Doping Molecular Monolayers: Effects on Electrical Transport Through Alkyl Chains on Silicon

n‐Si/C_nH_{2n + 1}/Hg junctions (n = 12, 14, 16 and 18) can be prepared with sufficient quality to assure that the transport characteristics are not anymore dominated by defects in the molecular monolayers. With such organic monolayers we can, using electron, UV and X‐ray irradiation, alter the charge transport through the molecular junctions on n‐ as well as on p‐type Si. Remarkably, the quality of the self‐assembled molecular monolayers following irradiation remains sufficiently high to provide the same very good protection of Si from oxidation in ambient atmosphere as provided by the pristine films. Combining spectroscopic (UV photoemission spectroscopy (UPS), X‐ray photoelectron spectroscopy (XPS), Auger, near edge‐X‐ray absorption fine structure (NEXAFS)) and electrical transport measurements, we show that irradiation induces defects in the alkyl films, most likely C?C bonds and C? C crosslinks, and that the density of defects can be controlled by irradiation dose. These altered intra‐ and intermolecular bonds introduce new electronic states in the highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gap of the alkyl chains and, in the process, dope the organic film. We demonstrate an enhancement of 1–2 orders of magnitude in current. This change is clearly distinguishable from the previous observed difference between transport through high quality and defective monolayers. A detailed analysis of the electrical transport at different temperatures shows that the dopants modify the transport mechanism from tunnelling to hopping. This study suggests a way to extend significantly the use of monolayers in molecular electronics.     

4D Printing at the Microscale

3D printing of adaptive and dynamic structures, also known as 4D printing, is one of the key challenges in contemporary materials science. The additional dimension refers to the ability of 3D printed structures to change their properties—for example, shape—over time in a controlled fashion as the result of external stimulation. Within the last years, significant efforts have been undertaken in the development of new responsive materials for printing at the macroscale. However, 4D printing at the microscale is still in its early stages. Thus, this progress report will focus on emerging materials for 4D printing at the microscale as well as their challenges and potential applications. Hydrogels and liquid crystalline and composite materials have been identified as the main classes of materials representing the state of the art of the growing field. For each type of material, the challenges and critical barriers in the material design and their performance in 4D microprinting are discussed. Importantly, further necessary strategies are proposed to overcome the limitations of the current approaches and move toward their application in fields such as biomedicine, microrobotics, or optics.     

Highly Porous Materials as Tunable Electrocatalysts for the Hydrogen and Oxygen Evolution Reaction

The facile preparation of highly porous, manganese doped, sponge‐like nickel materials by salt melt synthesis embedded into nitrogen doped carbon for electrocatalytic applications is shown. The incorporation of manganese into the porous structure enhances the nickel catalyst's activity for the hydrogen evolution reaction in alkaline solution. The best catalyst demonstrates low onset overpotential (0.15 V) for the hydrogen evolution reaction along with high current densities at higher potentials. In addition, the possibility to alter the electrocatalytic properties of the materials from the hydrogen to oxygen evolution reaction by simple surface oxidation is shown. The surface area increases up to 1200 m²g^?1 after mild oxidation accompanied by the formation of nickel oxide on the surface. A detailed analysis shows a synergetic effect of the oxide formation and the material's surface area on the catalytic performance in the oxygen evolution reaction. In addition, the synthesis of cobalt doped sponge‐like nickel materials is also delineated, demonstrating the generality of the synthesis. The facile salt melt synthesis of such highly porous metal based materials opens new possibilities for the fabrication of diverse electrode nanostructures for electrochemical applications.     

Bioinspired Scaffolds with Varying Pore Architectures and Mechanical Properties

Scaffolds with potential biological applications having a variety of microstructural and mechanical properties can be fabricated by freezing colloidal solutions into porous solids. In this work, the structural and mechanical properties of TiO₂ freeze cast with different soluble additives, including polyethylene glycol, NaOH or HCl, and isopropanol alcohol, are characterized to determine the effects of slurry viscosity, pH, and alcohol concentration on the freezing process. TiO₂ powders mixed with water and these different additives are directionally frozen in a mold, then sublimated and sintered to create the porous scaffolds. The different scaffolds are characterized to compare the compressive strength, modulus, porosity, and pore morphology. For all scaffolds, the overall porosity remains constant (80–85%). By changing the concentration of each additive, the lamellar thickness, pore area, and aspect ratio vary significantly, showing inverse relationships to both the compressive strength and modulus. The strength is predicted from the pore aspect ratio of the scaffolds when subjected to compressive loading with the primary failure mode identified as Euler buckling. TiO₂ scaffolds freeze cast with different soluble additives are suitable for biomedical applications, such as bone replacements, requiring high porosity and specific pore morphologies.     

