Adapting the semi-explicit assembly solvation model for estimating water-cyclohexane partitioning with the SAMPL5 molecules

We describe here some tests we made in the SAMPL5 communal event of ‘Semi-Explicit Assembly’ (SEA), a recent method for computing solvation free energies. We combined the prospective tests of SAMPL5 with followup retrospective calculations, to improve two technical aspects of the field variant of SEA. First, SEA uses an approximate analytical surface around the solute on which a water potential is computed. We have improved and simplified the mathematical model of that surface. Second, some of the solutes in SAMPL5 were large enough to need a way to treat solvating waters interacting with ‘buried atoms’, i.e. interior atoms of the solute. We improved SEA with a buried-atom correction. We also compare SEA to Thermodynamic Integration molecular dynamics simulations, so that we can sort out force field errors.     

Artarborol, a nor-caryophyllane sesquiterpene alcohol from Artemisia arborescens. stereostructure assignment through concurrence of NMR data and computational analysis

A nor-caryophyllane derivative, artarborol, has been isolated from wormwood (Artemisia arborescens) and its stereostructure established by using a combination of chemical derivatization, NMR data, molecular modeling, and quantum-mechanical calculations. In particular, comparison of experimental 13C NMR data with a Boltzmann-weighed average of 13C NMR chemical shifts, calculated by ab initio DFT method, supported the stereochemical assignment.     

DMT-MM mediated functionalisation of the non-reducing end of glycosaminoglycans

Efficient functionalisation of the non-reducing end of uronic acid derivatives and glycosaminoglycan-derived disaccharides using peptide coupling has been achieved, mediated by the water-soluble agent DMT-MM.     

Nearest-neighbor oxygen distances in liquid water and ice observed by x-ray Raman based extended x-ray absorption fine structure

We report the nearest-neighbor oxygen-oxygen radial distribution function (NN O-O RDF) of room temperature liquid water and polycrystalline ice Ih (-16.8 degrees C) obtained by x-ray Raman based extended x-ray absorption fine structure (EXAFS) spectroscopy. The spectra of the two systems were taken under identical experimental conditions using the same procedures to obtain the NN O-O RDFs. This protocol ensured a measurement of the relative distance distribution with very small systematic errors. The NN O-O RDF of water is found to be more asymmetric (tail extending to longer distances) with longer average distance (2.81 A for water and 2.76 A for ice) but a slightly shorter peak position (2.70 A for water and 2.71 A for ice). The refinement also showed a small but significant contribution from the linear O-H-O multiple scattering signal. The high sensitivity to short range distances of the EXAFS probe will set further restrictions to the range of possible models of liquid water.     

A Universal Cassette-Based System for the Dissolution of Solid Targets

Cyclotron-based radionuclides production by using solid targets has become important in the last years due to the growing demand of radiometals, e.g., ⁶⁸Ga, ⁸⁹Zr, ^43/47Sc, and ^52/54Mn. This shifted the focus on solid target management, where the first fundamental step of the radiochemical processing is the target dissolution. Currently, this step is generally performed with commercial or home-made modules separated from the following purification/radiolabelling modules. The aim of this work is the realization of a flexible solid target dissolution system to be easily installed on commercial cassette-based synthesis modules. This would offer a complete target processing and radiopharmaceutical synthesis performable in a single module continuously. The presented solid target dissolution system concept relies on an open-bottomed vial positioned upon a target coin. In particular, the idea is to use the movement mechanism of a syringe pump to position the vial up and down on the target, and to exploit the heater/cooler reactor of the module as a target holder. All the steps can be remotely controlled and are incorporated in the cassette manifold together with the purification and radiolabelling steps. The performance of the device was tested by processing three different irradiated targets under different dissolution conditions.     

The Boson peak interpretation and evolution in confined amorphous water

We study the evolution of the Boson peak for water confined in cement paste obtained by means of Inelastic Neutron Scattering from room temperature to the deep supercooled regime. We analyze the data in terms of a universal-like model, developed for glass forming liquids in the frame of the energy landscape. In such a way it is possible to discriminate between the fragile and strong glass forming character of supercooled liquids and the dynamical crossover, fragile to strong, between them. Hence, we confirm the link between the Boson peak and the water polymorphism. In particular, the main result is represented by a crossover from a local energetic minima configuration to that characteristic of saddle points on going towards the deep supercooled regime up to the dynamical arrest.     

