A kinetic study of the formation of smectic phases in novel liquid crystal ionogens

[EN] A multi-rate non-isothermal kinetic analysis of the isotropic-melt to liquid crystalline phase transition of novel liquid crystalline ionogenic copolymers, LCIs, the 10-(4-methoxyazobenzene-4'-oxy)decyl methacrylate]-co-2-(acrylamido-2-methyl-1-propanesulfonic acid)s, 10-MeOAzB/AMPS, copolymers, has been performed by means of calorimetric experiments. An analytical methodology which includes the study of the phase transition rate parameter, the determination of the activation energies by using Kissinger and Flynn-Wall-Ozawa models, and the study of the phase transition kinetics by the use of the Avrami theory, has been applied. The formation of the mesophases from the isotropic state occurred close to thermodynamic equilibrium. The results evidence the presence of several individual processes in the formation of liquid crystalline phases from the melt and a strong dependence of phase transition rates and activation energies with acid contents. A decrease in the phase transition rate, related to a decrease in the overall change of the transition entropy, has been observed. The final inhibition of the liquid crystal (LC) behaviour is ascribed to an exponential increase in the activation energy of the phase transition, promoted by strong acid aggregation. An optimum composition of the 10-MeOAzB/AMPS copolymers to achieve the dual characteristics of LCIs (ionogenic and liquid crystalline behaviour) requires acid concentrations capable of promoting structure-forming effects on the LC phases and the evolution of phase separated morphologies.The authors would like to acknowledge the Spanish Ministry of Science and Innovation, through the Research Projects ENE2007-67584-C03, UPOVCE-3E-013, ENE2011-28735-C02-01, IT-2009-0074 and three FPI and FPU predoctoral grants, and the financial support of the Generalitat Valenciana, through the Grisolia and Forteza programs and the ACOMP/2011/189 program. The Vice-rectorate for Research of UPV is also thanked for additional support through the PAID 05-09-4331, PAID-05-11/2806, and PAID 06-11-2037 projects.Martinez-Felipe, A.; Badia, J.; Santonja Blasco, L.; Imrie, C.; Ribes Greus, MD. (2013). A kinetic study of the formation of smectic phases in novel liquid crystal ionogens. European Polymer Journal. 49(6):1553-1563. https://doi.org/10.116/j.eurpolymj.2013.01.021S1553156349

Mechanical and thermal performance of PLA and PHBV based biopolymers as potential alternatives to PET

[EN] The evaluation of the mechanical and thermal properties of poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), polylactide (PLA) and their biocomposites (containing 30%wt of sisal in their composition) has been studied and compared to poly(ethylene terephthalate) (PET). The addition of sisal to the biopolymeric matrix increased the elastic stiffness of the bio-composites achieving a performance which is comparable to PET. All biocomposites presented lower traction resistance and elongation values respect to PET.The addition of natural fibers improved the thermal stability of PHBV-based samples. The trigger of decomposition happened at lower temperatures respect to PET, but always far above their melting point ensuring a good performance of the composites at high processing temperatures. The apparent activation energies for the biocomposites in inert conditions respect to those for PET indicates a more suitable scenario from the energetic valorisation point of view.Moliner, C.; Badia, J.; Bosio, B.; Arato, E.; Lagazzo, A.; Capurro, M.; Ribes-Greus, A. (2017). Mechanical and thermal performance of PLA and PHBV based biopolymers as potential alternatives to PET. Chemical Engineering Transactions. 57:1417-1422. https://doi.org/10.3303/CET1757237S141714225

Mechanical recycling of polylactide, upgrading trends and combination of valorization techniques

