Photocuring of cycloaliphatic epoxy formulations using polyesters with multiarm star topology as additives

Multiam star polyesters were synthesized by growing poly(ε‐caprolactone) (PCL) arms from hyperbranched polyesters cores of different molecular weight and used as polymeric modifiers in UV‐curable cationic formulations based on a biscycloaliphatic epoxy resin. The effect of the multiarm stars on the curing kinetics has been investigated by real‐time FTIR. The thermal‐mechanical properties of the photocured thermosets have been studied with calorimetry and dynamomechanical and thermogravimetric analysis. Impact strength tests have been performed to assess their effect on the toughness of the cured materials. An accelerative effect of these modifiers has been observed as a consequence of the participation of the hydroxyl groups of the modifiers in the cationic curing of the epoxy resin. A modest increase in toughness accompanied by a decrease in the glass transition are observed, as a consequence of the incorporation of the modifiers into the network structure, leading to homogeneous, in situ reinforced materials. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40005.     

The use of multiarm star‐like polymers in the preparation of epoxy thermosets by UV‐cationic photopolymerization. Effect of the arms of the star in the curing process and in the final properties and morphology

New epoxy thermosets have been prepared via cationic UV‐photopolymerization introducing two different multiarm star‐like polymers. Both stars have a poly(glycidol) core but one has poly(methylmetacrylate) arms and the other poly(ε?caprolactone) ones. The characterization of the curing process has been performed by Real‐Time FTIR and photo‐DSC, observing a slight reduction in the curing rate on increasing the proportion of star. The thermosets prepared were characterized by gel content determination, DMTA and TGA, and finally the morphology observed by FE‐SEM, demonstrating the formation of nanophases in the case of the star with poly(ε?caprolactone) arms. POLYM. ENG. SCI., 54:17–23, 2014. © 2013 Society of Plastics Engineers     

Dispersive mixing efficiency of an elongational flow mixer on PP/EPDM blends: Morphological analysis and correlation with viscoelastic properties

Polypropylene and ethylene‐propylene‐diene terpolymer (PP/EPDM) blends were melt compounded in a new mixing device, designed in our laboratory under the trademark of RMX®, which predominantly generates elongational flows. Dispersion of the EPDM minor phase in PP was carried out in both RMX® and in an internal mixer (Haake Rheomix 600) at equivalent specific mixing energies and the resultant morphologies obtained by SEM were analyzed and compared. A better dispersive mixing efficiency of the RMX® mixer, i.e., lower D_n and D_v of the dispersed EPDM phase was observed. The impact of elongational flow was more pronounced for blends having a high viscosity ratio p, indicating an enhanced droplet break‐up mechanism, which was attributed to the combination of high shear rates inside the mixing element and important elongational flows in the convergent/divergent zones. The morphology of the blends was correlated with their linear viscoelastic properties by using the Palierne model. Very good agreement was found for the PP/EPDM 80/20 blends but for higher EPDM content, the Palierne model failed to describe the rheological behavior, which was attributed to percolation of the minor phase with increasing the concentration. Higher elasticity at low frequencies was observed for blends processed in the RMX®, which was attributed to a higher generated interfacial area. POLYM. ENG. SCI., 54:1444–1457, 2014. © 2013 Society of Plastics Engineers     

Stabilization of nano-TiO2 aqueous dispersions with poly(ethylene glycol)-b-poly(4-vinyl pyridine) block copolymer and their incorporation in photocatalytic acrylic varnishes

In this work, TiO₂ nanoparticles were dispersed and stabilized in water using a novel type of dispersant based on tailor-made amphiphilic block copolymers of poly(ethylene glycol)-block-poly(4-vinyl pyridine) (mPEG-b-P4VP) prepared by atom transfer radical polymerization (ATRP). The performance of this new block copolymer as dispersant was compared to a polyelectrolyte dispersant commonly used for TiO₂, sodium salt of polyacrylic acid (Na-PAA). The effect of dispersion technique and type and amount of dispersant on deagglomeration and stability of the TiO₂ aqueous suspensions were studied. After incorporation in a standard waterborne acrylic varnish formulation, dry film transparency, photocatalytic activity, and nanoparticle cluster size were also evaluated. The results show that mPEG-b-P4VP copolymer with appropriate block lengths can have a better performance than Na-PAA in terms of aqueous dispersion stabilization and cluster size reduction in the acrylic matrix. This translates into higher film transparency and photocatalytic performance.     

A taxonomic-based joint species distribution model for presence-only data

Species distribution models (SDMs) are an important class of model for mapping taxa spatially and are a key tool for tackling biodiversity loss. However, most common SDMs depend on presence–absence data and, despite the accumulation and exponential growth of biological occurrence data across the globe, the available data are predominantly presence-only (i.e. they lack real absences). Although presence-only SDMs do exist, they inevitably require assumptions about absences of the considered taxa and they are specified mostly for single species and, thus, do not exploit fully the information in related taxa. This greatly limits the utility of global biodiversity databases such as GBIF. Here, we present a Bayesian-based SDM for multiple species that operates directly on presence-only data by exploiting the joint distribution between the multiple ecological processes and, crucially, identifies the sampling effort per taxa which allows inference on absences. The model was applied to two case studies. One, focusing on taxonomically diverse taxa over central Mexico and another focusing on the monophyletic family Cactacea over continental Mexico. In both cases, the model was able to identify the ecological and sampling effort processes for each taxon using only the presence observations, environmental and anthropological data.     

