• Boesen Myers posted an update 6 months ago

    In the presence of alkynes (CHC-R2), iodide chain-end polymers (Polymer-I) were successfully transformed to vinyl iodide chain-end polymers (polymer-CHCR2-I) in a single step via organocatalysis. This reaction is completely metal-free and easy to carry out without using special reagents or special conditions. The polymers encompassing polyacrylates and polymethacrylate, and additional functionalities (e.g., OH and CF3) were also incorporated into the R2 moiety. The obtained Polymer-CHCR2-I further served as a useful precursor for copper-catalyzed cross-coupling reactions with various thiols (R3-SH) to yield vinyl sulfide chain-end polymers (polymer-CHCR2-SR3) with various R3 moieties. Interestingly, under selected conditions, this organocatalysis also offered block-like copolymers containing a conjugated oligo-alkyne segment and a non-conjugated polyacrylate segment. Exploiting the unique structure, the block-like copolymer was used as an efficient dispersant of carbon nanotubes.We analysed the influence of obesity, sex and sex steroids on the postprandial responses of circulating energy homeostasis mediators and their receptors to different macronutrient challenges. Seventeen women with polycystic ovary syndrome (PCOS, 8 with obesity), 17 non-hyperandrogenic control women (8 with obesity) and 19 control men (9 with obesity) were submitted, on alternate days, to isocaloric (300 kcal) oral glucose, lipid and protein loads. We evaluated serum ghrelin, leptin, soluble leptin receptor and adiponectin levels and the leukocyte gene expression of ghrelin (GHRL) and its receptor (GHSR), leptin receptor (LEPR) and adiponectin receptor 1 (ADIPOR1) during the macronutrient challenges. The postprandial responses of circulating energy homeostasis mediators were entirely different than those of their related genes. After macronutrient loads the postprandial response of serum energy homeostasis mediators showed a generalized physiological decrease that was blunted in subjects with obesity but was not influenced by sex, sex hormones or PCOS. However, gene expression of GHRL, LEPR and ADIPOR1 showed a marked increase following the ingestion of glucose compared with lipids and proteins, regardless of obesity and sex steroids. The physiological decrease after macronutrient loads, that was deregulated in obesity, did not reflect the acute leukocyte gene expression mainly after glucose, and may suggest a possible role for ghrelin, leptin and adiponectin in the postprandial inflammatory process.Between 150 and 230.6 K, bulk supercooled water freezes upon cooling, and amorphous ice crystallizes upon heating bulk water thus exists only in its stable ice form. To circumvent this problem, experiments are generally performed on water adsorbed in SiO2 based porous systems. In this work, we take advantage of Monte Carlo simulations to explore this metastable supercooled region inaccessible to experiments. Using three rigid, non-polarizable water models, namely SPC, TIP4P and TIP4P/2005, we investigate the isobaric specific heat capacity (Cp), between 100 and 300 K, of bulk water and water films of few monolayers adsorbed on different SiO2 surfaces a smooth surface, a non-hydroxylated (0001) surface of quartz, and a fully hydroxylated (001) surface of cristobalite. As Cp is directly related to the entropy fluctuations and we focus on low temperatures, the convergence of the Monte Carlo simulations is a critical point of this work. Dansylcadaverine mouse Also, due to the small mass of the hydrogen atoms, quantum corrections are taken into account, and lead to an excellent agreement of the simulated and experimental Cp values at low temperature (100 K region). Altogether, we conclude that, in bulk, Cp is shown to exhibit a broad peak around 225 K for the SPC and TIP4P models, and around 250 K for the TIP4P/2005 model, in qualitative agreement with the experimentally observed features in Cp measurements. For interfacial water, in all cases, the broad Cp peak disappears. This result, at odds with experimental observations, suggests that disorder and hydrogen bonding at the interface (not yet taken into account) have a fundamental role in confined water transitions.Cs2Au2I6, a lead-free photovoltaic material, has been synthesized via controlled and systematic addition of hydroiodic acid (HI) to CsAuCl4. X-ray diffraction studies suggest the formation of Cs2Au2I6 when a threshold concentration of HI is added to CsAuCl4. The final compound shows good stability against light, oxygen and moisture and at temperatures up to 140 °C without any phase degradation. The stability of Cs2Au2I6 is also confirmed by its high negative formation energy and the convex hull diagram constructed using Density Functional Theory (DFT). Absorption studies suggest an abrupt band shift from 2.31 eV to 1.06 eV when HI concentration reaches the threshold limit (∼100 μl). A sharp absorption edge was found for Cs2Au2I6 with an Urbach energy of 59 meV, indicating lower structural disorder and higher crystallinity.The efficacy of ongoing anticancer treatment is often compromised by some barriers, such as low drug content, nonspecific release of drug delivery system, and multidrug resistance (MDR) effect of tumors. Herein, in the research a novel functionalized PEG-based polymer cystine-(polyethylene glycol)2-b-(poly(2-methacryloyloxyethyl ferrocenecarboxylate)2) (Cys-(PEG45)2-b-(PMAOEFC)2) with multi-stimuli sensitive mechanism was constructed, in which doxorubicin (DOX) was chemical bonded through Schiff base structure to provide acid labile DOX prodrug (DOX)2-Cys-(PEG45)2-b-(PMAOEFC)2. Afterwards, paclitaxel (PTX) and its diselenide bond linked PTX dimer were encapsulated into the prodrug through physical loading, to achieve pH and triple redox responsive (DOX)2-Cys-(PEG45)2-b-(PMAOEFC)2@PTX and (DOX)2-Cys-(PEG45)2-b-(PMAOEFC)2@PTX dimer with ultrahigh drugs content. The obtained nanovehicles could self-assemble into globular micelles with good stability based on fluorescence spectra and TEM observation. Moreover, there was a remarkable “reassembly-disassembly” behavior caused by phase transition of micelles under the mimic cancerous physiological environment.

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