Rethinking the application of the first nucleation theorem to particle formation

The critical cluster is the threshold size above which a cluster will be more likely to grow than to evaporate. In field and laboratory measurements of new particle formation, the number of molecules of a given species in the critical cluster is commonly taken to be the slope of the log-log plot of the formation rate versus the concentration of the species. This analysis is based on an approximate form of the first nucleation theorem, which is derived with the assumption that there are no minima in the free energy surface prior to the maximum at the critical size. However, many atmospherically relevant systems are likely to exhibit such minima, for example, ions surrounded by condensable vapour molecules or certain combinations of acids and bases. We have solved numerically the birth-death equations for both an electrically neutral one-component model system with a local minimum at pre-critical sizes and an ion-induced case. For the ion-induced case, it is verified that the log-log slope of the nucleation rate versus particle concentration plot gives accurately the difference between the cluster sizes at the free energy maximum and minimum, as is expected from the classical form of the ion-induced nucleation rate. However, the results show that applying the nucleation theorem to neutral systems with stable pre-nucleation clusters may lead to erroneous interpretations about the nature of the critical cluster.     

Hydrogen activation by 2-boryl-N,N-dialkylanilines: a revision of Piers' ansa-aminoborane

Two 2-[bis(pentafluorophenyl)boryl]-N,N-dialkylanilines reported here exemplify a new class of intramolecular frustrated B/N Lewis pairs. A structure closely related to this class structure was synthesized in 2003 by Piers et al. but was unable to activate H(2). The new aminoboranes can activate hydrogen at near ambient conditions; besides, one of them can hydrogenate imines and enamines in a catalytic fashion demonstrating the validity of the original Piers' approach to hydrogen activation with ansa-aminoboranes.     

Cascade linear phase recursive half-band filters implement the most efficient digital down converter

The digital down converter (DDC) is a fundamental component in modern DSP based receivers. The basic architecture is the DSP implementation of the Edwin Armstrong heterodyne circuit. It is formed by three processes, a quadrature heterodyne, a pair of low-pass filters, and an M-to-1 down sampler. The index M is the ratio of input to output bandwidth of the filtering process. When M is large, the filtering is often performed in two sub-filters: a cascade integrator comb (CIC) filter that performs most of the down sampling followed by a pair of half-band filters that perform spectral correction, some final bandwidth reduction, and the remainder of the down-sampling. The attraction of the CIC filter is that it performs the filtering without multiplies. In this paper we present two alternate filter structures that offer significant computational advantages over the conventional CIC based DDC. These architectures offer the minimum power implementation of a DDC and likely will find great value in battery operated radio receivers.     

Quantitative characterization of critical nanoclusters nucleated on large single molecules

First order phase transitions involve nucleation, formation of nanoscale regions of a new phase within a metastable parent phase. Using the heterogeneous nucleation theorem we show how clusters formed by nucleation on single molecules evolve from the gas phase and determine the critical size beyond which condensation starts to form aerosol particles. Our experiments reveal the activation of molecules into droplets to happen via formation of critical clusters substantially larger than the seed molecule. The nanosized critical clusters were found to be well predicted by the Kelvin-Thomson relation pointing directly to the key step in the phase transition.     

BRST Quantization of Unimodular Gravity

We study the quantization of two versions of unimodular gravity, namely fully diffeomorphism-invariant unimodular gravity and unimodular gravity with fixed metric determinant, utilizing standard path integral approach. We derive the BRST symmetry of effective actions corresponding to several relevant gauge conditions. We observe that for some gauge conditions, the restricted gauge structure may complicate the formulation and effective actions, in particular, if the chosen gauge conditions involve the canonical momentum conjugate to the induced metric on the spatial hypersurface. The BRST symmetry is extended further to the finite field-dependent BRST transformation, in order to establish the mapping between different gauge conditions in each of the two versions of unimodular gravity.     

Quantitative liver iron measurement by magnetic resonance imaging: in vitro and in vivo assessment of the liver to muscle signal intensity and the R2* methods

Purpose

To evaluate the liver-to-muscle signal intensity and R2* methods to gain a transferable, clinical application for liver iron measurement.

Materials and Methods

Sixteen liver phantoms and 33 human subjects were examined using three 1.5-T MRI scanners from two different vendors. Phantom-to-muscle and liver-to-muscle signal intensity ratios were analyzed to determine MRI estimated phantom and hepatic iron concentration (M-PIC and M-HIC, respectively). R2* was calculated for the phantoms and the liver of human subjects. Seven patients' biochemical hepatic iron concentration was obtained.

Results

M-PIC and R2* results of three scanners correlated linearly to phantom iron concentrations (r=0.984 to 0.989 and r=0.972 to 0.981, respectively), and no significant difference between the scanners was found (P=.482 and P=.846, respectively) in vitro. The patients' R2* correlated linearly to M-HIC of the standard scanner (r=0.981). M-HIC values did not differ from those obtained from the biopsy specimens (P=.230). The difference in M-HIC was significant, but the difference in R2* was not significant between the scanners (P<.0001 and P=.505, respectively) in vivo.

Conclusion

Both methods, M-HIC and R2*, are reliable iron concentration indicators with linear dependence on iron concentration in vivo and in vitro. The R2* method was found to be comparable among different scanners. Transferability testing is needed for the use of the methods at various scanners.     

Second-order stochastic dominance constrained portfolio optimization: Theory and computational tests

Due to the definition of second-order stochastic dominance (SSD) in terms of utility theory, portfolio optimization with SSD constraints is of major practical interest. We contribute to the field in two ways: first, we present a self-contained theory with some new results and new proofs of known results; second, we perform a set of tests for computational efficiency. We provide new and simple arguments for the formulation of SSD constraints in a mathematical programming framework. For many individuals, an SSD constraint may seem too severe wherefore various relaxations (ASSD), have been proposed. We introduce yet another relaxation, directional SSD, where a candidate portfolio is admissible if a step from the benchmark in the direction of the candidate yields a dominating portfolio. Optimal step size depends on individual preferences reflected by the objective function. We compare computational efficiency of seven approaches for SD constrained portfolio problems, including SSD and ASSD constrained cases.     

Spectrally optimal illuminations for diabetic retinopathy detection in retinal imaging

Optical Review - Retinal photography is a standard method for recording retinal diseases for subsequent analysis and diagnosis. However, the currently used white light or red-free retinal imaging...     

Analysis of nitromethane from samples exposed in vitro to chloropicrin by stable isotope dilution headspace gas chromatography with mass spectrometry

Chloropicrin (trichloronitromethane) is a widely used soil fumigant and an old chemical warfare agent. The metabolism of chloropicrin is not well known in mammals but nitromethane has been shown to be one of its main metabolites. Here, a fast and simple headspace gas chromatography with mass spectrometry method was applied for the measurement of nitromethane from aqueous samples. The analytical method was validated using stable isotope labeled internal standard and a small sample volume of 260 μL. No conventional sample preparation steps were needed. The method was accurate (relative standard deviations ≤1.5%) and linear (R² = 0.9996) within the concentration range of 0.1?6.0 μg/mL. This method was used to measure nitromethane in in vitro incubations with human and pig liver cell fractions containing enzymes for xenobiotic metabolism, exposed to chloropicrin. The results indicate that the presence of glutathione is necessary for the formation of nitromethane from chloropicrin. Also, nitromethane was formed mostly in liver cytosol fractions, but not in microsomal fractions after the incubation with chloropicrin. Our results suggest that although nitromethane is not the unequivocal biomarker of chloropicrin exposure, this method could be applied for screening the elevated levels in humans after chloropicrin exposure.