Ultrahigh Efficiency Fluorescent Single and Bi‐Layer Organic Light Emitting Diodes: The Key Role of Triplet Fusion

A new family of anthracene core, highly fluorescent emitters is synthesized which include diphenylamine hole transport end groups. Using a very simple one or two layer organic light emitting diode (OLED) structure, devices without outcoupling achieve an external quantum efficiency of 6% and photonic efficiencies of 20 cd/A. The theoretical maximum efficiency of such devices should not exceed 3.55%. Detailed photophysical characterization shows that for these anthracene based emitters 2T₁≤T_n and so in this special case, triplet fusion can achieve a singlet production yield of 0.5. Indeed, delayed electroluminescence measurements show that triplet fusion contributes 59% of all singlets produced in these devices. This demonstrates that when triplet fusion becomes very efficient, fluorescent OLEDs even with very simple structures can approach an internal singlet production yield close to the theoretical absolute maximum of 62.5% and rival phosphorescent‐based OLEDs with the added advantage of much improved stability.     

A fully pipelined RLS-based array for channel equalization

It is shown that several recursive least squares (RLS) type equalization algorithms such as, e.g., decisiondirected schemes and orthogonalized constant modulus algorithms, possess a common algorithmic structure and are therefore rather straightforwardly implemented on an triangular array (filter structure) for RLS estimation with inverse updating. While the computational complexity for such algorithms isO(N ²), whereN is the problem size, the throughput rate for the array implementation isO(1), i.e., independent of the problem size. Such a throughput rate cannot be achieved with standard (Gentleman-Kung-type) RLS/QR-updating arrays because of feedback loops in the computational schemes.     

Separation and quantification of olefins and diolefins in cracked petroleum fractions using silver-ion high performance liquid chromatography

A method using normal phase high performance liquid chromatography for the analysis of olefins and diolefins in cracked petroleum samples is proposed and validated in this work. A silver-impregnated silica column is used to separate olefin and diolefin species, resulting in accurate quantification of both group-types. Separations are completed using an isocratic hexane mobile phase, with no sample clean up or backflushing required. Results from the analysis of 11 model compounds are shown, as well as quantification data for four representative samples; figures of merit are also described.     

Blind Source Separation and Equiprobabilistic Topographic Maps

Recently, a number of heuristic techniques have been devised in order to overcome some of the limitations of the Blind Source Separation (BSS) algorithms that are rooted in the theory of Independent Component Analysis (ICA). They are usually based on topographic maps and designed to separate mixtures of signals with either sub-Gaussian or super-Gaussian source densities. In the sub-Gaussian case, the coordinates of the winning neurons in the topographic map represent the estimates of the source signal amplitudes. In the super-Gaussian case, one relies on the topographic map's ability to detect the source directions in mixture space which, in turn, correspond to the column vectors of the mixing matrix in the linear case. We will introduce a new topographic map-based heuristic for super-Gaussian BSS. It relies on the tendency of the mixture samples to cluster around the source directions. We will demonstrate its performance on linear and mildly non-linear mixtures of speech signals, including the case where there are less mixtures than sources to be separated (non-square BSS).     

PET imaging-based evaluation of aerosol drugs and their delivery devices: nasal and pulmonary studies

Three-dimensional (3-D) positron emission tomography (PET) imaging of inhaled radiolabeled aerosol in the nasal or pulmonary regions provides an in vivo measurement of drug distribution using the drug itself as the tracer. Repeated or dynamic PET scans over the time after inhalation provides us with further information about the fate of the deposited drug. These quantitative measurements are sufficient to describe the performance of a drug or device and they are obtained in a noninvasive fashion, which cannot be achieved by using any other methods. Using this PET-imaging paradigm, we conducted a sequence of drug studies to evaluate the performance of aerosol drugs and delivery devices; to compare the performance of similar drugs from different manufacturers; to assess the similarity between different formulations and propellants for the same drug; to appraise delivery devices such as spacers and nebulizers, etc. This paper reviews only the imaging and data analysis techniques developed for the above-mentioned studies that include multi-modality image registration, region definition and region-based data analysis, and nonregion-based data analysis. We separated the techniques into nasal and pulmonary studies because of the uniqueness of each group. Specific drugs or devices are not identified and no result about drug performance is given because the imaging and data analysis methodology, which is the focus of this paper, applies to all these studies regardless of the drugs or their delivery devices. The quantitative data are used as the scientific basis for evaluation although we also developed visualization techniques to enhance the results drawn from the data.