Electrostatic Surface Charging by Water Dewetting.

Water dewetting generates static electricity. We reviewed historical experiments of this phenomenon, and we studied the charging of polymer slides and metal electrode supported polymer films withdrawn vertically from a pool of aqueous solutions. For pure water, charging was negative and surface charge densities increased with the speed of dewetting, which we explain by the thermally activated entrainment of nanometer-sized water droplets or clusters charged by unbalanced adsorbed electric double-layer ions. Surface charge densities increased for reduced polymer film thickness following a power law, which we explain by reduced discharge of the entrained water volumes. At low salinity c ≲ 10 µM, charging was proportional to electrokinetic interfacial charge densities: the negative charging was increased for alkaline solutions and for most salts at µM concentrations and the charge polarity was inversed to positive for a cationic surfactant, a salt with a highly positively charged cation, and for a strong acid at approximately pH 4. Charging was reduced again for c ≳ 100 µM, especially at high dewetting speeds and for chaotropic ions, which we explain by the entrainment of larger and more discharged droplets. We determined adsorption energies of the charged water clusters on the dewetted surface from thermally stimulated discharge of the charged polymer slides and we show that the surface charge distribution, imaged by charged toner powders and measured microscopically by Kelvin probe force microscopy, is a record of the dewetting process that provides spatial and kinetic information about the three-phase contact line motion.

Olfactory training with Aromastics: olfactory and cognitive effects.

PURPOSE: The olfactory system can be successfully rehabilitated with regular, intermittent stimulation during multiple daily exposures to selected sets of odors, i.e., olfactory training (OT). OT has been repeatedly shown to be an effective tool of olfactory performance enhancement. Recent advancements in studies on OT suggest that its beneficial effects exceed olfaction and extend to specific cognitive tasks. So far, studies on OT provided compelling evidence for its effectiveness, but there is still a need to search for an optimal OT protocol. The present study examined whether increased frequency of OT leads to better outcomes in both olfactory and cognitive domains. METHOD: Fifty-five subjects (28 females; Mage = 58.2 ± 11.3 years; 26 patients with impaired olfaction) were randomly assigned to a standard (twice a day) or intense (four times a day) OT. Olfactory and cognitive measurements were taken before and after OT. RESULTS: OT performed twice a day was more effective in supporting olfactory rehabilitation and interventions targeted to verbal semantic fluency than OT performed four times a day, even more so in subjects with lower baseline scores. CONCLUSIONS: OT is effective in supporting olfactory rehabilitation and interventions targeted to verbal semantic fluency. However, it may be prone to a ceiling effect, being efficient in subjects presenting with lower baseline olfactory performance and lower verbal semantic fluency.

Structural origins of the cohesive energy in metal-terpyridine oligomer thin-films.

FeII-terpyridine based oligomers have attracted considerable interest as key constituents for the realization of highly robust, ultra-thin ordered layers of metal center oligomers (MCOs) for organic electronics applications. By using molecular simulations and nanotribology investigations, we report on the origins of the surprisingly high mechanical and thermal stability in this type of MCO layers, which finds its expression in nanowear resistance values of up to 1.5 µN for the MCO films, as well as in a thermal stability of two-terminal MCO junctions to temperatures up to ∼100 °C under electrical load. A theoretical analysis of the fundamental cohesive forces among the constituents within the context of an electrostatic model reveal that the cohesive energy is essentially based on Coulomb interactions among the ionic constituents of the oligomers, leading to an estimated cohesive energy per molar mass of 0.0132 eV mol g-1 for MCO layers that advantageously compare to the 0.0061 eV mol g-1 reported for pentacene crystals.

Cytochrome c biosensor--a model for gas sensing.

