Dependence of collision‐induced dissociation energy on molecular degrees of freedom as a means to assess relative binding affinity in multivalent complexes

In collision‐induced dissociation mass spectrometry experiments, the collision energy required for dissociation linearly depends on the degrees of freedom in the precursor ion. The magnitude of the slope of this relationship previously has been shown to qualitatively correlate to the relative binding strength of a noncovalently bound, monovalent complex. The goal of the work presented here is to determine if a similar methodology can be applied for assessing relative binding strengths in multivalent species. We have tested the method on complexes formed from 18‐crown‐6 and a variety of protonated, primary alkylamines, [C_nH_2n+1NH₃]⁺ (n = 9, 12, 14, 16 and 18) and alkyldiamines, [H₃NC_nH_2nNH₃]²⁺ (n = 3, 5, 6, 9 and 12), and compared our results with dissociation energies calculated using density functional theory at the B3LYP/6‐31G* level. We found that the method correctly assessed the stronger crown ether/headgroup interaction in the two divalent species (1:1 and 2:1 complexes formed from the diaminoalkanes) compared with the weaker interaction in the monovalent species (1:1 complexes formed from mono‐aminoalkanes). However, the experimental method could not distinguish between the binding strengths of the two divalent complexes, perhaps because their calculated dissociation energies were quite similar. Our preliminary results suggest that this method could potentially be used for a quick and simple analysis of binding strengths in multivalent species if the binding strengths of the species are significantly different from one another. Copyright © 2011 John Wiley & Sons, Ltd.     

Dependence of electrical performance on structural organization in polymer field effect transistors

Organic semiconductors (OSCs) are strong contenders for use in printed, flexible electronics. Although organic electronic materials have been studied for many years, the physics of charge transport is still under investigation. This is in part due to variability resulting from the large variety of molecules that can be synthesized and inconsistency in electrical characterization due to device and processing conditions. Molecular ordering in OSCs is known to alter the charge transport characteristics and attention to long range and short range ordering provides clues as to the nature of transport pathways. Here, we study ordered regioregular poly(3‐hexylthiophene‐2,5‐diyl) films carefully prepared to obtain a set of three samples with incrementally increasing order on identical transistor architectures. Ordering was characterized using a variety of short and long range techniques to probe the coherence and number of crystallites formed during processing, and the correlation between these different measures of order are quantified. We observe three changes in transistor behavior that show a shift from non‐ideal to more textbook‐like characteristics with increasing order: reduction of the contact resistance, shift to field‐independent mobility, and a shift from a diode‐like (S‐shaped) to linear response at low lateral fields. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1063–1074     

Evidence of upward spread of suppression in DPOAE measurements

Measurements of DPOAE level in the presence of a suppressor were used to describe a pattern that is qualitatively similar to population studies in the auditory nerve and to behavioral studies of upward spread of masking. DPOAEs were measured in the presence of a suppressor (f3) fixed at either 2.1 or 4.2 kHz, and set to each of seven levels (L3) from 20 to 80 dB SPL. In the presence of a fixed f3 and L3 combination, f2 was varied from about 1 oct below to at least 1/2 oct above f3, while L2 was set to each of 6 values (20-70 dB SPL). L1 was set according to the equation L1 = 0.4L2 + 39 [Janssen et al., J. Acoust. Soc. Am. 103, 3418-3430 (1998)]. At each L2, L1 combination, DPOAE level was measured in a control condition in which no suppressor was presented. Data were converted into decrements (the amount of suppression, in dB) by subtracting the DPOAE level in the presence of each suppressor from the DPOAE level in the corresponding control condition. Plots of DPOAE decrements as a function of f2 showed maximum suppression when f2 approximately = f3. As L3 increased, the suppressive effect spread more towards higher f2 frequencies, with less spread towards lower frequencies relative to f3. DPOAE decrement versus L3 functions had steeper slopes when f2 > f3, compared to the slopes when f2 < f3. These data are consistent with other findings that have shown that response growth for a characteristic place (CP) or frequency (CF) depends on the relation between CP or CF and driver frequency, with steeper slopes when driver frequency is less than CF and shallower slopes when driver frequency is greater than CF. For a fixed amount of suppression (3 dB), L3 and L2 varied nearly linearly for conditions in which f3 approximately = f2, but grew more rapidly for conditions in which f3 < f2, reflecting the basal spread of excitation to the suppressor. The present data are similar in form to the results observed in population studies from the auditory nerve of lower animals and in behavioral masking studies in humans.     

Large force fluctuations in a flowing granular medium

We study fluctuations in the force at the boundary of a 2D granular flow. The forces are mainly impulsive at all flow rates. The probability distribution of impulses decays exponentially at large impulses, as do the forces in a static granular medium. At small impulses, the distribution evolves continuously with flow rate with no indication of the transition from collisional flow to intermittently jamming flows. However, the distribution of the time interval between collisions tends to a power law, P(tau) - tau(-3/2), showing a clear dynamical signature of the approach to jamming.     

Order-parameter and the discontinuous antiferro-paramagnetic transition in manganese oxide

Studies of monodomain manganese oxide by neutron diffraction and strain gauge measurements show that the antiferro-paramagnetic transition is clearly discontinuous. At the transition the order-parameter drops by about 60 percent of the T = 0 K value.     

The magnetic properties of FexCo1-x and FexTi1-x alloys

High pressures and high magnetic field behaviour give indications on the nature of magnetism encountered in transition metal alloys. We present experiments performed under pressure up to 7 kbar, in fields up to 150 kOe, between 1.4 K and 300 K. The results are used to discuss the occurence of ferromagnetism in Fe_xCo_10xSi and Fe_xCo_1-xTi systems. These systems exhibit two critical concentrations for the onset of ferromagnetism. Their magnetic properties are very sensitive to magnetic fields and high pressures and this allows us to characterize them as weak itinerant ferromagnets. A more localized behaviour is evidenced for the iron rich alloys and the appearance to ferromagnetism is different for cobalt rich side and for iron rich one.     

Oligoacenes: theoretical prediction of open-shell singlet diradical ground states

A series of oligoacenes from benzene to decacene were studied computationally with DFT and CASSCF methods. In contrast to the common view that acenes are closed-shell systems or may have a triplet ground state, these results offer the first theoretical predictions for the singlet ground state and diradical character for oligoacenes. The nature of the ground states of these molecules arises from the disjoint nature of the NBMOs that are singly occupied in the diradical.