Detector-Based Calibration Method for High-Accuracy Solar UV Measurements

A novel method for calibrating the absolute responsivity of solar UV spectroradiometers has been developed and tested. The method is based on calibrated filter radiometers constructed from a detector, a precision aperture, a band-pass filter and devices for temperature stabilization. The filter radiometers utilize a trap detector with very low reflectance. The filter and the detector can therefore be characterized separately. As an example the detector-based calibration is compared at 312 nm wavelength with lamp-based calibration by measuring the irradiance of a deuterium lamp with both the filter radiometer and the lamp-calibrated spectroradiometer. The agreement between the results is at the level of 1%, well within the estimated uncertainties of both methods.     

Motion of positrons in metals

In this review we discuss the different aspects of positron annihilation in metals that involve the dynamics of positron motion before annihilation. The emphasis is on the theory, but also some experimental evidence is quoted. The topics covered are: slowing down and thermalization, effective mass, temperature dependence of positron vacancy trapping, positron channeling, and escape of low energy positrons from metal surfaces.     

Molecular Pacman: folding, inclusion, and X-ray structures of tri- and tetraamino piperazine cyclophanes

Reaction of piperazine and 1,3-bis(bromomethyl)-2-nitrobenzene under high-dilution conditions yields cyclic trimeric trinitro, tetrameric tetranitro, and pentameric pentanitro piperazine cyclophanes. Reduction of the nitro groups with SnCl(2) under acidic conditions produces the corresponding triamino and tetraamino piperazine cyclophanes. The solution studies of both nitro and amino piperazine cyclophanes at 30 degrees C by (1)H NMR spectroscopy shows symmetrical structures owing to the fast conformational exchange, whereas the low temperature studies of the tetraamino piperazine cyclophane reveals interesting dynamic behavior that indicates additional intramolecular interactions. Careful crystallizations of the trimeric trinitro and triamino and the tetrameric tetraamino cyclophanes resulted in crystals suitable for X-ray diffraction studies. In the crystalline state the amino-functionalized cyclophanes manifest an extraordinary circular intramolecular hydrogen-bonding network that leads to a fixed 3D structure. Hydrogen bonding in the triamino trimer leads to orientation of all three of the amino groups on the same side of the macrocycle, namely, the rcc conformation, whereas the tetraamino tetramer folds into a more compact shell-like conformation. During the crystallization process one acetonitrile guest is enclosed into the cavity of the tetraamino cyclophane, which gives a crystalline inclusion complex with remarkable resemblance to the famous Pacman motif. The folding, which mimics the behavior of some cyclic peptides and pyrroles, is induced by intramolecular hydrogen bonding from the amino groups to the tertiary amine groups of the piperazines. The cavity of the tetraamino tetramer is markedly smaller than in the corresponding, but nonfolded, tetranitro tetramer and the guest/host volume ratio (packing coefficient) for the acetonitrile and the cavity is approximately 50 %, which indicates a good size match for acetonitrile inclusion.     

Piezoelectric effect in GaAs nanowires: experiment and theory

The anomalous piezoelectric effect in GaAs nanowires was detected (the piezoelectric strain coefficient up to d₃₃ ≈ 26 pC/N) that is 12 times larger than the theoretically estimated value. This result is explained by the dominant content of the phase with the wurtzite‐type crystal structure in GaAs nanowires and an increased pressing force by the contact layer on the nanowire. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

It from bit: AI and the laws of nature

The present rate of growth of powerful AI systems motivates an accurate comparison between the notion of computers and the workings of natural sciences. Statements such as “intelligence doesn't require flesh, blood or carbon atoms” or “it's computation all the way down” incite a substrate-independent view, providing shortcuts for Darwinian evolution and the possible appearance of sentient machines. This view is discussed and contrasted from a quantum chemical perspective. The qualitative difference between the developed AI and the evolved HI is recognized and the importance of a material constituent, formulated in terms of energy-temperature, conjugate to an immaterial ingredient, in the context of time-entropy, is pointed out as a necessary feature. The popular dictum “it from bit” does not appear valid unless amended with its obverse “bit from it.”     

Relationship between subjective voice complaints and acoustic parameters in female teachers'' voices

The aim of the study was to identify the acoustic correlates of female teachers' subjective voice complaints by recording their voices in their working environment. The subjects made recordings during lessons (N = 10) and breaks (N = 11). The subjects were divided into 2 groups: those with few voice complaints (FC group) and those with many voice complaints (MC group). The speech sample made in the breaks was maximally sustained /a/, from which fundamental frequency (F0), jitter, and shimmer were analyzed. The classroom samples were analyzed for F0, sound pressure level (SPL), and F0 time (the active vibration time of the vocal folds). Additionally, an index for assessing voice loading is presented. The results revealed a tendency of the MC group to have higher F0 and lower SPL and perturbation values than the FC group. The index values correlated moderately with the subjective vocal complaints.     

Oligoamide Foldamers as Helical Chloride Receptors—the Influence of Electron‐Withdrawing Substituents on Anion‐Binding Interactions

The anion‐binding properties of three closely related oligoamide foldamers were studied using NMR spectroscopy, isothermal titration calorimetry and mass spectrometry, as well as DFT calculations. The ¹H NMR spectra of the foldamers in [D₆]acetone solution revealed partial preorganization by intramolecular hydrogen bonding, which creates a suitable cavity for anion binding. The limited size of the cavity, however, enabled efficient binding by the inner amide protons only for the chloride anion resulting in the formation of a thermodynamically stable 1:1 complex. All 1:1 chloride complexes displayed a significant favourable contribution of the entropy term. Most likely, this is due to the release of ordered solvent molecules solvating the free foldamer and the anion to the bulk solution upon complex formation. The introduction of electron‐withdrawing substituents in foldamers 2 and 3 had only a slight effect on the thermodynamic constants for chloride binding compared to the parent receptor. Remarkably, the binding of chloride to foldamer 3 not only produced the expected 1:1 complex but also open aggregates with 1:2 (host:anion) stoichiometry.