Macrophage-Mediated Melanoma Reduction after HP-NAP Treatment in a Zebrafish Xenograft Model

The Helicobacter pylori Neutrophil Activating Protein (HP-NAP) is endowed with immunomodulatory properties that make it a potential candidate for anticancer therapeutic applications. By activating cytotoxic Th1 responses, HP-NAP inhibits the growth of bladder cancer and enhances the anti-tumor activity of oncolytic viruses in the treatment of metastatic breast cancer and neuroendocrine tumors. The possibility that HP-NAP exerts its anti-tumor effect also by modulating the activity of innate immune cells has not yet been explored. Taking advantage of the zebrafish model, we examined the therapeutic efficacy of HP-NAP against metastatic human melanoma, limiting the observational window to 9 days post-fertilization, well before the maturation of the adaptive immunity. Human melanoma cells were xenotransplanted into zebrafish embryos and tracked in the presence or absence of HP-NAP. The behavior and phenotype of macrophages and the impact of their drug-induced depletion were analyzed exploiting macrophage-expressed transgenes. HP-NAP administration efficiently inhibited tumor growth and metastasis and this was accompanied by strong recruitment of macrophages with a pro-inflammatory profile at the tumor site. The depletion of macrophages almost completely abrogated the ability of HP-NAP to counteract tumor growth. Our findings highlight the pivotal role of activated macrophages in counteracting melanoma growth and support the notion that HP-NAP might become a new biological therapeutic agent for the treatment of metastatic melanomas.     

Immunotherapy for Biliary Tract Cancer in the Era of Precision Medicine: Current Knowledge and Future Perspectives

Biliary tract cancers (BTC) represent a heterogeneous and aggressive group of tumors with dismal prognosis. For a long time, BTC has been considered an orphan disease with very limited therapeutic options. In recent years a better understanding of the complex molecular landscape of biology is rapidly changing the therapeutic armamentarium. However, while 40–50% of patients there are molecular drivers susceptible to target therapy, for the remaining population new therapeutic options represent an unsatisfied clinical need. The role of immunotherapy in the continuum of treatment of patients with BTC is still debated. Despite initial signs of antitumor-activity, single-agent immune checkpoint inhibitors (ICIs) demonstrated limited efficacy in an unselected population. Therefore, identifying the best partner to combine ICIs and predictive biomarkers represents a key challenge to optimize the efficacy of immunotherapy. This review provides a critical analysis of completed trials, with an eye on future perspectives and possible biomarkers of response.     

Modeling of the dynamic mechanical properties of semicrystalline thermoplastic matrix composites

The modeling of the viscoelastic properties of semicrystalline polymeric matrix composites is discussed. Different mathematical models are applied to describe the development of the storage modulus, measured by dynamic mechanical analysis, as a function of the crystalline content during isothermal crystallization experiments. Best results are obtained with an empirical power law model developed in this work. The application of the Halpin-Tsai equation and of a theoretical model, based on a combination of parallel-series arrangements of viscoelastic elements representing the crystalline and amorphous phases, is also discussed. The main objective of this research is the comparison between experimental results obtained by differential scanning calorimetry and dynamic mechanical analysis during crystallization processes.     

The Role of Testosterone in the Elderly: What Do We Know?

Testosterone is the most important hormone in male health. Aging is characterized by testosterone deficiency due to decreasing testosterone levels associated with low testicular production, genetic factors, adiposity, and illness. Low testosterone levels in men are associated with sexual dysfunction (low sexual desire, erectile dysfunction), reduced skeletal muscle mass and strength, decreased bone mineral density, increased cardiovascular risk and alterations of the glycometabolic profile. Testosterone replacement therapy (TRT) shows several therapeutic effects while maintaining a good safety profile in hypogonadal men. TRT restores normal levels of serum testosterone in men, increasing libido and energy level and producing beneficial effects on bone density, strength and muscle as well as yielding cardioprotective effects. Nevertheless, TRT could be contraindicated in men with untreated prostate cancer, although poor findings are reported in the literature. In addition, different potential side effects, such as polycythemia, cardiac events and obstructive sleep apnea, should be monitored. The aim of our review is to provide an updated background regarding the pros and cons of TRT, evaluating its role and its clinical applicability in different domains.     

Instrumental evaluation of defective texture in dry-cured hams

In the first experiment, the effect of the stress relaxation time on texture evaluation of biceps femoris (BF) muscle from dry-cured hams was studied. The specimens were compressed to 25% of their original height and the crosshead speed was 5mm/s. The force decay versus time was recorded and Peleg's model was fitted with different relaxation times. Whatever relaxation time was used, Peleg's model did not describe simultaneously the initial fall of force and the asymptotic tendency of force decay correctly. The initial force and force decay at 2s and at 90s are proposed to assess texture in dry-cured ham. In the second experiment, stress relaxation (SR) and texture profile analysis (TPA) tests were performed on BF and semimembranosus (SM) muscles of 10 hams with abnormal softness and 10 hams with normal texture, at different assay conditions: sample temperature (4°C or 20°C); compression crosshead speed (1mm/s or 10mm/s). The instrumental texture test and the assay conditions that detected defective textures better depended on the muscle considered: for BF muscle the SR test at 4°C and at 1mm/s and for SM muscle the TPA test at 10mm/s at both 4°C or 20°C.