Synthesis of novel room temperature chiral ionic liquids. application as reaction media for the heck arylation of aza-endocyclic acrylates.

New achiral and chiral RTILs were prepared using novel and/or optimized synthetic routes. These new series of imidazolinium, imidazolium, pyridinium and nicotine-derived ionic liquids were fully characterized including differential scanning calorimetry (DSC) analysis. The performance of these achiral and chiral room temperature ionic liquids (RTILs) was demonstrated by means of the Heck arylation of endocyclic acrylates employing arenediazonium salts and aryl iodides. The Heck arylations performed in the presence of these ionic entities, either as a solvent or as an additive, were effective leading to complete conversion of the substrate and good to excellent yield of the Heck adduct. In spite of the good performances, no asymmetric induction was observed in any of the cases studied. Two new diastereoisomeric NHC-palladium complexes were prepared in good yields from a chiral imidazolium salt and their structure characterized by X-ray diffraction. Overall, the Heck arylations employing arenediazonium tetrafluoroborates in RTILs were more effective than the traditional protocols employing aryl iodides in terms of reactivity and yields

ART2 et apprentissage de séquences de mots : l'ordre compte

ISBN : 978-2-9532965-0-1Un réseau Adaptive Resonance Theory a été utilisé pour simuler l'apprentissage des formes orthographiques des mots vus par les enfants. Il a été démontré qu'une modélisation par carte auto-organisatrice permet de rendre compte des performances de l'enfant si on conserve les probabilités d'apparition des mots de la base d'apprentissage. Nous montrons dans cet article avec ART2, que l'ordre d'apparition des mots joue aussi un rôle significatif dans la discrimination des mots plus ou moins orthographiquement voisins. Il en découle une hypothése de construction de corpus favorable é l'apprentissage de la lecture de ce type de mots

Thermo-mechanical analysis of dental silicone polymers

Soft lining materials are used to replace the inner surface of a conventional complete denture, especially for weak elderly patients, with delicate health who cannot tolerate the hard acrylic denture base. Most of these patients have fragile supporting mucosa, excessive residual ridge resorption, particularly on the mandibular arch. The application of a soft liner to the mandibular denture allows absorbing impact forces during mastication and relieving oral mucosa. Actually, the silicone rubbers constitute the main family of commercialised soft lining materials. This study was conducted to understand the relationships between the mechanical properties and the physical structure of polysiloxanes. For this purpose, a series of polysiloxanes of various chemical compositions have been investigated. The evolution of their physical structure as a function of temperature has been followed by differential scanning calorimetry (DSC). In order to facilitate comparisons, the mechanical modulus has been analysed upon the same heating rate using dynamic mechanical analysis (DMA). Polysiloxanes actually commercialised as soft denture liners are three-dimensional networks: the flexibility of chains allows a crystalline organisation in an amorphous phase leading to the low value of the shear modulus. The dynamic mechanical analysis shows that they are used in the rubbery state. So, polysiloxanes have steady mechanical properties during physiological utilisation

Conformational and thermal characterization of left ventricle remodeling post-myocardial infarction

Adverse cardiac remodeling after myocardial infarction (MI) causes impaired ventricular function and heart failure. Histopathological characterization is commonly used to detect the location, size and shape of MI sites. However, the information about chemical composition, physical structure and molecular mobility of peri- and infarct zones post-MI is rather limited. The main objective of this work was to explore the spatiotemporal biochemical and biophysical alterations of key cardiac components post-MI. The FTIR spectra of healthy and remote myocardial tissue shows amides A, I, II and III associated with proteins in freeze-died tissue as major absorptions bands. In infarcted myocardium, the spectrum of these main absorptions was deeply altered. FITR evidenced an increase of the amide A band and the distinct feature of the collagen specific absorption band at 1338cm-1 in the infarct area at 21days post-MI. At 21days post-MI, it also appears an important shift of amide I from 1646cm-1 to 1637cm-1 that suggests the predominance of the triple helical conformation in the proteins. The new spectra bands also indicate an increase in proteoglycans, residues of carbohydrates in proteins and polysaccharides in ischemic areas. Thermal analysis indicates a deep increase of unfreezable water/freezable water in peri- and infarcted tissues. In infarcted tissue is evidenced the impairment of myofibrillar proteins thermal profile and the emergence of a new structure. In conclusion, our results indicate a profound evolution of protein secondary structures in association with collagen deposition and reorganization of water involved in the scar maturation of peri- and infarct zones post-MI

Pharmacology of airways and vessels in lung slices in situ: role of endogenous dilator hormones

Small airway and vessels play a critical role in chronic airway and pulmonary vascular diseases, but their pharmacology has not been well characterised. We have studied airway and vascular responses in rat lung slices and separately in vitro using myography. In lung slices, under basal conditions, acetylcholine contracted airways, but had no vascular effect. The thromboxane mimetic, U46619 contracted both vessels and airways. In the presence of U46619, acetylcholine dilated vessels, but further contracted airways, an effect that was blocked by the nitric oxide synthase inhibitor L-N(G)-nitro-L-arginine or apamin plus charybdotoxin, which inhibit endothelial-derived hyperpolarising factor. Airway responses in lung slices were unaffected by L-N(G)nitro-L-arginine methyl ester, indomethacin or apamin plus charybdotoxin. By contrast, apamin plus charybdotoxin contracted bronchi studied in isolation. Our observations are the first to identify mechanisms of endothelium dependent dilations in precision cut lung slices and the potential for transverse hormonal communication between airways and vessels

