Key role of molecular kinetic energy in early stages of pentacene island growth

Organic molecular beam deposition is studied systematically at thermal and hyperthermal regimes aiming at investigating the role of molecular kinetic energy on the growth mechanism of pentacene submonolayers on SiO _x /Si. We show that the kinetic energy of the impinging molecule (E _k ) plays a crucial role in determining island structure and shape, distribution of island sizes, the crystalline quality of the first monolayer, and even the growth mode of subsequent layers. With increasing E _k , the island structure changes from fractal to nonfractal, the shape becomes more anisotropic and the island size more uniform, pointing to correlated island growth. Moreover, while 3D island growth is observed for thermal organic molecular beam deposition, supersonic molecular beam deposition gives rise to layer-by-layer growth, at least for the first two layers. When E _k ≥5.0 eV, the first monolayer is composed of large single crystalline domains which can extend over up to 10 μm, inferred from comparing atomic force micrographs of height and net transverse shear force. In these growth conditions both the high surface diffusivity and energy redistribution play a major role. We propose a mechanism where the energy dissipation occurring during the molecule–surface collision leads to the reorientation of whole islands during island coalescence, resulting in the elimination of grain boundaries.     

A regioselective approach toward the synthesis of pharmacologically important quinone-containing heterocyclic systems

An inexpensive and regioselective approach to dihydrothieno[3,2-g]quinoline-4,9-dione is reported. A combination of a mild version of Skraup reaction with a sequential substitution/Michael addition allowed the selective preparation in acceptable yield of a pharmacologically important quinone derivative, previously obtained only in trace and together with the other regioisomer.     

Diastereomeric half-sandwich Ru(II) cationic complexes containing amino amide ligands. Synthesis, solution properties, crystal structure and catalytic activity in transfer hydrogenation of acetophenone

The cationic complexes [(η⁶-arene)Ru(N,O-amino amide)X]Y (arene = p-cymene or indane; N,O-amino amide = (l)-proline amide or (l)-phenylalanine amide; X = Cl or I; Y = Cl, I or PF₆) have been synthesised and fully characterized by spectroscopic and analytical methods. In several cases (1a, 3a, 4a, 4b, 5) the metal configuration has been definitively established by X-ray analysis on single crystal. The lability of the metal center in solution has been studied by ¹H NMR and CD techniques. The highest configurational stability has been found in the complexes of the type [(η⁶-indane)Ru(N,O-proline amide)Cl]Y (4a,b). The complexes 1b, 2a-b, 3b, 4b and 5 are good precatalysts for the transfer hydrogenation of acetophenone in basic i-PrOH, with ee up to 76% at 30 °C. An ESI(+)-MS study of pre-catalytic solutions has provided useful information on the catalytic mechanism.     

Summability of Connected Correlation Functions of Coupled Lattice Fields

We consider two nonindependent random fields \(\psi \) and \(\phi \) defined on a countable set Z. For instance, \(Z=\mathbb {Z}^d\) or \(Z=\mathbb {Z}^d\times I\), where I denotes a finite set of possible “internal degrees of freedom” such as spin. We prove that, if the cumulants of \(\psi \) and \(\phi \) enjoy a certain decay property, then all joint cumulants between \(\psi \) and \(\phi \) are \(\ell _2\)-summable in the precise sense described in the text. The decay assumption for the cumulants of \(\psi \) and \(\phi \) is a restricted \( \ell _1\) summability condition called \(\ell _1\)-clustering property. One immediate application of the results is given by a stochastic process \(\psi _t(x)\) whose state is \(\ell _1\)-clustering at any time t: then the above estimates can be applied with \(\psi =\psi _t\) and \(\phi =\psi _0\) and we obtain uniform in t estimates for the summability of time-correlations of the field. The above clustering assumption is obviously satisfied by any \(\ell _1\)-clustering stationary state of the process, and our original motivation for the control of the summability of time-correlations comes from a quest for a rigorous control of the Green–Kubo correlation function in such a system. A key role in the proof is played by the properties of non-Gaussian Wick polynomials and their connection to cumulants     

Metabolomic Profiling of Fresh Goji (Lycium barbarum L.) Berries from Two Cultivars Grown in Central Italy: A Multi-Methodological Approach

