EPR and pulsed ENDOR study of intermediates from reactions of aromatic azides with group 13 metal trichlorides

The reactions of group 13 metal trichlorides with aromatic azides were examined by CW EPR and pulsed ENDOR spectroscopies. Complex EPR spectra were obtained from reactions of aluminium, gallium and indium trichlorides with phenyl azides containing a variety of substituents. Analysis of the spectra showed that 4-methoxy-, 3-methoxy- and 2-methoxyphenyl azides all gave ‘dimer’ radical cations [ArNHC6H4NH2]+• and trimers [ArNHC6H4NHC6H4NH2]+• followed by polymers. 4-Azidobenzonitrile, with its electron-withdrawing substituent, did not react. In general the aromatic azides appeared to react most rapidly with AlCl3 but this reagent tended to generate much polymer. InCl3 was the least reactive group 13 halide. DFT computations of the radical cations provided corroborating evidence and suggested that the unpaired electrons were accommodated in extensive π-delocalised orbitals. A mechanism to account for the reductive conversion of aromatic azides to the corresponding anilines and thence to the dimers and trimers is proposedPublisher PDFPeer reviewe

Hilbert's 16th Problem for Quadratic Systems. New Methods Based on a Transformation to the Lienard Equation

Fractionally-quadratic transformations which reduce any two-dimensional quadratic system to the special Lienard equation are introduced. Existence criteria of cycles are obtained

Influence of age at weaning and nutritive value of weaning diet on growth performance and caecal traits in rabbits

[EN] To investigate the relationship between dietary nutrient concentration and weaning age on growth performance and caecal characteristics of rabbits, a trial was carried out on 64 litters (eight rabbits/litter) comparing two weaning ages (25 vs. 34 d) and two diets (HC: high concentrated and LC: low concentrated diet) offered to the kits from 18 to 34 d of age. At 34 d of age 54 animals per group were caged individually and all were fed the LC diet until 45 d of age. All animals were then fed a standard fattening diet (37% neutral detergent fiber, 3.4% ether extract and 18.0% crude protein on dry matter basis) until slaughter at 80 d. The digestibility trial was performed from 56 to 60 d of age on another group of 16 rabbits (8 per diet). During the experimental period (18-80 d of age), feed intake and animal weights were recorded. Caecal volatile fatty acids were measured at 45 and 80 d of age, while microbiological analysis was performed at 25 and 34 d on healthy suckling rabbits. Digestibility of dry matter, protein, neutral detergent fiber, fat and energy was higher in rabbits fed the HC diet (by 7.7, 7.4, 13.1, 26.7, 10.6%, respectively; P<0.001) than in those fed the LC diet. Growth rate and feed conversion ratio (FCR) from 18 to 34 d improved by 7.7 and 9.5% in rabbits fed HC in comparison to the LC diet, respectively (P¿0.061). Diet offered around weaning did not influence growth rate or FCR from 34 to 80 d of age. Rabbits weaned earlier increased feed intake (by 67.8%) from 25 to 34 d, but reduced growth rate (by 26.8%) compared to animals weaned at 34 d (P<0.001). Early weaning reduced live weight during the entire fattening period (P¿0.018), as well as the FCR (by 4%; P<0.001). Caecal pH was lower at 45 d of age in rabbits weaned at 25 d than in those weaned at 34 d (5.53 vs. 5.83; P=0.019). Treatments did not affect total caecal VFA concentration, but HC diet decreased caecal acetic concentration and increased butyric acid level compared to the LC diet at 45 d (P¿0.001). HC diet tended to reduce caecal counts of Enterobacteriacae (P=0.093), while it did not affect facultative anaerobic bacteria, E. Coli and Costridium spp. The LC diet increased at 25 d the number of Clostridium perfringens in comparison with the HC group at the same age and in comparison with animals fed both two diets at 34 d (P<0.001). The values of E. Coli and Enterobacteriaceae increased (P¿0.008) from 25 to 34 d of age, whereas that of Clostridium spp. decreased. Weaning at 25 d increased mortality from 18 to 34 d compared with rabbits weaned at 34 d (7.02 vs. 2.46%, P=0.017). However, during the fattening period (34-80 d) rabbits weaned earlier showed lower mortality (7.41 vs. 17.6%; P=0.024).This work has been realized within the CUNISVEZZ research project financed by the Agricultural Department of the Regione Lombardia as part of the 2004 research and development plan, d.g.r. 30/04/2004 n. VII/17326. The authors wish to thank Nicoletta Cesari for her technical assistance.Cesari, V.; Grilli, G.; Ferrazzi, V.; Toschi, I. (2009). Influence of age at weaning and nutritive value of weaning diet on growth performance and caecal traits in rabbits. World Rabbit Science. 17(4):195-205. https://doi.org/10.4995/wrs.2009.64419520517

Spin-dependent direct gap emission in tensile-strained Ge films on Si substrates

The circular polarization of direct gap emission of Ge is studied in optically-excited tensile-strained Ge-on-Si heterostructures as a function of doping and temperature. Owing to the spin-dependent optical selection rules, the radiative recombinations involving strain-split light (cG-LH) and heavy hole (cG-HH) bands are unambiguously resolved. The fundamental cG-LH transition is found to have a low temperature circular polarization degree of about 85% despite an off-resonance excitation of more than 300 meV. By photoluminescence (PL) measurements and tight binding calculations we show that this exceptionally high value is due to the peculiar energy dependence of the optically-induced electron spin population. Finally, our observation of the direct gap doublet clarifies that the light hole contribution, previously considered to be negligible, can dominate the room temperature PL even at low tensile strain values of about 0.2%

