High‐Performance n‐Channel Organic Transistors Using High‐Molecular‐Weight Electron‐Deficient Copolymers and Amine‐Tailed Self‐Assembled Monolayers

While high‐performance p‐type semiconducting polymers are widely reported, their n‐type counterparts are still rare in terms of quantity and quality. Here, an improved Stille polymerization protocol using chlorobenzene as the solvent and palladium(0)/copper(I) as the catalyst is developed to synthesize high‐quality n‐type polymers with number‐average molecular weight up to 10⁵ g mol^?1. Furthermore, by sp²‐nitrogen atoms (sp²‐N) substitution, three new n‐type polymers, namely, pBTTz, pPPT, and pSNT, are synthesized, and the effect of different sp²‐N substitution positions on the device performances is studied for the first time. It is found that the incorporation of sp²‐N into the acceptor units rather than the donor units results in superior crystalline microstructures and higher electron mobilities. Furthermore, an amine‐tailed self‐assembled monolayer (SAM) is smoothly formed on a Si/SiO₂ substrate by a simple spin‐coating technique, which can facilitate the accumulation of electrons and lead to more perfect unipolar n‐type transistor performances. Therefore, a remarkably high unipolar electron mobility up to 5.35 cm² V^?1 s^?1 with a low threshold voltage (≈1 V) and high on/off current ratio of ≈10⁷ is demonstrated for the pSNT‐based devices, which are among the highest values for unipolar n‐type semiconducting polymers.     

Ultrahigh Photocatalytic Rate at a Single‐Metal‐Atom‐Oxide

Metal oxides, as one of the mostly abundant and widely utilized materials, are extensively investigated and applied in environmental remediation and protection, and in energy conversion and storage. Most of these diverse applications are the result of a large diversity of the electronic states of metal oxides. Noticeably, however, many metal oxides present obstacles for applications in catalysis, mainly due to the lack of efficient active sites with desired electronic states. Here, the fabrication of single‐tungsten‐atom‐oxide (STAO) is demonstrated, in which the metal oxide's volume reaches its minimum as a unit cell. The catalytic mechanism in the STAO is determined by a new single‐site physics mechanism, named as quasi‐atom physics. The photogenerated electron transfer process is enabled by an electron in the spin‐up channel excited from the highest occupied molecular orbital to the lowest unoccupied molecular orbital +1 state, which can only occur in STAO with W⁵⁺. STAO results in a record‐high and stable sunlight photocatalytic degradation rate of 0.24 s^?1, which exceeds the rates of available photocatalysts by two orders of magnitude. The fabrication of STAO and its unique quasi‐atom photocatalytic mechanism lays new ground for achieving novel physical and chemical properties using single‐metal‐atom oxides (SMAO).     

Schleifbearbeitung von Hart‐Weich‐Verbunden – Finite‐Elemente‐Simulation des Schleifprozesses von hybriden Schichtverbunden

Grinding of ceramic‐metal‐compounds – finite element analysis simulation of the grinding process of hybrid stratified compounds In this paper, the subproject TP 8 “Grinding of ceramic‐metal‐compounds” is been introduced. An adapted grinding strategy should be created for the production of a ceramic‐cemented carbide compound drill. This aim should be obtained with experimental analysis and the use of finite element analysis to simulate the grinding process of ceramic‐cemented carbide compound drill. Furthermore a basic approach for simulating the grinding process of hybrid stratified compounds is been presented, which should be a basis for a finite element analysis simulation of a grinding process of ceramic‐cemented carbide compound drill.     

Microfluidic Skin‐on‐a‐Chip Models: Toward Biomimetic Artificial Skin

The role of skin in the human body is indispensable, serving as a barrier, moderating homeostatic balance, and representing a pronounced endpoint for cosmetics and pharmaceuticals. Despite the extensive achievements of in vitro skin models, they do not recapitulate the complexity of human skin; thus, there remains a dependence on animal models during preclinical drug trials, resulting in expensive drug development with high failure rates. By imparting a fine control over the microenvironment and inducing relevant mechanical cues, skin‐on‐a‐chip (SoC) models have circumvented the limitations of conventional cell studies. Enhanced barrier properties, vascularization, and improved phenotypic differentiation have been achieved by SoC models; however, the successful inclusion of appendages such as hair follicles and sweat glands and pigmentation relevance have yet to be realized. The present Review collates the progress of SoC platforms with a focus on their fabrication and the incorporation of mechanical cues, sensors, and blood vessels.     