The upcoming introduction of polylactides in the fractions of polymer waste encourages technologists to ascertain its valorization at the best quality conditions. Mechanical recycling of PLA represents one of the most cost-effective methodologies, but the recycled materials are usually directed to downgraded applications, due to the inherent thermomechanical degradation affecting its mechanical, thermal and rheological performance. In this review, the current state of mechanical recycling of PLA is reported, with special emphasis on a multi-scale comparison among different studies. Additionally, the applications of physical and chemical upgrading strategies, as well as the chances to blend and/ or composite recycled PLA are considered. Moreover, the different valorization techniques that can be combined to optimize the value of PLA goods along its life cycle are discussed. Finally, a list of different opportunities to nurture the background of the mechanical recycling of PLA is proposed, in order to contribute to the correct waste management of PLA wastes

Relative amounts of antagonistic splicing factors, hnRNP A1 and ASF/SF2, change during neoplastic lung growth: implications for pre-mRNA processing

Pre-mRNA processing is an important mechanism for globally modifying cellular protein composition during tumorigenesis. To understand this process during lung cancer, expression of two key pre-mRNA alternative splicing factors was compared in a mouse model of early lung carcinogenesis and during regenerative growth following reversible lung injury. Heterogeneous nuclear ribonucleoprotein (hnRNP) A1 and alternative splicing factor/splicing factor 2 (ASF/SF2) act antagonistically to modulate splice site selection. Both hnRNP A1 and ASF/SF2 contents rose in adenomas and during injury-induced hyperplasia compared to control lungs, as measured by immunoblotting. While both proteins increased similarly during compensatory hyperplasia, hnRNP A1 increased to a much greater extent than ASF/SF2 in tumors, resulting in a 6-fold increase of the hnRNP A1 to ASF/SF2 ratio. Immunohistochemical analysis showed that hnRNP A1 localized exclusively within tumor nuclei, while ASF/SF2 appeared in cytoplasm and/or nuclei, depending on the growth pattern of the tumor cells. We also demonstrated cancer-associated changes in the pre-mRNA alternative splicing of CD44, a membrane glycoprotein involved in cell-cell and cell-extracellular matrix interactions. hnRNP A1 and ASF/SF2 expression is thus differentially altered in neoplastic lung cells by mechanisms that do not strictly arise from increased cell division. These changes are influenced by tumor histology and may be associated with production of variant CD44 mRNA isoforms

A gene-alteration profile of human lung cancer cell lines

ABSTRACT: Aberrant proteins encoded from genes altered in tumors drive cancer development and may also be therapeutic targets. Here we derived a comprehensive gene-alteration profile of lung cancer cell lines. We tested 17 genes in a panel of 88 lung cancer cell lines and found the rates of alteration to be higher than previously thought. Nearly all cells feature inactivation at TP53 and CDKN2A or RB1, whereas BRAF, MET, ERBB2, and NRAS alterations were infrequent. A preferential accumulation of alterations among histopathological types and a mutually exclusive occurrence of alterations of CDKN2A and RB1 as well as of KRAS, epidermal growth factor receptor (EGFR), NRAS, and ERBB2 were seen. Moreover, in nonsmall- cell lung cancer (NSCLC), concomitant activation of signal transduction pathways known to converge in mammalian target of rapamycin (mTOR) was common. Cells with single activation of ERBB2, PTEN, or MET signaling showed greater sensitivity to cell-growth inhibition induced by erlotinib, LY294002, and PHA665752, respectively, than did cells featuring simultaneous activation of these pathways, underlining the need for combined therapeutic strategies in targeted cancer treatments. In conclusion, our gene-alteration landscape of lung cancer cell lines provides insights into how gene alterations accumulate and biological pathways interact in cancer. Hum Mutat 30, 1199–1206, 2009. & 2009Wiley-Liss, Inc

A kinetic study of the formation of smectic phases in novel liquid crystal ionogens