This work is about gas biosensing with a cytochrome c biosensor. Emphasis is put on the analysis of the sensing process and a mathematical model to make predictions about the biosensor response. Reliable predictions about biosensor responses can provide valuable information and facilitate biosensor development, particularly at an early development stage. The sensing process comprises several individual steps, such as phase partition equilibrium, intermediate reactions, mass-transport, and reaction kinetics, which take place in and between the gas and liquid phases. A quantitative description of each step was worked out and finally combined into a mathematical model. The applicability of the model was demonstrated for a particular example of methanethiol gas detection by a cytochrome c biosensor. The model allowed us to predict the optical readout response of the biosensor from tabulated data and data obtained in simple liquid phase experiments. The prediction was experimentally verified with a planar three-electrode electro-optical cytochrome c biosensor in contact with methanethiol gas in a gas tight spectroelectrochemical measurement cell.

Smells Influence Perceived Pleasantness but Not Memorization of a Visual Virtual Environment.

The present study aimed to investigate whether the perception of still scenes in a virtual environment in congruent versus incongruent condition can be influenced by odors. Ninety healthy participants were divided into three groups, including two experimental virtual reality (VR) environments: a rose garden, an orange basket, and a control condition. In each VR condition, participants were exposed to a rose odor, an orange odor, or no odor, resulting in congruent, incongruent, and control conditions. Participants were asked to describe (a) the content of the VR scene and rate its overall pleasantness and (b) the smell and to rate its intensity and pleasantness. For each condition, participants were tested twice. During the second test, participants provided ratings and descriptions of the content of the VR scenes without being exposed to odors or VR environments. Virtual scenarios tended to be remembered as more pleasant when presented with congruent odors. Furthermore, participants used more descriptors in congruent scenarios than in incongruent scenarios. Eventually, rose odor appeared to be remembered as more pleasant when presented within congruent scenarios. These findings show that olfactory stimuli in congruent versus incongruent conditions can possibly modulate the perception of the pleasantness of visual scenes but not the memorization.

Differential tumor biological role of the tumor suppressor KAI1 and its splice variant in human breast cancer cells.

The tetraspanin and tumor suppressor KAI1 is downregulated or lost in many cancers which correlates with poor prognosis. KAI1 acts via physical/functional crosstalk with other membrane receptors. Also, a splice variant of KAI1 (KAI1-SP) has been identified indicative of poor prognosis. We here characterized differential effects of the two KAI1 variants on tumor biological events involving integrin (αvß3) and/or epidermal growth factor receptor (EGF-R). In MDA-MB-231 and -435 breast cancer cells, differential effects were documented on the expression levels of the tumor biologically relevant integrin αvß3 which colocalized with KAI1-WT but not with KAI1-SP. Cellular motility was assessed by video image processing, including motion detection and vector analysis for the quantification and visualization of cell motion parameters. In MDA-MB-231 cells, KAI1-SP provoked a quicker wound gap closure and higher closure rates than KAI1-WT, also reflected by different velocities and average motion amplitudes of singular cells. KAI1-SP induced highest cell motion adjacent to the wound gap borders, whereas in MDA-MB-435 cells a comparable induction of both KAI1 variants was noticed. Moreover, while KAI1-WT reduced cell growth, KAI1-SP significantly increased it going along with a pronounced EGF-R upregulation. KAI1-SP-induced cell migration and proliferation was accompanied by the activation of the focal adhesion and Src kinase. Our findings suggest that splicing of KAI1 does not only abrogate its tumor suppressive functions, but even more, promotes tumor biological effects in favor of cancer progression and metastasis.

Surface Energy and Work Function Control of AlOx/Al Surfaces by Fluorinated Benzylphosphonic Acids.

