyloid fibrillar aggregates, but can also coaggregate under environmental stress conditions such as elevated temperature. The aggregation between β‐Lg and κ‐CN is proposed to proceed via disulfide bond formation leading to amorphous aggregates, although the exact mechanism is not known. Herein, using a range of biophysical techniques, it is shown that β‐Lg and κ‐CN coaggregate to form morphologically distinct co‐amyloid fibrillar structures, a phenomenon previously limited to protein isoforms from different species or different peptide sequences from an individual protein. A new mechanism of aggregation is proposed whereby β‐Lg and κ‐CN not only form disulfide‐linked aggregates, but also amyloid fibrillar coaggregates. The coaggregation of two structurally unrelated proteins into cofibrils suggests that the mechanism can be a generic feature of protein aggregation as long as the prerequisites for sequence similarity are met.     

Facile Synthesis of γ‐In2Se3 Nanoflowers toward High Performance Self‐Powered Broadband γ‐In2Se3/Si Heterojunction Photodiode

An effective colloidal process involving the hot‐injection method is developed to synthesize uniform nanoflowers consisting of 2D γ‐In₂Se₃ nanosheets. By exploiting the narrow direct bandgap and high absorption coefficient in the visible light range of In₂Se₃, a high‐quality γ‐In₂Se₃/Si heterojunction photodiode is fabricated. This photodiode shows a high photoresponse under light illumination, short response/recovery times, and long‐term durability. In addition, the γ‐In₂Se₃/Si heterojunction photodiode is self‐powered and displays a broadband spectral response ranging from UV to IR with a high responsivity and detectivity. These excellent performances make the γ‐In₂Se₃/Si heterojunction very interesting as highly efficient photodetectors.