Tuning the optical absorption of potential blue emitters

The quest for more efficient blue emitters to be applied in organic light-emitting diodes is one of the challenging tasks of contemporary nanotechnologies. An approach to enhance substantially the intrinsic efficiency of luminescent organic molecules is the so-called thermally activated delayed fluorescence. A prerequisite for its occurrence is a vanishing energy separation between the first singlet and triplet excited states. A series of donor–acceptor molecules is investigated theoretically within this study in order to validate a molecular model for design of efficient organic blue emitters with closely spaced singlet and triplet excited states. The model is based on meta-linkage of the donor and acceptor residues to a spacer ensuring frontier molecular orbitals partitioning. The optimal geometries of the molecules are obtained with density functional theory (B3LYP/6-31G^*) and the singlet and triplet absorption spectra are simulated within the time-dependent density functional framework. The excited singlet-triplet energy gap is estimated and correlated to structural and energetic characteristics of the donors and acceptors. Several requirements for achieving high-energy triplet states at the molecular level in such donor–acceptor systems are outlined, the main being disjoint character of the molecular orbitals on the spacer and sufficient energy separation of the two topmost occupied orbitals. It is shown that by variation of the acceptor moiety the optical absorption transitions of the compounds can be fine-tuned in a systematic fashion. Molecules with degenerate singlet and triplet first excited states are proposed, combining bisdimethylaminotriphenylamine or phenoxazine as donors with diphenyloxadiazole or diphenyl-2,2′-bipyridine as acceptors. Bipolar molecules derived from this model could be used as prospective building blocks for efficient emissive materials in blue organic light-emitting diodes.     

Atomic Insights into the Enhanced Surface Stability in High Voltage Cathode Materials by Ultrathin Coating

Surface properties of electrode materials play a critical role in the function of batteries. Therefore, surface modifications, such as coatings, have been widely used to improve battery performance. Understanding how these coatings function to improve battery performance is crucial for both scientific research and applications. In this study the electrochemical performance of coated and uncoated LiNi_0.5Mn_1.5O₄ (LNMO) electrodes is correlated with ensemble‐averaged soft X‐ray absorption spectroscopy (XAS) and spatially resolved scanning transmission electron microscopy‐electron energy loss spectroscopy (STEM‐EELS) to illustrate the mechanism of how ultrathin layer Al₂O₃ coatings improve the cycle life of LiNi_0.5Mn_1.5O₄. Mn²⁺ evolution on the surface is clearly observed in the uncoated sample, which results from the reaction between the electrolytic solution and the surfaces of LiNi_0.5Mn_1.5O₄ particles, and also possibly atomic structure reconstructions and oxygen loss from the surface region in LiNi_0.5Mn_1.5O₄. The coating effectively suppresses Mn²⁺ evolution and improves the battery performance by decelerating the impedance buildup from the surface passivation. This study demonstrates the importance of combining ensemble‐averaged techniques (e.g., XAS) with localized techniques (e.g., STEM‐EELS), as the latter may yield unrepresentative information due to the limited number of studied particles, and sheds light on the design of future coating processes and materials.     

Ultrathin Polydopamine Films with Phospholipid Nanodiscs Containing a Glycophorin A Domain

Cellular membranes have long served as an inspiration for nanomaterial research. The preparation of ultrathin polydopamine (PDA) films with integrated protein pores containing phospholipids and an embedded domain of a membrane protein glycophorin A as simplified cell membrane mimics is reported. Large area, ultrathin PDA films are obtained by electropolymerization on gold surfaces with 10–18 nm thickness and dimensions of up to 2.5 cm². The films are transferred from gold to various other substrates such as nylon mesh, silicon, or substrates containing holes in the micrometer range, and they remain intact even after transfer. The novel transfer technique gives access to freestanding PDA films that remain stable even at the air interfaces with elastic moduli of ≈6–12 GPa, which are higher than any other PDA films reported before. As the PDA film thickness is within the range of cellular membranes, monodisperse protein nanopores, so‐called “nanodiscs,” are integrated as functional entities. These nanodisc‐containing PDA films can serve as semi‐permeable films, in which the embedded pores control material transport. In the future, these simplified cell membrane mimics may offer structural investigations of the embedded membrane proteins to receive an improved understanding of protein‐mediated transport processes in cellular membranes.     