The performance of organic electronic devices can be significantly improved by modifying metal electrodes with organic monolayers, which alter the physical and chemical nature of the interface between conductor and semiconductor. In this paper we examine a series of 12 phosphonic acid compounds deposited on the native oxide layer of aluminum (AlOx/Al), an electrode material with widespread applications in organic electronics. This series includes dodecylphosphonic acid as a reference and 11 benzylphosphonic acids, seven of which are fluorinated, including five newly synthesized derivatives. The monolayers are experimentally characterized by contact angle goniometry and by X-ray photoemission spectroscopy (XPS), and work function data obtained by low-intensity XPS are correlated with molecular dipoles obtained from DFT calculations. We find that monolayers are formed with molecular areas ranging from 17.7 to 42.9 Å(2)/molecule, and, by the choice of appropriate terminal groups, the surface energy can be tuned from 23.5 mJ/m(2) to 70.5 mJ/m(2). Depending on the number and position of fluorine substituents on the aromatic rings, a variation in the work function of AlOx/Al substrates over a range of 0.91 eV is achieved, and a renormalization procedure based on molecular density yields a surprising agreement of work function changes with interface dipoles as expected from Helmholtz' equation. The ability to adjust energetics and adhesion at organic semiconductor/AlOx interfaces has immediate applications in devices such as OLEDs, OTFTs, organic solar cells, and printed organic circuits.

Challenges and Opportunities in the Development of Aptamers for TNFα.

RNA aptamers for tumor necrosis factor-alpha (TNFα), for which functionality was demonstrated in L929 cells, show only little affinity for the protein in vitro. Detailed investigation of the aptamer-protein interaction by surface plasmon resonance and quartz crystal microbalance analysis revealed that affinity is not the only crucial parameter for efficacy and functionality of those aptamers. Instead, the sensitive equilibrium of the monomeric and homotrimeric form of soluble TNFα decides on aptamer binding. Our results show that the field of application and the source of TNFα have to be carefully defined before selection of aptamer sequences.

Ultrarobust Thin-Film Devices from Self-Assembled Metal-Terpyridine Oligomers.

Ultrathin molecular layers of Fe(II) -terpyridine oligomers allow the fabrication of large-area crossbar junctions by conventional electrode vapor deposition. The junctions are electrically stable for over 2.5 years and operate over a wide range of temperatures (150-360 K) and voltages (±3 V) due to the high cohesive energy and packing density of the oligomer layer. Electrical measurements reveal ideal Richardson-Shottky emission in surprising agreement with electrochemical, optical, and photoemission data.

Impact of micropatterned surfaces on neuronal polarity.

Experimental control over cellular polarity in a neuronal network is a promising tool to study synapse formation and network behavior. We aimed to exploit a mechanism described by Stenger et al. [J. Neurosci. Methods 82 (1998) 167] to manipulate the direction of axonal versus dendritic outgrowth on a micropattern. The group had used laser ablation to create patterns of aminated silanes for cell attachment on a background of repellent fluorinated silanes. The pattern offered continuous adhesive pathways for axonal and interrupted pathways for dendritic outgrowth. By microcontact printing, we created similar patterns containing continuous and interrupted pathways consisting of extracellular matrix proteins on a background of polystyrene. Neuronal polarity was determined on the functional level through double patch clamp measurements, detecting synapses and their orientation. Although our pattern reproduced the properties that were assumed to be critical for the described effect, namely contrasting pathways of different adhesiveness, we failed to reproduce the above results. It is indicated that other qualities of alternative pathways than mere differences in adhesiveness are required to orient neuronal polarity in vitro. We suggest that the effect observed by Stenger et al. has to be attributed to less universal characteristics of the micropattern, e.g. to the specific chemical groups that were utilized.

Fabrication of Homogeneous High-Density Antibody Microarrays for Cytokine Detection.

