Solvent‐Dependent Structure of the I3− Ion Derived from Photoelectron Spectroscopy and Ab Initio Molecular Dynamics Simulations

Ab initio molecular dynamics (MD) simulations of the solvation of LiI₃ in four different solvents (water, methanol, ethanol, and acetonitrile) are employed to investigate the molecular and electronic structure of the I₃^? ion in relation to X‐ray photoelectron spectroscopy (XPS). Simulations show that hydrogen‐bond rearrangement in the solvation shell is coupled to intramolecular bond‐length asymmetry in the I₃^? ion. By a combination of charge analysis and I 4 d core‐level XPS measurements, the mechanism of the solvent‐induced distortions has been studied, and it has been concluded that charge localization mediates intermolecular interactions and intramolecular distortion. The approach involving a synergistic combination of theory and experiment probes the solvent‐dependent structure of the I₃^? ion, and the geometric structure has been correlated with the electronic structure.     

Structural and morphological studies on the deformation behavior of polypropylene/multi‐walled carbon nanotubes nanocomposites prepared through ultrasound‐assisted melt extrusion process

Structural and morphological behavior under stress–strain of polypropylene/multi‐walled carbon nanotubes (PP/MWCNTs) nanocomposites prepared through ultrasound‐assisted melt extrusion process was studied by means of optical microscopy, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, small angle X‐ray scattering (SAXS), and wide angle X‐ray scattering (WAXS). A high ductile behavior was observed in the PP/MWCNT nanocomposites with low concentration of MWCNTs. This was related to an energy‐dissipating mechanism, achieved by the formation of an ordered PP‐CNTs interphase zone and crystal oriented structure in the undeformed samples. Different strain‐induced‐phase transformations were observed by ex situ SAXS/WAXS, characterizing the different stages of structure development during the deformation of PP and PP/MWCNTs nanocomposites. The high concentration of CNTs reduced the strain behavior of PP due to the agglomeration of nanoparticles. A structural pathway relating the deformation‐induced phase transitions and the dissipation energy mechanism in the PP/MWCNTs nanocomposites at low concentration of nanoparticles was proposed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 475–491     

Ultrafast gas chromatography coupled to electronic nose to identify volatile biomarkers in exhaled breath from chronic obstructive pulmonary disease patients: A pilot study

An analytical method to identify volatile organic compounds (VOCs) in the exhaled breath from patients with a diagnosis of chronic obstructive pulmonary disease (COPD) using a ultrafast gas chromatography system equipped with an electronic nose detector (FGC eNose) has been developed. A prospective study was performed in 23 COPD patients and 33 healthy volunteers; exhalation breathing tests were performed with Tedlar bags. Each sample was analyzed by FCG eNose and the identification of VOCs was based on the Kovats index. Raw data were reduced by principal component analysis (PCA) and canonical discriminant analysis [canonical analysis of principal coordinates (CAP)]. The FCG eNose technology was able to identify 17 VOCs that distinguish COPD patients from healthy volunteers. At all stages of PCA and CAP the discrimination between groups was obvious. Chemical prints were correctly classified up to 82.2%, and were matched with 78.9% of the VOCs detected in the exhaled breath samples. Receiver operating characteristic curve analysis indicated the sensitivity and specificity to be 96% and 91%, respectively. This pilot study demonstrates that FGC eNose is a useful tool to identify VOCs as biomarkers in exhaled breath from COPD patients. Further studies should be performed to enhance the clinical relevance of this quick and ease methodology for COPD diagnosis.     

Spatio-Temporal Variation of the Bacterial Communities along a Salinity Gradient within a Thalassohaline Environment (Saline di Tarquinia Salterns,Italy)

The “Saline di Tarquinia” salterns have been scarcely investigated regarding their microbiological aspects. This work studied the structure and composition of their bacterial communities along the salinity gradient (from the nearby sea through different ponds). The communities showed increasing simplification of pond bacterial diversity along the gradient (particularly if compared to those of the sea). Among the 38 assigned phyla, the most represented were Proteobacteria, Actinobacteria and Bacteroidetes. Differently to other marine salterns, where at the highest salinities Bacteroidetes dominated, preponderance of Proteobacteria was observed. At the genus level the most abundant taxa were Pontimonas, Marivita, Spiribacter, Bordetella, GpVII and Lentibacter. The α-diversity analysis showed that the communities were highly uneven, and the Canonical Correspondence Analysis indicated that they were structured by various factors (sampling site, sampling year, salinity, and sampling month). Moreover, the taxa abundance variation in relation to these significant parameters were investigated by Generalized Linear Models. This work represents the first investigation of a marine saltern, carried out by a metabarcoding approach, which permitted a broad vision of the bacterial diversity, covering both a wide temporal span (two years with monthly sampling) and the entire salinity gradient (from the nearby sea up to the crystallisation ponds).     