The metabolite profile of fresh Goji berries from two cultivars, namely Big Lifeberry (BL) and Sweet Lifeberry (SL), grown in the Lazio region (Central Italy) and harvested at two different periods, August and October, corresponding at the beginning and the end of the maturation, was characterized by means of nuclear magnetic resonance (NMR) and electrospray ionization Fourier transform ion cyclotron resonance (ESI FT-ICR MS) methodologies. Several classes of compounds such as sugars, amino acids, organic acids, fatty acids, polyphenols, and terpenes were identified and quantified in hydroalcoholic and organic Bligh-Dyer extracts. Sweet Lifeberry extracts were characterized by a higher content of sucrose with respect to the Big Lifeberry ones and high levels of amino acids (glycine, betaine, proline) were observed in SL berries harvested in October. Spectrophotometric analysis of chlorophylls and total carotenoids was also carried out, showing a decrease of carotenoids during the time. These results can be useful not only to valorize local products but also to suggest the best harvesting period to obtain a product with a chemical composition suitable for specific industrial use. Finally, preliminary studies regarding both the chemical characterization of Goji leaves generally considered a waste product, and the biological activity of Big Lifeberry berries extracts was also investigated. Goji leaves showed a chemical profile rich in healthy compounds (polyphenols, flavonoids, etc.) confirming their promising use in the supplements/nutraceutical/cosmetic field. MG63 cells treated with Big Lifeberry berries extracts showed a decrease of iNOS, COX-2, IL-6, and IL-8 expression indicating their significant biological activity.     

Synthesis of analogues of ochratoxin A

Four analogues of ochratoxin A (OTA) differing for the aminoacidic moiety were synthesised using ochratoxin α (OTα) as the starting material. The condensation reaction between protected amino acids and OTα, carried out in the presence of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC???HCl) and N-hydroxybenzotriazole (HOBt) as coupling agents, followed by deprotection and PTLC purification afforded OTA alanine, leucine, serine and tryptophane analogues in satisfactory yields (33-47%, based on OTα).     

An unprecedented switching of the second-order nonlinear optical response in aggregate bis(salicylaldiminato)zinc(II) Schiff-base complexes

A luminescent bis(salicylaldiminato)zinc(II) Schiff-base complex, 1, is characterized by a concentration dependent second-order nonlinear optical response, related to the degree of aggregation of the complex in a dichloromethane solution. The formation of the monomeric adduct, by addition of a Lewis base, such as pyridine, to concentrated solutions of 1, leads to a switch-on of the quadratic hyperpolarizability. This represents an unprecedented mode of NLO switching in molecular materials.     

Treatment of Human Glioblastoma U251 Cells with Sulforaphane and a Peptide Nucleic Acid (PNA) Targeting miR-15b-5p: Synergistic Effects on Induction of Apoptosis

Glioblastoma multiforme (GBM) is a lethal malignant tumor accounting for 42% of the tumors of the central nervous system, the median survival being 15 months. At present, no curative treatment is available for GBM and new drugs and therapeutic protocols are urgently needed. In this context, combined therapy appears to be a very interesting approach. The isothiocyanate sulforaphane (SFN) has been previously shown to induce apoptosis and inhibit the growth and invasion of GBM cells. On the other hand, the microRNA miR-15b is involved in invasiveness and proliferation in GBM and its inhibition is associated with the induction of apoptosis. On the basis of these observations, the objective of the present study was to determine whether a combined treatment using SFN and a peptide nucleic acid interfering with miR-15b-5p (PNA-a15b) might be proposed for increasing the pro-apoptotic effects of the single agents. To verify this hypothesis, we have treated GMB U251 cells with SFN alone, PNA-a15b alone or their combination. The cell viability, apoptosis and combination index were, respectively, analyzed by calcein staining, annexin-V and caspase-3/7 assays, and RT-qPCR for genes involved in apoptosis. The efficacy of the PNA-a15b determined the miR-15b-5p content analyzed by RT-qPCR. The results obtained indicate that SFN and PNA-a15b synergistically act in inducing the apoptosis of U251 cells. Therefore, the PNA-a15b might be proposed in a “combo-therapy” associated with SFN. Overall, this study suggests the feasibility of using combined treatments based on PNAs targeting miRNA involved in GBM and nutraceuticals able to stimulate apoptosis.