Cytokine proteins are known as biomarker molecules, characteristic of a disease or specific body condition. Monitoring of the cytokine pattern in body fluids can contribute to the diagnosis of diseases. Here we report on the development of an array comprised of different anti-cytokine antibodies on an activated solid support coupled with a fluorescence readout mechanism. Optimization of the array preparation was done in regard of spot homogeneity and spot size. The proinflammatory cytokines Tumor Necrosis Factor alpha (TNFα) and Interleukin 6 (IL-6) were chosen as the first targets of interest. First, the solid support for covalent antibody immobilization and an adequate fluorescent label were selected. Three differently functionalized glass substrates for spotting were compared: amine and epoxy, both having a two-dimensional structure, and the NHS functionalized hydrogel (NHS-3D). The NHS-hydrogel functionalization of the substrate was best suited to antibody immobilization. Then, the optimization of plotting parameters and geometry as well as buffer media were investigated, considering the ambient analyte theory of Roger Ekins. As a first step towards real sample studies, a proof of principle of cytokine detection has been established.

Organic dipole layers for ultralow work function electrodes.

The alignment of the electrode Fermi level with the valence or conduction bands of organic semiconductors is a key parameter controlling the efficiency of organic light-emitting diodes, solar cells, and printed circuits. Here, we introduce a class of organic molecules that form highly robust dipole layers, capable of shifting the work function of noble metals (Au and Ag) down to 3.1 eV, that is, ∼1 eV lower than previously reported self-assembled monolayers. The physics behind the considerable interface dipole is elucidated by means of photoemission spectroscopy and density functional theory calculations, and a polymer diode exclusively based on the surface modification of a single electrode in a symmetric, two-terminal Au/poly(3-hexylthiophene)/Au junction is presented. The diode exhibits the remarkable rectification ratio of ∼2·10(3), showing high reproducibility, durability (>3 years), and excellent electrical stability. With this evidence, noble metal electrodes with work function values comparable to that of standard cathode materials used in optoelectronic applications are demonstrated.

Conductance modulation in tetraaniline monolayers by HCl-doping and by field-enhanced dissociation of H2O.

Oligoanilines are interesting candidates for organic electronics, as their conductivity can be varied by several orders of magnitude upon protonic doping. Here we demonstrate that tetraaniline self-assembled monolayers exhibit an unprecedented conductance on/off ratio of ∼710 (at +1 V) upon doping of the layers from the emeraldine base to the emeraldine salt form. Furthermore, a pronounced asymmetry in the current-voltage characteristics indicates dynamic doping of the tetraaniline layer by protons generated through field-enhanced dissociation of water molecules, a phenomenon known as the second Wien effect. These results point toward oligoanilines as promising substitutes for polyaniline layers in next-generation thin film devices.

Cell-free expression of a mammalian olfactory receptor and unidirectional insertion into small unilamellar vesicles (SUVs).

Although the identification of the multigene family encoding mammalian olfactory receptors were identified more than 20 years ago, we are far from understanding olfactory perception because of the difficulties in functional expression of these receptors in heterologous cell systems. Cell-free (CF) or in vitro expression systems offer an elegant alternative route to cell based protein expression, as the functional expression of membrane proteins can be directly achieved from the genetic template without the need of cell cultivation and protein isolation. Here we investigated in detail the cell-free expression and membrane insertion of the olfactory receptor OR5 in dependence of different experimental conditions like probing different origins of the cell-free expression system (from bacteria, via plants and insects toward mammalian system) and lipid composition of the respective extracts. We provided substantial biochemical indications by radioactive labeling based on [(35)S]-methionine, followed by proteolytic digestion, and we found that the insertion of the olfactory receptor OR5 into liposomes resulted in an unidirectional orientation with the binding side exposed into the aqueous space, resembling the native orientation in the cilia of the olfactory neurons. We report the different results in synthesis capacity for the different in vitro systems employed as we like to demonstrate the first in vitro kit toward and ex situ and ex vivo odorant receptor array.

Efficient electronic coupling and improved stability with dithiocarbamate-based molecular junctions.