Dielectric relaxations in PEEK by combined dynamic dielectric spectroscopy and thermally stimulated current

The molecular dynamics of a quenched poly (ether ether ketone) (PEEK) was studied over a broad frequency range from 10-3 to 106 Hz by combining dynamic dielectric spectroscopy (DDS) and thermo-stimulated current (TSC) analysis. The dielectric relaxation losses e00 KK has been determined from the real part e0 T(x) thanks to Kramers–Kronig transform. In this way, conduction and relaxation processes can be analyzed independently. Two secondary dipolar relaxations, the c and the b modes, corresponding to non-cooperative localized molecular mobility have been pointed out. The main a relaxation appeared close to the glass transition temperature as determined by DSC; it has been attributed to the delocalized cooperative mobility of the free amorphous phase. The relaxation times of dielectric relaxations determined with TSC at low frequency converge with relaxation times extracted from DDS at high frequency. This correlation emphasized continuity of mobility kinetics between vitreous and liquid state. The dielectric spectroscopy exhibits the ac relaxation, near 443 K, which has been associated with the rigid amorphous phase confined by crystallites. This present experiment demonstrates coherence of the dynamics of the PEEK heterogeneous amorphous phase between glassy and liquid state and significantly improve the knowledge of molecular/dynamic structure relationships

On publicness theory and its implications for supply chain integration:The case of criminal justice supply chains

The literature has extensively discussed whether and how public organizations differ from private ones. Publicness theory argues that the degree of publicness is determined by ownership, funding, goal setting, and control structure of an organization. However, these theoretical ideas have not yet been extended to the interorganizational level. The need for further research is reflected in the sustained debate on the applicability of for-profit management approaches in public contexts and supply chains. Starting from the premise of the dimensional publicness theory, this study focuses on theory elaboration. We focus our empirical study on the criminal justice supply chain, which encompasses the process of bringing a criminal case to court. This chain provides an interesting public case to explore how specific dimensions of publicness affect or limit supply chain integration mechanisms. The results of our series of embedded cases focusing on Dutch criminal justice supply chains show that control structures, embodied in laws and regulations, define the governance of relationships between supply chain partners. In addition to these formalized ties, extensive known for-profit information and operational integration mechanisms can be observed, along with limited relational integration. Surprisingly, although similar integration mechanisms are used as in for-profit contexts, integration serves a different role in several of the relationships investigated: dealing with tensions stemming from the specific goal setting and stakeholders of criminal justice chains. Although our findings specifically relate to criminal justice supply chains, they have important implications for other supply chains using contracts and laws and those being selective in applying supply chain integration in cases of contrasting objectives. Moreover, we provide a stepping-stone for the extension of publicness theory to the interorganizational level

Prevalence and Characteristics of Asthma-COPD Overlap in Routine Primary Care Practices

Rationale: Adults may exhibit characteristics of both asthma and chronic obstructive pulmonary disease (COPD), a situation recently described as asthma-COPD overlap (ACO). There is a paucity of information about ACO in primary care. Objectives: To estimate the prevalence and describe characteristics of individuals withACOin primary care practices among patients currently diagnosed with asthma, COPD, or both; and to compare the prevalence and characteristics of ACO among the three source populations. Methods: The Respiratory Effectiveness Group conducted a crosssectional study of individuals ≥40 years old and with ≥2 outpatient primary care visits over a 2-year period in theUKOptimum Patient Care Research Database. Patients were classified into one of three source populations based on diagnostic codes: 1) COPD only, 2) both asthma and COPD, or 3) asthma only.ACOwas defined as the presence of all of the following 1) age ≥40 years, 2) current or former smoking, 3) postbronchodilator airflow limitation (forced expiratory volume in 1 second/ forced vital capacity <0.7), and 4) ≥12% and ≥200 ml reversibility in post-bronchodilator forced expiratory volume in 1 second. Results: Among 2,165 individuals (1,015 COPD only, 395 with both asthma and COPD, and 755 asthma only), the overall prevalence of ACO was 20% (95% confidence interval, 18-23%). Patients with ACO had a mean age of 70 years (standard deviation, 11 yr), 60% were men, 73% were former smokers (the rest were current smokers), and 66% were overweight or obese. Comorbid conditions were common in patients with ACO, including diabetes (53%), cardiovascular disease (36%), hypertension (30%), eczema (23%), and rhinitis (21%). The prevalence of ACO was higher in patients with a diagnosis of both asthma and COPD (32%) compared with a diagnosis of COPD only (20%; P<0.001) or asthma only (14%; P<0.001). Demographic and clinical characteristics of ACO varied across these three source populations. Conclusions: One in five individuals with a diagnosis of COPD, asthma, or both asthma and COPD in primary care settings have ACO based on the Respiratory Effectiveness Group ACO Working group criteria. The prevalence and characteristics of patients with ACO varies across the three source populations

Morality tales: young women's narratives on offending, self-worth and desistance

This article emerges from a study of female offenders’ participation in police-facilitated restorative justice in one county in England. The qualitative study, presented here, is based on life history interviews with twelve women and focuses on three morality tales that emerged through narrative analysis: ‘offending as play,’ ‘the strong woman’ and ‘work and a normal life.’ The women used these tales to protect self-worth and justify ‘bad’ behavior in order to counter professional responses which they viewed as stigmatising. The paper concludes with implications for practice with girls and women who offend, which may benefit police, probation and social workers