A multi-rate non-isothermal kinetic analysis of the isotropic-melt to liquid crystalline phase transition of novel liquid crystalline ionogenic copolymers, LCIs, the 10-(4-methoxyazobenzene-4′-oxy)decyl methacrylate]-co-2-(acrylamido-2-methyl-1-propanesulfonic acid)s, 10-MeOAzB/AMPS, copolymers, has been performed by means of calorimetric experiments. An analytical methodology which includes the study of the phase transition rate parameter, the determination of the activation energies by using Kissinger and Flynn-Wall-Ozawa models, and the study of the phase transition kinetics by the use of the Avrami theory, has been applied. The formation of the mesophases from the isotropic state occurred close to thermodynamic equilibrium. The results evidence the presence of several individual processes in the formation of liquid crystalline phases from the melt and a strong dependence of phase transition rates and activation energies with acid contents. A decrease in the phase transition rate, related to a decrease in the overall change of the transition entropy, has been observed. The final inhibition of the liquid crystal (LC) behaviour is ascribed to an exponential increase in the activation energy of the phase transition, promoted by strong acid aggregation. An optimum composition of the 10-MeOAzB/AMPS copolymers to achieve the dual characteristics of LCIs (ionogenic and liquid crystalline behaviour) requires acid concentrations capable of promoting structure-forming effects on the LC phases and the evolution of phase separated morphologies

Resumen ejecutivo del Documento de Consenso de la Sociedad Española de Enfermedades Infecciosas y Microbiología Clínica (SEIMC) y de la Asociación Española de Cirujanos (AEC) en profilaxis antibiótica en cirugía

La profilaxis antibiótica en cirugía es una de las medidas más eficaces para la prevención de la infección de localización quirúrgica, aunque su uso es con frecuencia inadecuado, pudiendo incrementar el riesgo de infección, toxicidades y resistencias bacterianas. Debido al avance en las técnicas quirúrgicas y la emergencia de microorganismos multirresistentes las actuales pautas de profilaxis precisan ser revisadas. La Sociedad Española de Enfermedades Infecciosas (SEIMC), conjuntamente con la Asociación Española de Cirujanos (AEC) ha revisado y actualizado las recomendaciones de profilaxis antimicrobiana para adaptarlas a cada tipo de intervención quirúrgica y a la epidemiología actual. En este documento se recogen las recomendaciones de los antimicrobianos utilizados en profilaxis en los diferentes procedimientos, las dosis, la duración, la profilaxis en huéspedes especiales, y en situación epidemiológica de multirresistencia, de tal forma que permitan un manejo estandarizado, un uso racional, seguro y efectivo de los mismos en la cirugía electiva. Antibiotic prophylaxis in surgery is one of the most effective measures for preventing surgical site infection, although its use is frequently inadequate and may even increase the risk of infection, toxicities and antimicrobial resistance. As a result of advances in surgical techniques and the emergence of multidrug-resistant organisms, the current guidelines for prophylaxis need to be revised. The Sociedad Española de Enfermedades Infecciosas (Spanish Society of Infectious Diseases and Clinical Microbiology) (SEIMC) together with the Asociación Española de Cirujanos (Spanish Association of Surgeons) (AEC) have revised and updated the recommendations for antibiotic prophylaxis in surgery to adapt them to any type of surgical intervention and to current epidemiology. This document gathers together the recommendations on antimicrobial prophylaxis in the various procedures, with doses, duration, prophylaxis in special patient groups, and in epidemiological settings of multidrug resistance to facilitate standardized management and the safe, effective and rational use of antibiotics in elective surgery