Molecular electronic devices require stable and highly conductive contacts between the metal electrodes and molecules. Thiols and amines are widely used to attach molecules to metals, but they form poor electrical contacts and lack the robustness required for device applications. Here, we demonstrate that dithiocarbamates provide superior electrical contact and thermal stability when compared to thiols on metals. Ultraviolet photoelectron spectroscopy and density functional theory show the presence of electronic states at 0.6 eV below the Fermi level of Au, which effectively reduce the charge injection barrier across the metal-molecule interface. Charge transport measurements across oligophenylene monolayers reveal that the conductance of terphenyl-dithiocarbamate junctions is two orders of magnitude higher than that of terphenyl-thiolate junctions. The stability and low contact resistance of dithiocarbamate-based molecular junctions represent a significant step towards the development of robust, organic-based electronic circuits.

Low-temperature fabrication of dye-sensitized solar cells by transfer of composite porous layers.

Dye-sensitized solar cells have established themselves as a potential low-cost alternative to conventional solar cells owing to their remarkably high power-conversion efficiency combined with 'low-tech' fabrication processes. As a further advantage, the active layers consisting of nanoporous TiO2 are only some tens of micrometres thick and are therefore in principle suited for flexible applications. However, typical flexible plastic substrates cannot withstand the process temperatures of up to 500 degrees C commonly used for sintering the TiO2 nanoparticles together. Even though some promising routes for low-temperature sintering have been proposed, those layers cannot compete as regards electrical properties with layers obtained with the standard high-temperature process. Here we show that by a lift-off technique, presintered porous layers can be transferred to an arbitrary second substrate, and the original electrical properties of the transferred porous layers are maintained. The transfer process is greatly assisted by the application of composite layers comprising nanoparticles and nanorods.

Metal-enhanced up-conversion fluorescence: effective triplet-triplet annihilation near silver surface.

Up-conversion phenomena are traditionally related to two- or multiphoton processes occurring under relatively high excitation intensities. Here we present the first results of ultralow excitation intensity (in order of Wcm(-2)) continuous-wave (CW) excited up-conversion fluorescence in Kretschmann surface plasmon geometry. The active system is a blue-emitting polymer matrix blended with metalated porphyrine macrocycles. The up-conversion fluorescence is a consequence of a two-particle triplet-triplet annihilation process (TTA).

Odd-even chain length-dependent order in pH-switchable self-assembled layers.

The reversible self-assembly of a series of bipolar amphiphiles, alpha,omega-bis(3- or 4-amidinophenoxy)alkanes (chain length n = 5-12), on mercaptoalkanoic acid-functionalized gold surfaces (chain length n = 10, 11, 14, 15) has been studied by in-situ ellipsometry, IR reflection absorption spectroscopy (IRAS), and atomic force microscopy (AFM). The layer order, amphiphile orientation, and tendency to form bilayers depends on the position of the amidine substituent, the alkyl chain length of both the amidine amphiphile and the underlying acid self-assembled monolayer (SAM), and whether the amidine alkyl chain contained an even or odd number of methylene groups. Thus, para-substituted bisbenzamidines containing more than six methylene groups (n>6) and with an odd number (n = 7, 9, 11) tended to form bilayered structures, whereas those containing an even number formed monolayers when adsorbed on SAMs of the long-chain acids (n = 14, 15). This behavior also correlated with the average tilt angle of the benzene moieties of the amphiphiles, as estimated by IRAS. The odd-numbered chains gave lower tilt angles than the even-numbered ones, and a possible model that accounts for these results is proposed. IRAS also revealed a higher order of the odd-numbered chains and an increasing hydrogen-bonding contribution with increasing chain length. Additional evidence for the proposed bilayered assemblies and their reversibility was obtained by AFM. Images obtained from the assembly of decamidine on a SAM of mercaptohexadecanoic acid in a pH 9 borate buffer revealed domains of similar size to that of the underlying acid SAM (20-30 nm), but less densely packed. By acidifying the solution, the second layer was destabilized and a very smooth layer with few defects appeared. Further acidification to pH 3 also destabilized the first layer.