Controlling the Microstructure of Conjugated Polymers in High‐Mobility Monolayer Transistors via the Dissolution Temperature

It remains a challenge to precisely tailor the morphology of polymer monolayers to control charge transport. Herein, the effect of the dissolution temperature (T_dis) is investigated as a powerful strategy for morphology control. Low T_dis values cause extended polymer aggregation in solution and induce larger nanofibrils in a monolayer network with more pronounced π–π stacking. The field‐effect mobility of the corresponding monolayer transistors is significantly enhanced by a factor of four compared to devices obtained from high T_dis with a value approaching 1 cm² V^?1 s^?1. Besides that, the solution kinetics reveal a higher growth rate of aggregates at low T_dis, and filtration experiments further confirm that the dependence of the fibril width in monolayers on T_dis is consistent with the aggregate size in solution. The generalizability of the T_dis effect on polymer aggregation is demonstrated using three other conjugated polymer systems. These results open new avenues for the precise control of polymer aggregation for high‐mobility monolayer transistors.     

Imaging the In Vivo Degradation of Tissue Engineering Implants by Use of Supramolecular Radiopaque Biomaterials

For in situ tissue engineering (TE) applications it is important that implant degradation proceeds in concord with neo‐tissue formation to avoid graft failure. It will therefore be valuable to have an imaging contrast agent (CA) available that can report on the degrading implant. For this purpose, a biodegradable radiopaque biomaterial is presented, modularly composed of a bisurea chain‐extended polycaprolactone (PCL2000‐U4U) elastomer and a novel iodinated bisurea‐modified CA additive (I‐U4U). Supramolecular hydrogen bonding interactions between the components ensure their intimate mixing. Porous implant TE‐grafts are prepared by simply electrospinning a solution containing PCL2000‐U4U and I‐U4U. Rats receive an aortic interposition graft, either composed of only PCL2000‐U4U (control) or of PCL2000‐U4U and I‐U4U (test). The grafts are explanted for analysis at three time points over a 1‐month period. Computed tomography imaging of the test group implants prior to explantation shows a decrease in iodide volume and density over time. Explant analysis also indicates scaffold degradation. (Immuno)histochemistry shows comparable cellular contents and a similar neo‐tissue formation process for test and control group, demonstrating that the CA does not have apparent adverse effects. A supramolecular approach to create solid radiopaque biomaterials can therefore be used to noninvasively monitor the biodegradation of synthetic implants.     

Pressure drop effects on selectivity and resolution in packed column supercritical fluid chromatography

The influence of pressure drop on retention, selectivity, plate height and resolution was investigated systematically in packed supercritical fluid chromatography (SFC) using pure carbon dioxide as the mobile phase. Numerical methods developed previously which enabled the prediction of pressure gradients, diffusivities, capacity factors, plate heights and resolutions along the length of the column were used for the model calculations. The effects of inlet pressure and supercritical fluid flow rate on selectivity and resolution are studied. In packed column SFC with pure carbon dioxide as the mobile phase, the pressure drop can have a significant effect on resolution. The flow rate is shown to have a larger effect than generally realized. The calculated data are shown to be in good agreement with the experimental results. Finally, the variation of the chromatographic parameters along a 5.5 meter long model SFC column is illustrated. The possibilities and limitations of using long packed columns in SFC are discussed. It is demonstrated that long columns with large plate numbers do not necessarily yield better separations.     

Synthesis of oligosaccharides catalyzed by thermostable β-glucosidase fromPyrococcus furiosus

Focusing on CO₂ fixation, photoautotrophic cultivation of the red algaPorphyridium cruentum was investigated by means of a batch culture under a 5% CO₂-enriched atmosphere. The algal growth kinetics was successfully described with a logistic model, and simulation of a continuous culture under the optimum growth conditions (30°C, 12 klux and 1.18 g-cells/L) showed that the algal CO₂-fixation activity could reach 0.66 g-CO₂/(L X d). Under the same growth conditions, eicosapentaenoic acid (20:5 n-3, EPA) and arachidonic acid (20:4 n-6, ARA) yields were similarly calculated to be 3.6 mg-EPA/(L X d) and 6.5 mg-ARA/(L X d), respectively.     