Highly Conductive Carbon Nanotube‐Graphene Hybrid Yarn

An efficient procedure for the fabrication of highly conductive carbon nanotube/graphene hybrid yarns has been developed. To start, arrays of vertically aligned multi‐walled carbon nanotubes (MWNT) are converted into indefinitely long MWNT sheets by drawing. Graphene flakes are then deposited onto the MWNT sheets by electrospinning to form a composite structure that is transformed into yarn filaments by twisting. The process is scalable for yarn fabrication on an industrial scale. Prepared materials are characterized by electron microscopy, electrical, mechanical, and electrochemical measurements. It is found that the electrical conductivity of the composite MWNT‐graphene yarns is over 900 S/cm. This value is 400% and 1250% higher than electrical conductivity of pristine MWNT yarns or graphene paper, respectively. The increase in conductivity is asssociated with the increase of the density of states near the Fermi level by a factor of 100 and a decrease in the hopping distance by an order of magnitude induced by grapene flakes. It is found also that the MWNT‐graphene yarn has a strong electrochemical response with specific capacitance in excess of 111 Fg^?1. This value is 425% higher than the capacitance of pristine MWNT yarn. Such substantial improvements of key properties of the hybrid material can be associated with the synergy of MWNT and graphene layers in the yarn structure. Prepared hybrid yarns can benefit such applications as high‐performance supercapacitors, batteries, high current capable cables, and artificial muscles.     

Dynamic spectrum access in terrestrial TV band: assessment of prospects in Kenya

Wireless connectivity has become a significant part of human life all over the world, both in developing and developed countries. In order to provide sufficient coverage without the densification of cellular networks, relatively low carrier frequencies should be used. This paper considers the reuse of the digital terrestrial television (DTT) band for cellular system operation in Kenya, while protecting incumbent TV signal reception according to the Dynamic Spectrum Alliance (DSAL) rules. A state of the art model for DTT coverage and allowed cellular system power calculation is tested using real data for Kenya. Suggestions regarding future DSAL rules amendments are provided. Moreover, the amount of spectrum resources available for cellular system operation in the DTT band in Kenya is estimated against varying system parameters.

     

Length scales and size distributions in dynamic fragmentation

The shatter of a cherished wine glass on impact with the kitchen tile, the spallation in the high-energy collision of atomic nuclei, the fragmentation of the Shoemaker-Levi comet on passage of the Roche limit of the Jovian gravitational field, collectively span vast length scales, yet are each examples of dynamic fragmentation with a number of commonalities. In the above examples, as well as many other dynamic fragmentation events, the consequence is the breakage of the body into some number of fragments that are distributed over size. At the heart of a satisfactory theory is the prediction of the number of fragments and the statistical distribution of these fragments over size. A theory based on energy principles is found to provide length scales that govern both the characteristic fragment size and the distribution spread. Fundamental failure and fracture properties of the material are central in determining the nature of the fragment size distribution. Fragment size distributions can range from relatively tight exponential functions to power-law relations spanning a number of decades in fragment size. The fragment distribution and the dynamic fracture processes leading to power-law distributions bear striking similarities to hydrodynamic turbulence. Onset of fracture asymptotes to a range of length scales in which destruction is self-similar and fractal, requiring that consequences, including the fragment size distributions, exhibit a power-law dependence on the length scale. The theory is described and supporting experimental evidence is provided.     

Flow Rate Limitation of Steady Convective Dominated Open Capillary Channel Flows Through a Groove

An open capillary channel is a structure that establishes a liquid flow path when the capillary pressure caused by surface tension forces dominates in comparison to the hydrostatic pressure induced by gravitational or residual accelerations. To maintain a steady flow through the channel the capillary pressure of the free surface has to balance the pressure difference between the liquid and the surrounding constant pressure gas phase. Due to convective and viscous momentum transport the pressure along the flow path of the liquid decreases and causes the free surface to bend inwards. The maximum flow rate through the channel is reached when the free surface collapses and gas ingestion occurs near the outlet. This stability limit depends on the geometry of the channel and the properties of the liquid. In this paper we present an experimental setup which is used in the low-gravity environment of the Bremen Drop Tower. Experiments with convective dominated systems have been performed where the flow rate was increased up to the maximum value. In comparison to this we present a one-dimensional theoretical model to determine important characteristics of the flow, such as the free surface shape and the limiting flow rate. Furthermore we present an explanation for the mechanism of flow rate limitation for these flow conditions which is similar to the choking problem for compressible gas flows.     

Effects of initial albumen quality and mineral oil–chitosan emulsion coating on internal quality and shelf‐life of eggs during room temperature storage

Effects of mineral oil (MO) and mineral oil–chitosan emulsion (MO:CH = 25:75) as coatings on internal quality and shelf‐life of eggs were evaluated during 5‐week storage at 25 °C. Eggs with three different initial albumen qualities [Haugh unit (HU): H = 87.8, M = 75.6 and L = 70.9] were evaluated. As storage time increased, HU and yolk index values decreased whereas weight loss increased. Coating with MO and/or 25:75 MO:CH emulsion could preserve the internal quality for at least 4 more weeks for H‐eggs and at least 3 more weeks for M and/or L‐eggs, all with weight losses <0.92%. All coated eggs had >70% positive purchase intent, and their colour differences at week 0 could not be detected by naked human eye (ΔE^* < 3.0, noncoated eggs as reference). Consumers significantly differentiated freshly MO‐coated from noncoated eggs on overall surface appearance. This study demonstrated that MO and 25:75 MO:CH emulsion coatings could preserve internal quality and prolong shelf‐life of eggs.