Platelet‐to‐lymphocyte ratio better predicts inflammation than neutrophil‐to‐lymphocyte ratio in end‐stage renal disease patients

Neutrophil‐to‐lymphocyte ratio (NLR) was introduced as a potential marker to determine inflammation in end‐stage renal disease (ESRD) patients. Recently, platelet‐to‐lymphocyte ratio (PLR) and NLR were found to positively correlated with inflammatory markers including tumor necrosis factor‐α (TNF‐α) and interleukin (IL)‐6 in cardiac and noncardiac patients. Data regarding PLR and its association with inflammation are lacking in hemodialysis (HD) and peritoneal dialysis (PD) patients. Hence, we aimed to determine the relationship between PLR, NLR, and inflammation in ESRD patients. This was a cross‐sectional study involving 62 ESRD patients (29 females, 33 males; mean age, 49.6 ± 14.6 years) receiving PD or HD for ≥6 months in the Dialysis Unit of Necmettin Erbakan University. PLR, NLR, C‐reactive protein, TNF‐α, IL‐6 levels were measured. PLR, NLR, serum high sensitive C‐reactive protein, IL‐6, and TNF‐α levels were significantly higher in PD patients when compared with HD patients. ESRD patients with PLR ≥ 140 had significantly higher NLR, IL‐6, and TNF‐α levels when compared to patients with PLR < 139. In the bivariate correlation analysis, PLR was positively correlated with NLR, IL‐6, and TNF‐α in this population. When we compared the association of PLR and NLR with IL‐6 (r = 0.371, P = 0.003 vs. r = 0.263, P = 0.04, respectively) and TNF‐α (r = 0.334, P = 0.008 vs. r = 0.273, P = 0.032, respectively), PLR was found to be superior to NLR in terms of inflammation in ESRD patients. Simple calculation of PLR can predict inflammation better than NLR in ESRD patients.     

Multifunctional POSS‐Based Nano‐Photo‐Initiator for Overcoming the Oxygen Inhibition of Photo‐Polymerization and for Creating Self‐Wrinkled Patterns

Oxygen inhibition remains a challenge in photo‐curing technology despite the expenditure of considerable effort in developing a convenient, efficient, and low‐cost prevention method. Here, a novel strategy to prevent oxygen inhibition is presented; it is based on the self‐assembly of multifunctional nano‐photo‐initiators (F₂‐POSS‐(SH)₄‐TX/EDB) at the interface of air and the liquid monomer. These nano‐photo‐initiators consist of a thiol‐containing polyhedral oligomeric silsesquioxane (POSS) skeleton onto which fluorocarbon chains and thioxanthone and dimethylaminobenzoate (TX/EDB) photo‐initiator moieties are grafted. Real‐time Fourier‐transform infrared spectroscopy (FT‐IR) is used to investigate the photo‐polymerization of various acrylate monomers that are initiated by F₂‐POSS‐(SH)₄‐TX/EDB and its model analogues in air and in N₂. FT‐IR results show that F₂‐POSS‐(SH)₄‐TX/EDB decreases the effects of oxygen inhibition. X‐ray photo‐electron spectroscopy and atomic force microscopy reveal that the self‐assembly of F₂‐POSS‐(SH)₄‐TX/EDB at the air/(liquid monomer) interface forms a cross‐linked top layer via thiol–ene polymerization; this layer acts as a physical barrier against the diffusion of oxygen from the surface into the bulk layer. A mismatch in the shrinkage between the top and bulk layers arise as a result of the different types of photo‐cross‐linking reactions. Subsequently, the surface develops a wrinkled pattern with a low surface energy. This strategy exhibits considerable potential for preventing oxygen inhibition, and the wrinkled pattern may prove very useful in photo‐curing technology.     

