A comparison of spin relaxation and local motion between symmetrically and asymmetrically ring-substituted bisphenol units in dissolved polycarbonates

Carbon-13 and proton spin-lattice relaxation times were measured at two field strengths on solutions 10% by weight of two polycarbonates in C₂D₂Cl₄ from ?20 to +120°C. The first polycarbonate is an asymmetrically substituted form with one chlorine on one of the two phenylene aromatic rings of the bisphenol unit, whereas the second polycarbonate is symmetrically substituted with two chlorines on each of the two rings. The nuclear spin relaxation data are interpreted in terms of several local motions likely in these polymers. Segmental motion was described by the Hall–Helfand correlation function. Segmental motion in the monosubstituted polycarbonate is somewhat slower than in unsubstituted polycarbonate, whereas segmental motion in the tetrasubstituted polycarbonate is considerably slower. Phenylene ring rotation is observed in unsubstituted polycarbonate and in the monosubstituted polycarbonate above 40°C. Below 40°C in the monosubstituted species, and at all temperatures in the tetrasubstituted species, ring rotation is replaced by ring libration as the predominant motion contributing to spin lattice relaxation. In addition, the rotational motion of the two types of rings in the asymmetric monosubstituted form are very similar although not identical. The substituted ring is slightly less mobile than the rings of unsubstituted polycarbonate. This indicates a strong coupling of ring motion, although the coupling leads to less than synchronous motion. Methyl group rotation is present in both polymers and is little affected by the various structural modifications.     

The synthesis and thermal polymerization of 4,4′-diethynylphenyl ether

Diethynylphenyl ether (DEPE) was synthesized and its thermal polymerization studied by NMR, IR, and DSC techniques. DEPE is a crystalline solid that melts at 72–73°C and undergoes polymerization beginning at about 150°C. The heat of polymerization measured by DSC was 53 ± 2 kcal/mole. Thermomechanical analysis (TMA) of the fully cured resin showed softening behavior at temperatures in excess of 400°C. Weight loss up to 720°C was only 21%. A mechanism of polymerization based on the analysis of IR and NMR data for party polymerized material below 300°C is proposed.     

From a Medicinal Mushroom Blend a Direct Anticancer Effect on Triple-Negative Breast Cancer: A Preclinical Study on Lung Metastases

Bioactive metabolites isolated from medicinal mushrooms (MM) used as supportive treatment in conventional oncology have recently gained interest. Acting as anticancer agents, they interfere with tumor cells and microenvironment (TME), disturbing cancer development/progression. Nonetheless, their action mechanisms still need to be elucidated. Recently, using a 4T1 triple-negative mouse BC model, we demonstrated that supplementation with Micotherapy U-Care, a MM blend, produced a striking reduction of lung metastases density/number, paralleled by decreased inflammation and oxidative stress both in TME and metastases, together with QoL amelioration. We hypothesized that these effects could be due to either a direct anticancer effect and/or to a secondary/indirect impact of Micotherapy U-Care on systemic inflammation/immunomodulation. To address this question, we presently focused on apoptosis/proliferation, investigating specific molecules, i.e., PARP1, p53, BAX, Bcl2, and PCNA, whose critical role in BC is well recognized. We revealed that Micotherapy U-Care is effective to influence balance between cell death and proliferation, which appeared strictly interconnected and inversely related (p53/Bax vs. Bcl2/PARP1/PCNA expression trends). MM blend displayed a direct effect, with different efficacy extent on cancer cells and TME, forcing tumor cells to apoptosis. Yet again, this study supports the potential of MM extracts, as adjuvant supplement in the TNBC management.     

CW laser-induced photothermal conversion and shape transformation of gold nanodogbones in hydrated chitosan films

We investigate the photothermal conversion and transformation of gold nanoparticles with an initial dogbone shape after dispersion in hydrated chitosan films, which is a representative model of biological tissue, and excitation by a CW diode laser for 1 min. Gold nanodogbones are observed to undergo a distinct modification above a sharp threshold of ~11 W cm⁻² and 110 °C. Surprisingly, the very same modification is achieved up to at least 36 W cm⁻² and 250 °C. We use an analytical model derived from Gans theory to associate the change in color of the films with the change in shape statistics of these gold nanoparticles. This model proves both convenient and dependable. We interpret the photothermal transformation as a rearrangement of particles with a dogbone shape and an aspect ratio of 4.1 into rods with an aspect ratio of 2.5, where material from the end lobes of the dogbones may relocate to the waists of the rods. In turn, additional transitions to stable gold nanospheres may exhibit fairly slower kinetics.     

A new method for computing beam insolation on tilted surfaces in average sky conditions

Summary The hourly solar-radiation values recorded during nine years in the town of Genova, Italy, have been used to find a simple expression which gives the instantaneous solar-beam irradiance in average sky conditions. This expression is used to calculate average hourly and daily beam irradiations incident upon surfaces with various slopes and orientations.

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Riassunto Utilizzando i valori orari di radiazione solare registrati per nove anni a Genova è stata trovata una semplice espressione che esprime il valore istantaneo della radiazione diretta incidente al suolo in condizioni di cielo medie. Tale espressione è usata per calcolare i valori medi di radiazione oraria e giornaliera incidente su superfici variamente inclinate ed orientate.

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Резюме Значения солнечной радиации, зарегистрированные в течение девяти лет в Генуе (Италия), используются для нахождения простого выражения, которое дает мгновенный поток солнечной радиации при средних небесных условиях. Это выражение используется для вычисления средних ежечасных и ежедневных потоков солнечной радиации, падающих на поверхности при различных наклонах и ориентациях.

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Work financed by CNR-PFE, S.P. RERE, Tema N, under contract 79.01699.92. Student of the Scuola di Perfezionamento in Fisica c/o Istituto di Scienze Fisiche, Genova, Italy.     

Size and shape control in the overgrowth of gold nanorods

We report on a new sustainable approach to manipulate the optical behaviour and geometrical properties of gold nanorods in aqueous solutions by fine control of their overgrowth. In our approach, the overgrowth is realized by modulation of the reduction of the gold ions which are left as Au¹⁺ after the primary step of the synthesis (typically as much as ~80% of the gold ions available in the growth solution). The progress of the reduction requires the gradual addition of ascorbic acid, which transforms the Au¹⁺ into Au⁰ and may be performed in the original growth solution with no need for any further manipulation. By control of the total amount and rate of administration of the ascorbic acid, we prove the possibility to realize a systematic modulation of the average lengths, diameters, shapes (rod or dog-bone like), and light extinction of the nanoparticles. A slow overgrowth leads to a gradual enlargement of the lengths and diameters at almost constant shape. In contrast, a faster overgrowth results into a more complex modification of the overall shape of the gold nanorods.