Pure-tone threshold estimation from extrapolated distortion product otoacoustic emission I/O-functions in normal and cochlear hearing loss ears

A new method for direct pure-tone threshold estimation from input/output functions of distortion product otoacoustic emissions (DPOAEs) in humans is presented. Previous methods use statistical models relating DPOAE level to hearing threshold including additional parameters e.g., age or slope of DPOAE I/O-function. Here we derive a DPOAE threshold from extrapolated DPOAE I/O-functions directly. Cubic 2 f1-f2 distortion products and pure-tone threshold at f2 were measured at 51 frequencies between f2=500 Hz and 8 kHz at up to ten primary tone levels between L2=65 and 20 dB SPL in 30 normally hearing and 119 sensorineural hearing loss ears. Using an optimized primary tone level setting (L1 = 0.4L2 + 39 dB) that accounts for the nonlinear interaction of the two primaries at the DPOAE generation site at f2, the pressure of the 2 f1-f2 distortion product pDP is a linear function of the primary tone level L2. Linear regression yields correlation coefficients higher than 0.8 in the majority of the DPOAE I/O-functions. The linear behavior is sufficiently fulfilled for all frequencies in normal and impaired hearing. This suggests that the observed linear functional dependency is quite general. Extrapolating towards pDP=0 yields the DPOAE threshold for L2. There is a significant correlation between DPOAE threshold and pure-tone threshold (r=0.65, p<0.001). Thus, the DPOAEs that reflect the functioning of an essential element of peripheral sound processing enable a reliable estimation of cochlear hearing threshold up to hearing losses of 50 dBHL without any statistical data.     

Optical and redox properties of a series of 3,4-ethylenedioxythiophene oligomers

The optical and redox properties of a series of 3,4-ethylenedioxythiophene oligomers (EDOTn, n=1-4) and their beta,beta'-unsubstituted analogues (Tn, n=1-4) are described. Both series are end capped with phenyl groups to prevent irreversible alpha-coupling reactions during oxidative doping. Absorption and fluorescence spectra of both series reveal a significantly higher degree of intrachain conformational order in the EDOTn oligomers. Oxidation potentials (E(PA1) and E(PA2)) determined by cyclic voltammetry reveal that those of EDOTn are significantly lower than the corresponding Tn oligomers as a consequence of the electron-donating 3,4-ethylenedioxy substitution. Linear fits of E(PA1) and E(PA2) versus the reciprocal number of double bonds reveal significantly steeper slopes for the EDOTn than for the Tn oligomers. This could indicate a more effective conjugation for the EDOTn series, confirmed by the fact that coalescence of E(PA1) and E(PA2) is reached already at relatively short chain lengths ( approximately 5 EDOT units) in contrast to the Tn series (>10 thiophene units). The stepwise chemical oxidation of the EDOTn and Tn oligomers in solution was carried out to obtain radical cations and dications. The energies of the optical transitions of the radical cations and dications as determined by UV/Vis/NIR spectroscopy were similar for the two series. These spectroscopic observations are consistent with quantum-chemical calculations performed on the singly charged molecules. Cooling solutions containing T2.+, T3.+, EDOT2.+, and EDOT3.+ revealed the reversible formation of dimers, albeit with a somewhat different tendency, expressed in the values for the dimerization enthalpy.     

Real-space measurement of the potential distribution inside organic semiconductors

We demonstrate that the soft nature of organic semiconductors can be exploited to directly measure the potential distribution inside such an organic layer by scanning-tunneling microscope (STM) based spectroscopy. Keeping the STM feedback system active while reducing the tip-sample bias forces the tip to penetrate the organic layer. From an analysis of the injection and bulk transport processes it follows that the tip height versus bias trace obtained in this way directly reflects the potential distribution in the organic layer.     

Biased Diffusion with Correlated Noise

The diffusion of hard-core particles subject to a global bias is described by a nonlinear, anisotropic generalization of the diffusion equation with conserved, local noise. Using renormalization group techniques, we analyze the effect of an additional noise term, with spatially long-ranged correlations, on the long-time, long-wavelength behavior of this model. Above an upper critical dimension d _LR, the long-ranged noise is always relevant. In contrast, for d<d _LR, we find a weak noise regime dominated by short-range noise. As the range of the noise correlations increases, an intricate sequence of stability exchanges between different fixed points of the renormalization group occurs. Both smooth and discontinuous crossovers between the associated universality classes are observed, reflected in the scaling exponents. We discuss the necessary techniques in some detail since they are applicable to a much wider range of problems.