Luminescent blooming of dendronic carbon nanotubes through ion-pairing interactions with an Eu(III) complex

A multiwalled carbon nanotube (MWCNT) scaffold was covalently functionalized with a second-generation polyamidoamine (PAMAM) dendron, presenting four terminal amino groups per grafted aryl moiety. These reactive functions were alkylated to obtain a positively charged polycationic dendron/carbon nanotube system (d-MWCNTs?Cl), which eventually underwent anion exchange reaction with a negatively charged and highly luminescent Eu(III) complex ([EuL(4)]?NEt(4), in which L = (2-naphtoyltrifluoroacetonate)). This process afforded the target material d-MWCNTs?[EuL(4)], in which MWCNTs are combined with red-emitting Eu(III) centers through electrostatic interactions with the dendronic branches. Characterization of the novel MWCNT materials was accomplished by means of TGA and TEM, whereas d-MWCNTs?Cl and d-MWCNTs? [EuL(4)] further underwent XPS, SEM and Raman analyses. These studies demonstrate the integrity of the luminescent [EuL(4)](-) center in the luminescent hybrid, the massive load of the cationic binding sites, and the virtually complete anion-exchange into the final hybrid material. The occurrence of the ion-pairing interaction with MWCNTs was unambiguously demonstrated through DOSY NMR diffusion studies. Photophysical investigations show that MWCNTs?[EuL(4)] is a highly soluble and brightly luminescent red hybrid material in which MWCNTs act as photochemically inert scaffolds with negligible UV/Vis absorption, compared with the grafted Eu complex, and with no quenching activity. The high dispersibility of MWCNTs?[EuL(4)] in a polymer matrix makes it a promising luminophore for applications in material science.     

A Protocol for Accessing the β-Azidation of α,β-Unsaturated Carboxylic Acids

This contribution reports the preparation and use of a new immobilized catalyst, PS-DABCOF (9), which has been specifically designed to access for the first time the efficient β-azidation of α,β-unsaturated carboxylic acids.     

Evaluation of volatile constituents of Cochlospermum angolense

The chemical composition of the essential oils obtained from the leaves and roots of Cochlospermum angolense (Welw) growing wild in Angola was analyzed for the first time by capillary gas chromatography (GC) and gas chromatography/mass spectrometry (GC-MS). The investigation led to the identification of 67 and 130 compounds from the leaves and roots, respectively. Both oils were strongly characterized by the presence of sesquiterpenoids (68.8% in the leaves and 53.2% in the roots), while monoterpenoids were present in minor percentages (9.8% in the leaves and 26.2% in the root). The main constituents of the leaves were germacrene D (9.4%), alpha-cadinol (7.4%) and 10-epi-cubenol (6.2%), while the most abundant compounds in the root essential oil were the sesquiterpenes beta-caryophyllene (19.7%) and isoborneol (6.6%). The analysis by HS-SPME of the roots, leaves, fruits and seeds were also reported for the first time. Different volatile profiles were detected.     

On the Reducibility of the Weyl Algebra for a Semibounded Space

When the configuration space of a quantum particle is semibounded, the von Neumann algebra of the observables \({\mathcal{W}_+}\) is generated by a unitary group \({\{V(\beta) = {\rm exp}(-i\beta q)\},\,\beta\in\mathbb{R}}\) , and a semigroup {U(α)}, α ≥ 0, of isometries. We show that when \({\mathcal W_+}\) is a factor it is completely reducible into equivalent components, and that in each component the lower end x ₀ of the spectrum of q is the same. We give an algebraic characterization of x ₀ and also obtain a straightforward new proof that the irreducible representations of \({\mathcal W_+}\) with the same value of x ₀ are equivalent. In the general case \({\mathcal W_+}\) decomposes into the direct integral of factors which correspond to the possible values of x ₀.     

Improved T2* assessment in liver iron overload by magnetic resonance imaging

In the clinical MRI practice, it is common to assess liver iron overload by T2* multi-echo gradient-echo images. However, there is no full consensus about the best image analysis approach for the T2* measurements. The currently used methods involve manual drawing of a region of interest (ROI) within MR images of the liver. Evaluation of a representative liver T2* value is done by fitting an appropriate model to the signal decay within the ROIs vs. the echo time. The resulting T2* value may depend on both ROI placement and choice of the signal decay model. The aim of this study was to understand how the choice of the analysis methodology may affect the accuracy of T2* measurements. A software model of the iron overloaded liver was inferred from MR images acquired from 40 thalassemia major patients. Different image analysis methods were compared exploiting the developed software model. Moreover, a method for global semiautomatic T2* measurement involving the whole liver was developed. The global method included automatic segmentation of parenchyma by an adaptive fuzzy-clustering algorithm able to compensate for signal inhomogeneities. Global liver T2* value was evaluated using a pixel-wise technique and an optimized signal decay model. The global approach was compared with the ROI-based approach used in the clinical practice. For the ROI-based approach, the intra-observer and inter-observer coefficients of variation (CoVs) were 3.7% and 5.6%, respectively. For the global analysis, the CoVs for intra-observers and inter-observers reproducibility were 0.85% and 2.87%, respectively. The variability shown by the ROI-based approach was acceptable for use in the clinical practice; however, the developed global method increased the accuracy in T2* assessment and significantly reduced the operator dependence and sampling errors. This global approach could be useful in the clinical arena for patients with borderline liver iron overload and/or requiring follow-up studies.     