Electron‐Beam‐Driven III‐Nitride Plasmonic Nanolasers in the Deep‐UV and Visible Region

Plasmonic nanolasers based on wide bandgap semiconductors are presently attracting immense research interests due to the breaking in light diffraction limit and subwavelength mode operation with fast dynamics. However, these plasmonic nanolasers have so far been mostly realized in the visible light ranges, or most are still under optical excitation pumping. In this work, III‐nitride‐based plasmonic nanolasers emitting from the green to the deep‐ultraviolet (UV) region by energetic electron beam injection are reported, and a threshold as low as 8 kW cm^?2 is achieved. A fast decay time as short as 123 ps is collected, indicating a strong coupling between excitons and surface plasmon. Both the spatial and temporal coherences are observed, which provide a solid evidence for exciton‐plasmon coupled polariton lasing. Consequently, the achievements in III‐nitride‐based plasmonic nanolaser devices represent a significant step toward practical applications for biological technology, computing systems, and on‐chip optical communication.     

A Polymer Encapsulation Strategy to Synthesize Porous Nitrogen‐Doped Carbon‐Nanosphere‐Supported Metal Isolated‐Single‐Atomic‐Site Catalysts

A novel polymer encapsulation strategy to synthesize metal isolated‐single‐atomic‐site (ISAS) catalysts supported by porous nitrogen‐doped carbon nanospheres is reported. First, metal precursors are encapsulated in situ by polymers through polymerization; then, metal ISASs are created within the polymer‐derived p‐CN nanospheres by controlled pyrolysis at high temperature (200–900 °C). Transmission electron microscopy and N₂ sorption results reveal this material to exhibit a nanospheric morphology, a high surface area (≈380 m² g^?1), and a porous structure (with micropores and mesopores). Characterization by aberration‐corrected high‐angle annular dark‐field scanning transmission electron microscopy and X‐ray absorption fine structure confirms the metal to be present as metal ISASs. This methodology is applicable to both noble and nonprecious metals (M‐ISAS/p‐CN, M = Co, Ni, Cu, Mn, Pd, etc.). In particular, the Co‐ISAS/p‐CN nanospheres obtained using this method show comparable (E_1/2 = 0.838 V) electrochemical oxygen reduction activity to commercial Pt/C with 20 wt% Pt loading (E_1/2 = 0.834 V) in alkaline media, superior methanol tolerance, and outstanding stability, even after 5000 cycles.     

Organ‐on‐a‐Chip Systems: Microengineering to Biomimic Living Systems

“Organ‐on‐a‐chip” systems integrate microengineering, microfluidic technologies, and biomimetic principles to create key aspects of living organs faithfully, including critical microarchitecture, spatiotemporal cell–cell interactions, and extracellular microenvironments. This creative platform and its multiorgan integration recapitulating organ‐level structures and functions can bring unprecedented benefits to a diversity of applications, such as developing human in vitro models for healthy or diseased organs, enabling the investigation of fundamental mechanisms in disease etiology and organogenesis, benefiting drug development in toxicity screening and target discovery, and potentially serving as replacements for animal testing. Recent advances in novel designs and examples for developing organ‐on‐a‐chip platforms are reviewed. The potential for using this emerging technology in understanding human physiology including mechanical, chemical, and electrical signals with precise spatiotemporal controls are discussed. The current challenges and future directions that need to be pursued for these proof‐of‐concept studies are also be highlighted.     

All‐Solution‐Processed Metal‐Oxide‐Free Flexible Organic Solar Cells with Over 10% Efficiency

All‐solution‐processing at low temperatures is important and desirable for making printed photovoltaic devices and also offers the possibility of a safe and cost‐effective fabrication environment for the devices. Herein, an all‐solution‐processed flexible organic solar cell (OSC) using poly(3,4‐ethylenedioxythiophene):poly‐(styrenesulfonate) electrodes is reported. The all‐solution‐processed flexible devices yield the highest power conversion efficiency of 10.12% with high fill factor of over 70%, which is the highest value for metal‐oxide‐free flexible OSCs reported so far. The enhanced performance is attributed to the newly developed gentle acid treatment at room temperature that enables a high‐performance PEDOT:PSS/plastic underlying substrate with a matched work function (≈4.91 eV), and the interface engineering that endows the devices with better interface contacts and improved hole mobility. Furthermore, the flexible devices exhibit an excellent mechanical flexibility, as indicated by a high retention (≈94%) of the initial efficiency after 1000 bending cycles. This work provides a simple route to fabricate high‐performance all‐solution‐processed flexible OSCs, which is important for the development of printing, blading, and roll‐to‐roll technologies.     