Multivariate probit models for conditional claim-types

This paper considers statistical modeling of the types of claim in a portfolio of insurance policies. For some classes of insurance contracts, in a particular period, it is possible to have a record of whether or not there is a claim on the policy, the types of claims made on the policy, and the amount of claims arising from each of the types. A typical example is automobile insurance where in the event of a claim, we are able to observe the amounts that arise from say injury to oneself, damage to one’s own property, damage to a third party’s property, and injury to a third party. Modeling the frequency and the severity components of the claims can be handled using traditional actuarial procedures. However, modeling the claim-type component is less known and in this paper, we recommend analyzing the distribution of these claim-types using multivariate probit models, which can be viewed as latent variable threshold models for the analysis of multivariate binary data. A recent article by Valdez and Frees [Valdez, E.A., Frees, E.W., Longitudinal modeling of Singapore motor insurance. University of New South Wales and the University of Wisconsin-Madison. Working Paper. Dated 28 December 2005, available from: http://wwwdocs.fce.unsw.edu.au/actuarial/research/papers/2006/Valdez-Frees-2005.pdf] considered this decomposition to extend the traditional model by including the conditional claim-type component, and proposed the multinomial logit model to empirically estimate this component. However, it is well known in the literature that this type of model assumes independence across the different outcomes. We investigate the appropriateness of fitting a multivariate probit model to the conditional claim-type component in which the outcomes may in fact be correlated, with possible inclusion of important covariates. Our estimation results show that when the outcomes are correlated, the multinomial logit model produces substantially different predictions relative to the true predictions; and second, through a simulation analysis, we find that even in ideal conditions under which the outcomes are independent, multinomial logit is still a poor approximation to the true underlying outcome probabilities relative to the multivariate probit model. The results of this paper serve to highlight the trade-off between tractability and flexibility when choosing the appropriate model.     

Nanotubes from a vitamin C-based bolaamphiphile

A bolaform surfactant, 1,12-diascorbyl dodecanedioate (BOLA12), with ascorbic acid units as the polar headgroups was synthesized for the first time. Once dispersed in water above 0.5% w/w, BOLA12 forms hollow nanotubes as revealed by cryo-TEM experiments. These nanostructures transform into clear micellar solutions on heating. X-ray diffraction and SAXS experiments were performed both on the pure solid and on its aqueous dispersions. The critical aggregation concentration and the phase behavior were determined by conductivity and DSC experiments. The latter technique provided also the amount of strongly bound, solvating water molecules that surround the polar headgroups. BOLA12 shows the same reducing properties of ascorbic acid, as indicated by the antioxidant activity evaluated with the DPPH method. This feature was used for the reduction of Pd(II) ions on the surface of the nanoassemblies, which lead to the formation of large bundles homogeneously coated with palladium as observed in SEM micrographs.     

An independent component analysis-based approach on ballistocardiogram artifact removing

Interest about simultaneous electroencephalography (EEG) and functional magnetic resonance imaging (fMRI) data acquisition has rapidly increased during the last years because of the possibility that the combined method offers to join temporal and spatial resolution, providing in this way a powerful tool to investigate spontaneous and evoked brain activities. However, several intrinsic features of MRI scanning become sources of artifacts on EEG data. Noise sources of a highly predictable nature such as those related to the pulse MRI sequence and those determined by magnetic gradient switching during scanning do not represent a major problem and can be easily removed. On the contrary, the ballistocardiogram (BCG) artifact, a large signal visible on all EEG traces and related to cardiac activity inside the magnetic field, is determined by sources that are not fully stereotyped and causing important limitations in the use of artifact-removing strategies. Recently, it has been proposed to use independent component analysis (ICA) to remove BCG artifact from EEG signals. ICA is a statistical algorithm that allows blind separation of statistically independent sources when the only available information is represented by their linear combination. An important drawback with most ICA algorithms is that they exhibit a stochastic behavior: each run yields slightly different results such that the reliability of the estimated sources is difficult to assess. In this preliminary report, we present a method based on running the FastICA algorithm many times with slightly different initial conditions. Clustering structure in the signal space of the obtained components provides us with a new way to assess the reliability of the estimated sources.     

Dynamic fracture of concrete compact tension specimen: Experimental and numerical study

Compared to quasi-static loading concrete loaded by higher loading rates acts in a different way. There is an influence of strain-rate and inertia on resistance, failure mode and crack pattern. With increase of loading rate failure mode changes from mode-I to mixed mode. Moreover, theoretical and numerical investigations indicate that after the crack reaches critical velocity there is progressive increase of resistance and crack branching. These phenomena have recently been demonstrated and discussed by O?bolt et al. (2011) on numerical study of compact tension specimen (CTS) loaded by different loading rates. The aim of the present paper is to experimentally verify the results obtained numerically. Therefore, the tests and additional numerical studies on CTS are carried out. The experiments fully confirm the results of numerical prediction discussed in O?bolt et al. (2011). The same as in the numerical study it is shown that for strain rates lower than approximately 50/s the structural response is controlled by the rate dependent constitutive law, however, for higher strain rates crack branching and progressive increase of resistance is observed. This is attributed to structural inertia and not the rate dependent strength of concrete. Maximum crack velocity of approximately 800 m/s is measured before initiation of crack branching. The comparison between numerical and experimental results shows that relatively simple modeling approach based on continuum mechanics, rate dependent microplane model and standard finite elements is capable to realistically predict complex phenomena related to dynamic fracture of concrete.