Vertical Phase Separation in Small Molecule:Polymer Blend Organic Thin Film Transistors Can Be Dynamically Controlled

Blending of small‐molecule organic semiconductors (OSCs) with amorphous polymers is known to yield high performance organic thin film transistors (OTFTs). Vertical stratification of the OSC and polymer binder into well‐defined layers is crucial in such systems and their vertical order determines whether the coating is compatible with a top and/or a bottom gate OTFT configuration. Here, we investigate the formation of blends prepared via spin‐coating in conditions which yield bilayer and trilayer stratifications. We use a combination of in situ experimental and computational tools to study the competing effects of formulation thermodynamics and process kinetics in mediating the final vertical stratification. It is shown that trilayer stratification (OSC/polymer/OSC) is the thermodynamically favored configuration and that formation of the buried OSC layer can be kinetically inhibited in certain conditions of spin‐coating, resulting in a bilayer stack instead. The analysis reveals here that preferential loss of the OSC, combined with early aggregation of the polymer phase due to rapid drying, inhibit the formation of the buried OSC layer. The fluid dynamics and drying kinetics are then moderated during spin‐coating to promote trilayer stratification with a high quality buried OSC layer which yields unusually high mobility >2 cm² V^?1 s^?1 in the bottom‐gate top‐contact configuration.     

Application of local error method to SSSF simulation of vector propagation in dispersion compensated optical links

A local error method based on an analytical scheme previously developed for the scalar optical fiber channel is applied to the second-order symmetrized split-step Fourier simulation of polarization multiplexed signal propagation through dispersion compensated optical fiber links. It is found that the global simulation accuracy for the vector propagation can be satisfied using the local error bound from a scalar propagation model for the same global error over a large range of simulation accuracy, chromatic dispersion, and differential group delay. Furthermore, carefully designed numerical simulations are used to show that similar local simulation error are obtained for vector simulations and that the similar local error leads to higher computational efficiency compared to other prevalent step-size selection schemes. The scaling of the global simulation error with respect to the number of optical fiber spans is demonstrated, and global error control for multi-span simulations is proposed. Combining the local error and global error control, the developed simulation scheme can significantly speed up the time-consuming simulations in coherent optical fiber communication system analysis and design.     

Metal Organic Framework Crystals in Mixed‐Matrix Membranes: Impact of the Filler Morphology on the Gas Separation Performance

Mixed‐matrix membranes comprising NH₂‐MIL‐53(Al) and Matrimid or 6FDA‐DAM have been investigated. The metal organic framework (MOF) loading has been varied between 5 and 20 wt%, while NH₂‐MIL‐53(Al) with three different morphologies, nanoparticles, nanorods, and microneedles has been dispersed in Matrimid. The synthesized membranes have been tested in the separation of CO₂ from CH₄ in an equimolar mixture. At 3 bar and 298 K for 8 wt% MOF loading, incorporation of NH₂‐MIL‐53(Al) nanoparticles leads to the largest improvement compared to nanorods and microneedles. The incorporation of the best performing filler, i.e., NH₂‐MIL‐53(Al) nanoparticles, into the highly permeable 6FDA‐DAM has a larger effect, and the CO₂ permeability increases up to 85% with slightly lower selectivities for 20 wt% MOF loading. Specifically, these membranes have a permeability of 660 Barrer with a CO₂/CH₄ separation factor of 28, leading to a performance very close to the Robeson limit of 2008. Furthermore, a new non‐destructive technique based on Raman spectroscopy mapping is introduced to assess the homogeneity of the filler dispersion in the polymer matrix. The MOF contribution can be calculated by modeling the spectra. The determined homogeneity of the MOF filler distribution in the polymer is confirmed by focused ion beam scanning electron microscopy analysis.     

Composite Nanostructures of TiO2 and ZnO for Water Splitting Application: Atomic Layer Deposition Growth and Density Functional Theory Investigation

The commercialization of solar fuel devices requires the development of novel engineered photoelectrodes for water splitting applications which are based on redundant, cheap, and environmentally friendly materials. In the current study, a combination of titanium dioxide (TiO₂) and zinc oxide (ZnO) onto nanotextured silicon is utilized for a composite electrode with the aim to overcome the individual shortcomings of the respective materials. The properties of conformal coverage of TiO₂ and ZnO layers are designed on the atomic scale by the atomic layer deposition technique. The resulting photoanode shows not only promising stability but also nine times higher photocurrents than an equivalent photoanode with a pure TiO₂ encapsulation onto the nanostructured silicon. Density functional theory calculations indicate that segregation of TiO₂ at the ZnO surfaces is favorable and leads to the stabilization of the ZnO layers in water environments. In conclusion, the novel designed composite material constitutes a promising base for a stable and effective photoanode for the water oxidation reaction.     

Development and application of C60-fullerene bound silica for solid-phase extraction of biomolecules

Sample pretreatment is the most important procedure to remove the matrix for interfacing with mass spectrometry (MS). Additionally, for the samples with low concentration, the process of preconcentration is required before MS analysis. We have newly developed a solid-phase extraction stationary phase based on C60-fullerene covalently bound to silica for purification of biomolecules of different characteristics. Silica particles of different porosity are modified with aminopropyl linker and then covalently bound to C60-fullerenoacetic acid or C60-epoxyfullerenes. The developed materials have been successfully applied as an alternative to commercially available reversed-phase materials for solid-phase extraction. C60-fullerene silica is able to retain small and hydrophilic molecules like phosphopeptides, which can be easily lost by reversed-phase sorbents. The novel materials are applied for desalting and preconcentration of proteins and peptides, especially phosphopeptides. In addition, the C60-fullerene silica is applied for the solid-phase extraction of selected flavonoids with recoveries of approximately 99%. The recoveries are compared with the commercially available solid-phase extraction materials.     

Hybrid biosorbent: An innovative matrix to enhance the biosorption of Cd(II) from aqueous solution

To enhance the metal removing capacity of a fungus biosorbent, a new idea of producing a hybrid biosorbent (HB) matrix by combining two different biosorbents using a simple and low-cost immobilization technique was tested for the sorption of Cd(II). The two biosorbents, used as the building block for the production of HB matrix, were the fungal biomass of Phanerochaete chrysosporium (B1) and fibrous network of papaya wood (B2). Maximum independent biosorption capacity of B1 and B2 was noted, respectively, to be 71.36 and 17.62 mgCd(II)g(-1) biosorbent. However, when two biosorbents were hybridized to form HB matrix, the combined biosorption capacity (141.63 mgCd(II)g(-1) biosorbent) was increased by 98.47, 703.80%, respectively, as compared to the ability of B1 and B2 when used alone, and by 59.17% than the sum of separate individual abilities of biosorbents B1 and B2. The kinetics of equilibrium was fast, approximately 88% of Cd(II) biosorption taking place within 30 min. Biosorption kinetics and equilibria followed the pseudo-second order kinetics and Langmuir adsorption isotherms model. HB matrix was also shown to be highly effective in removing Cd(II) from aqueous solution in a continuous flow fixed-bed column bioreactor, both in batch and repeated cycles.     

Iterative Learning Control Utilizing the Error Prediction Method

In this paper, iterative learning control utilizing the error prediction method is proposed for a class of linear time varying systems subjected to disturbances. Prediction of the error is done by identifying the system time varying parameters. Convergence of the proposed method is analyzed and the uniform boundedness of tracking error is obtained in the presence of uncertainty and disturbances. It is shown that the learning algorithm not only guarantees the robustness, but also improves the learning rate despite the presence of disturbances. The effectiveness of the proposed method is presented by simulations.