Scaffold‐Free Liver‐On‐A‐Chip with Multiscale Organotypic Cultures

The considerable advances that have been made in the development of organotypic cultures have failed to overcome the challenges of expressing tissue‐specific functions and complexities, especially for organs that require multitasking and complex biological processes, such as the liver. Primary liver cells are ideal biological building blocks for functional organotypic reconstruction, but are limited by their rapid loss of physiological integrity in vitro. Here the concept of lattice growth used in material science is applied to develop a tissue incubator, which provides physiological cues and controls the 3D assembly of primary cells. The cues include a biological growing template, spatial coculture, biomimetic radial flow, and circulation in a scaffold‐free condition. The feasibility of recapitulating a multiscale physiological structural hierarchy, complex drug clearance, and zonal physiology from the cell to tissue level in long‐term cultured liver‐on‐a‐chip is demonstrated. These methods are promising for future applications in pharmacodynamics and personal medicine.     

Sol‐gel derived C‐SiC composites for re‐entry structures

Composites of carbon fibers, fabrics, or their precursors as reinforcement, and sol‐gel‐derived silicon carbide as matrix, have been developed, aiming at high‐temperature stable ceramics that can be utilized for re‐entry structures. These composites are produced via the sol‐gel process, starting with a sol‐gel reaction of a mixture of silane precursors. The sol‐gel‐derived resin is cast onto the reinforcement fibers/fabrics mat (carbon or its precursors) to produce a ‘green’ composite that is being cured. The ‘green’ composite is converted into a C‐SiC composite via a gradual heat‐pressure process under inert atmosphere, during which the organic substituents on the silicon atoms undergo internal oxidative pyrolysis via the schematic reaction: (SiRO_3/2)_n → SiC + CO₂ + H₂O The composition of the resultant silicon‐oxi‐carbide is tailorable via modifying the composition of the sol‐gel reactants. The reinforcement, when made of carbon precursors, is converted into carbon during the heat‐and‐pressure processing as well. The C‐SiC composites thus derived exhibit superior thermal stability and comparable thermal conductivity, combined with good mechanical strength features and failure resistance, which render them greatly applicable for re‐entry shielding, heat‐exchange pipes, and the like.     

Analysis of a rotation‐free 4‐node shell element

In this paper, a shell element for small and large deformations is presented based on the extension of the methodology to derive triangular shell element without rotational degrees of freedom (so‐called rotation‐free). As in our original triangular S3 element, the curvatures are computed resorting to the surrounding elements. However, the extension to a quadrilateral element requires internal curvatures in order to avoid singular bending stiffness. The quadrilateral area co‐ordinates interpolation is used to establish the required expressions between the rigid‐body modes of normal nodal translations and the normal through thickness bending strains at mid‐side. In order to propose an attractive low‐cost shell element, the one‐point quadrature is achieved at the centre for the membrane strains, which are superposed to the bending strains in the centred co‐rotational local frame. The membrane hourglass control is obtained by the perturbation stabilization procedure. Free, simply supported and clamped edges are considered without introducing virtual nodes or elements. Several numerical examples with regular and irregular meshes are performed to show the convergence, accuracy and the reasonable little sensitivity to geometric distortion. Based on an updated Lagrangian formulation and Newton iterations, the large displacements of the pinched hemispherical shell show the effectiveness of the proposed simplified element (S4). Finally, the deep drawing of a square box including large plastic strains with contact and friction completes the ability of the rotation‐free quadrilateral element for sheet‐metal‐forming simulations. Copyright © 2005 John Wiley & Sons, Ltd.