On the application of ICP-MS techniques for measuring uranium and plutonium: a Nordic inter-laboratory comparison exercise

Inductively coupled plasma mass spectrometry (ICP-MS) techniques are widely used for determination of long-lived radionuclides and their isotopic ratios in the nuclear fields. Uranium (U) and Plutonium (Pu) isotopes have been determined by many researchers with ICP-MS due to its relatively high sensitivity and short measurement time. In this work, an inter-laboratory comparison exercise among the Nordic countries was performed, focusing on the measurement of U and Pu isotopes in certified reference materials by ICP-MS. The performance and characters of different ICP-MS instruments are evaluated and discussed in this paper.     

Influence of polyoxometalate ligands on the nature of high-valent transition metal nitrido species. A theoretical analysis of experimentally known and unprecedented compounds

The electronic structure of group 6-8 transition metal (TM) nitrido derivatives [PW(11)O(39){TM(VI)N}](4-) is studied computationally and the potential reactivity of the polyoxoanions is discussed. The observed electrophilic reactivity for the Ru(VI) nitrido derivative is rationalized from frontier molecular orbital analysis. When we move to the left or down in the periodic table (TM = Os, Tc, Re, Mo and W) the electrophilic character of the polyoxometalate decreases or the cluster should be better regarded as a nucleophile. The DFT analysis of the redox properties suggests that the still unknown high-valent Mn(VI)N and Fe(VI)N units could be stabilized by the porphyrin-like ligand [PW(11)O(39)](7-) and their electronic structure indicates that these anions should have a high potential reactivity towards nucleophiles.     

Simultaneous determination of atracurium and its metabolite laudanosine in post-mortem fluids by liquid chromatography/multiple-stage mass spectrometry on an ion trap

A method was developed to accurately quantify atracurium (a non-depolarizing skeletal muscle relaxant) and its metabolite laudanosine in post-mortem specimens. Analytes were isolated from blood and tissues by liquid/liquid extraction after adding vecuronium as an internal standard. Chromatographic separation was accomplished by gradient elution in a Synergy Max RP 150 x 2.1 mm column. Positive ion electrospray ionization and mass spectrometric analyses were carried out in an ion trap mass spectrometer under collision-induced dissociation conditions. The method proved selective and sensitive, and was validated in post-mortem blood, heart, lung and liver in the range of 1-2000 ng/mL (blood) and 5-5000 ng/g (tissues); the limits of quantification obtained were 1 ng/mL in blood and 5 ng/g in tissues.     

A coarse graining method for the identification of transition rates between molecular conformations

The coarse graining method to be advocated in this paper consists of two main steps. First, the propagation of an ensemble of molecular states is described as a Markov chain by a transition probability matrix in a finite state space. Second, we obtain metastable conformations by an aggregation of variables via Robust Perron Cluster Analysis (PCCA+). Up to now, it has been an open question as to how this coarse graining in space can be transformed to a coarse graining of the Markov chain while preserving the essential dynamic information. In this article, we construct a coarse matrix that is the correct propagator in the space of conformations. This coarse graining procedure carries over to rate matrices and allows to extract transition rates between molecular conformations. This approach is based on the fact that PCCA+ computes molecular conformations as linear combinations of the dominant eigenvectors of the transition matrix.     

Tumor selectivity at short times following systemic administration of a liposomal temoporfin formulation in a murine tumor model

Meso-tetra(hydroxyphenyl)chlorin (mTHPC) (INN: Temoporfin) is one of the most potent photodynamically active substances in clinical use. Treatment protocols for Temoporfin-mediated photodynamic therapy often rely on drug-light intervals of several days in order for the photosensitizer to accumulate within the target tissue, though tumor selectivity is limited. Here, the mTHPC localization was studied at 2-8 h following systemic administration of a liposomal Temoporfin formulation (0.15 mg kg(-1) b.w.) in HT29 human colon adenocarcinoma in NMRI nu/nu mice. Photosensitizer distribution within tumor and internal organs was investigated by means of high performance liquid chromatography following chemical extraction, as well as in situ fluorescence imaging and point-monitoring fluorescence spectroscopy. For tumor tissue, the Temoporfin concentrations at 4 h (0.16+/-0.024 ng mg(-1)) and 8 h (0.18+/-0.064 ng mg(-1)) were significantly higher than at 2 h (0.08+/-0.026 ng mg(-1)). The average tumor-to-muscle and the tumor-to-skin selectivity were 6.6 and 2, respectively, and did not vary significantly with time after photosensitizer injection. In plasma, the Temoporfin concentration was low (0.07+/-0.07 ng mg(-1)) and showed no significant variation with time. Our results indicate a rapid biodistribution and clearance from the bloodstream. Within the same type of organ, data from both fluorescence methods generally exhibited a significant correlation with the extraction results.