Practice Recommendations for Diagnosis and Treatment of the Most Common Forms of Secondary Hypertension

The vast majority of hypertensive patients are never sought for a cause of their high blood pressure, i.e. for a \u2018secondary\u2019 form of arterial hypertension. This under detection explains why only a tiny percentage of hypertensive patients are ultimately diagnosed with a secondary form of arterial hypertension. The prevalence of these forms is, therefore, markedly underestimated, although, they can involve as many as one-third of the cases among referred patients and up to half of those with difficult to treat hypertension. The early detection of a secondary form is crucial, because if diagnosed in a timely manner, these forms can be cured at long-term, and even when cure cannot be achieved, their diagnosis provides a better control of high blood pressure, and allows prevention of hypertension-mediated organ damage, and related cardiovascular complications. Enormous progress has been made in the understanding, diagnostic\ua0work-up, and management of secondary hypertension in the last decades. The\ua0aim of this minireview is, therefore, to provide updated concise information on the screening, diagnosis, and management of the most common forms, including primary aldosteronism, renovascular hypertension, pheochromocytoma and paraganglioma, Cushing\u2019s syndrome, and obstructive sleep apnea

Determination of daptomycin in human plasma and breast milk by UPLC/MS-MS

During the lactation, the choice of a proper antibiotic is crucial since the drug can cross into breast milk causing toxicity to the infant. Therefore, an extraction protocol and LC/MS-MS method for the determination of daptomycin in human milk and plasma were developed, validated and applied to a case of a breastfeeding mother affected by a purulent acute soft skin infection treated with daptomycin. Because of daptomycin high protein binding and its high molecular weight, the optimisation of the extraction protocol and analytical conditions were deeply investigated, and several parameters were taken into account: in particular the type of extraction, internal standard, the type of organic modifier, pH of the aqueous solution, and gradient. The use of a protein precipitation protocol coupled to a C8-reverse phase LC-MS/MS allows for a reliable quantification of daptomycin in both plasma (in the range of 19\u2013199 \u3bcg/mL) and breast milk (in the range of 0.12\u20130.32 \u3bcg/mL). The determination of milk/plasma (M/P) ratio, which ranged from 0.002 to 0.006, allowed to assess that daptomycin, effective for the mother, was contemporarily safe for the breastfed newborn

Geometric and analytic views in existence theorems for optimal control. II. Distributed and boundary controls

Existence theorems are proved for Lagrange problems of optimization in a given domain G with possibly unbounded distributed controls in G and on the boundary of G , and with functional relations on G and on the boundary represented by closed operators, not necessarily linear. The case where the functional relations are partial differential equations is emphasized. Recent work concerning the reduction or elimination of seminormality requirements is taken into account. Many examples are given.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/45200/1/10957_2004_Article_BF00933208.pd

Validity and usability of a smart ball&#8211;driven serious game to monitor grip strength in independent elderlies

Telemonitoring is one of the most expedient answers to the strong need for preventive care imposed by the rapidly aging society. We propose an innovative solution to the detection of early signs of frailty by presenting a serious game controlled by a smart sensorized soft plastic ball, designed to achieve continuous home-based monitoring of muscle weakness in older adults. Design, development, and testing of the smart ball and of the game interface devised to guide the monitoring procedure are presented. Reliability and concurrent validity of the system in measuring maximal grip strength against the clinical standard Jamar\uae were evaluated. Serious game usability and acceptance were investigated on 26 elderlies. Smart ball and Jamar measurements were well correlated (0.76 and 0.80 for dominant and non-dominant hands) and test\u2013retest reliability of pressure measurements was excellent (intraclass correlation coefficient &gt;0.94). The serious game was well accepted by the 96.1 percent of participants, who provided a strongly positive usability score (87.7/100). The smart ball\u2013driven serious game demonstrated excellent reliability and good validity in measuring grip strength. The proposed smart ball\u2013driven serious game can be used for home self-monitoring of grip strength in elderlies

2-Methyl-β-cyclodextrin grafted ammonium chitosan: synergistic effects of cyclodextrin host and polymer backbone in the interaction with amphiphilic prednisolone phosphate salt as revealed by NMR spectroscopy

Reduced molecular weight chitosan was quaternized with 2-chloro-N,N-diethylethylamine to obtain a water soluble derivative (N+-rCh). Methylated-β-cyclodextrin (MCD), with 0.5 molar substitution, was covalently linked to N+-rCh through 1,6-hexamethylene diisocyanate spacer to give the derivatized ammonium chitosan N+-rCh-MCD. To shed light on the role of the cyclodextrin pendant in guiding binding interactions with amphiphilic active ingredients, corticosteroid prednisolone phosphate salt (PN) was considered. The deep inclusion of PN into cyclodextrin in PN/MCD model system was pointed out by analysis of 1H NMR complexation shifts, 1D ROESY spectra, and diffusion measurements (DOSY). By using proton selective relaxation rates measurements as investigation tool, the superior affinity of N+-rCh-MCD towards PN was demonstrated in comparison with parent ammonium chitosan N+-rCh

A nonhomogeneous boundary value problem in mass transfer theory

We prove a uniqueness result of solutions for a system of PDEs of Monge-Kantorovich type arising in problems of mass transfer theory. The results are obtained under very mild regularity assumptions both on the reference set $\Omega\subset\mathbf{R}^n$, and on the (possibly asymmetric) norm defined in $\Omega$. In the special case when $\Omega$ is endowed with the Euclidean metric, our results provide a complete description of the stationary solutions to the tray table problem in granular matter theory.Comment: 22 pages, 2 figure