Olive Trees By-Products as Sources of Bioactive and Other Industrially Useful Compounds: A Systematic Review

The need to produce an ever-increasing quantity of material products and food resulting from the planet globalization process has contributed to the spread of modern agriculture based on a linear production resulting in the generation of tons of waste. This huge amount of waste is generally accumulated in landfills, causing different environmental problems. Hence, researchers moved on to study the processes used to recover agro-industrial by-products within a circular and sustainable bio-economy concept. A systematic quest on Scopus and PubMed databases was performed to identify the data available to date on recycling agro-industrial by-products of Olea europaea L. This systematic review summarizes the knowledge regarding the use of olive trees by-products for producing animal feed, biocomposites, bioethanol, cellulose pulp, activated carbon, and as a fuel source for energy production. Furthermore, the data regarding the potential biological activity of extracts from olive roots, wood, bark, and pruning were analyzed. Olive trees by-products are, indeed, rich in molecules with antioxidant, antimicrobial, cardioprotective, and anticancer activity, representing a promising candidate for treat several human diseases.     

Proanthocyanidin glycosides from the leaves of Quercus ilex L. (Fagaceae)

From the polar extracts of the leaves of Quercus ilex L., two new proanthocyanidin glycosides, namely afzelechin-(4α→8)-catechin-3-O-β-glucopyranoside (1) and afzelechin-(4α→8)-catechin-3-O-α-rhamnopyranoside (2), were isolated in addition to catechin (3), proanthocyanidin B₃ (4), prodelphinidin C (5), dehydrodicatechin A (6), quercetin (7) and six known flavonol glucosides with their acylated derivatives (8-13) and ellagic acid (14). The structures of all isolated compounds were established by spectroscopic means, mainly 1D and 2D NMR, as well as LC/MS and HR-MS spectrometric analyses. The absolute configuration of compound 1 was determined by CD measurements. The proanthocyanidin glycosides are especially interesting, as they possess the sugar in the upper unit of the dimer, which is rare for this type of compounds.     

N^N^C platinum(II) and palladium(II) cyclometallates of 6,6′-diphenyl-2,2′-bipyridine, L: Crystal and molecular structure of [Pd(L-H)Cl]

Reaction of K₂[PtCl₄] or Na₂[PdCl₄] with 6,6′-diphenyl-2,2′-bipyridine, L, gives the cyclometallated species [Pt(L-H)Cl], 1, and [Pd(L-H)Cl], 2, respectively, where L-H is a terdentate N^N^C anionic ligand originated by direct activation of a C(sp²)-H bond. The crystal structure of 2 has been solved by X-ray diffraction and compared to that of the analogous complex [Pd(L′-H)Cl] L′ = 6-phenyl-2,2′-bipyridine. The second phenyl ring in 2 entails a considerable distortion of the coordination around the metal. A similar distortion is also to be expected in the analogous compound 1, due to the almost equal covalent radii of palladium(II) and platinum(II).From the complexes 1 and 2 the chloride can be displaced with AgBF₄ and substituted by CO or PPh₃ to give the corresponding cationic species. By reaction of 1 with Na[BH₄] substitution of H⁻ for Cl⁻ can be achieved: the rare hydrido complex [Pt(L-H)H], stabilized only by nitrogen ligands, was isolated in the solid state and fully characterized in solution. It is noteworthy that in the case of the 6-phenyl-2,2′-bipyridine the analogous terminal hydride [Pd(L′-H)H] is unstable. In platinum chemistry the reaction of 6-substituted 2,2′-bipyridines is known to give either N^N^C or N′^C(3) rollover cyclometallation, depending on the nature of the metal precursor. In the case of 6,6′-Ph₂-2,2′-bipy cyclometallation was also shown to undergo multiple C-H activation giving the C^N^C pincer complex [Pt(L-2H)(DMSO)]. The latter species can be related to complex 1: indeed its reaction with HCl produces complex 1 and [Pt(L-H)(DMSO)Cl], a rollover species with a pendant phenyl substituent.     

Experimental and numerical analysis in heat flow sensors calibration

Journal of Thermal Analysis and Calorimetry - The 2010/31/CE directive has highlighted the necessity to improve the energy efficiency in buildings, since they are responsible for 40% of energy...     

Oxidative Addition to Palladium(0) Made Easy through Photoexcited‐State Metal Catalysis: Experiment and Computation

Visible‐light induced, palladium catalyzed alkylations of α,β‐unsaturated acids with unactivated alkyl bromides are described. A variety of primary, secondary, and tertiary alkyl bromides are activated by the photoexcited palladium metal catalyst to provide a series of olefins at room temperature under mild reaction conditions. Mechanistic investigations and density functional theory (DFT) studies suggest that a photoinduced inner‐sphere mechanism is operative in which a barrierless, single‐electron transfer oxidative addition of the alkyl halide to Pd⁰ is key for the efficient transformation.