Dielectric spectroscopy of recycled polylactide

The effects of multiple mechanical recycling on amorphous polylactide (PLA) were simulated by means of five successive injection-grinding cycles. The influence of the induced thermo-mechanical degradation on the dielectric properties of PLA was analysed. The relaxation spectra were studied in terms of the complex dielectric permittivity (ε0 and ε00) and the dielectric loss tangent, tg(d) in the frequency range from 102 to 107 Hz over the temperature interval from 0 C to 140 C. It was possible to distinguish two relaxations zones, one at low temperatures and high frequencies (b relaxation) and another at higher temperatures and lower frequencies (a relaxation). The individual relaxations were characterised using the HavriliakeNegami model and the effect of conductivity at high temperatures was subtracted. The thermal activation of the b relaxations was explained on an Arrhenius model basis while the a relaxation was modelled using VogeleFulchereTammanneHesse (VFTH) equations. The study of the segmental dynamics showed a decrease in the fragility parameters, connected with the decrease of molar mass, along with an increase in the free volume, the higher the number of reprocessing cycles were applied, particularly up to the second reprocessing step. 2014 Elsevier Ltd. All rights reserved.The authors would like to acknowledge the Spanish Ministry of Economy and Competitiveness, through the Research Project ENE2011-28735-C02-01. The Vice-Rectorate for Research, Innovation and Technology Transfer of Universitat Politecnica de Valencia is also thanked for additional support through PAID-06-SP20120581 project.Badía Valiente, JD.; Monreal Mengual, L.; Sáenz De Juano Arbona, V.; Ribes Greus, MD. (2014). Dielectric spectroscopy of recycled polylactide. Polymer Degradation and Stability. 107:21-27. https://doi.org/10.1016/j.polymdegradstab.2014.04.023S212710

Dielectric spectroscopy of novel thiol-ene/epoxy thermosets obtained from allyl-modified hyperbranched poly(ethyleneimine) and diglycidylether of bisphenol A

[EN] Dielectric Thermal Analysis (DETA) of a series of new thermoset obtained by click chemistry was performed. The new thermosets were obtained by a dual-curing process consisting in a first photochemical thiol-ene, followed by a thermal thiol-epoxy starting from an allyl-terminated hyperbranched poly(ethyleneimine) (HBPEI) and different proportions of diglycidylether of bisphenol A (DGEBA) and the corresponding stoichiometric proportions of pentaerythritol tetrakis (3-mercaptopropionate, PETMP). The dielectric behaviour was obtained experimentally supressing the conductive effects. Two sub-Tg intramolecular non-cooperative gamma and beta relaxations and an intermolecular cooperative alpha-relaxation were detected. The gamma-relaxation was ascribed to the dipole orientation of the terminal thiol groups. Two gamma relaxations gamma(epo) and gamma(ene) were observed, according to the influence of the surroundings. Only thermosets with a content of flexible HBPEI/PETMP domains higher than a 50% w/w showed the gamma(ene) relaxation at lower temperatures and higher frequencies. The beta-relaxation was a non-Johari-Goldstein relaxation, ascribed to the dipole transfer of the linear -CH2-O-(C=O)-CH2-CH2- groups of the thiol constrained in the glassy state. The alpha-relaxation was ascribed to the long-term segmental movements of the thermosets, occurring during the transition from the glassy to the rubbery stage. A synergic effect of reducing the rigidity and compactness of the thermosets by the reduction of aromatic moieties of the DGEBA/PETMP units, and the increase of the flexibility induced by the addition of HBPEI/PETMP units affected the macromolecular movement of the thermosets.European Regional Development Funds and the Spanish Ministry of Science, Innovation and Universities for ENE2017-86711-C3-1-R, MAT2017-82849-C2-1-R, ENE2014-53734-C2-1-R, UPOV13-3E-1947 and projects. Ministry of Education for the FPU13/01916) for O. Gil-Castell. Generalitat de Catalunya for the 2017-SGR-77 project. Generalitat Valenciana for the APOSTD14/041 for JD Badia and GRISOLIA/2012/003 for R. Teruel-Juanes.Badia, J.; Teruel Juanes, R.; Acebo, C.; Gil-Castell, O.; Serra, A.; Ribes-Greus, A. (2019). Dielectric spectroscopy of novel thiol-ene/epoxy thermosets obtained from allyl-modified hyperbranched poly(ethyleneimine) and diglycidylether of bisphenol A. European Polymer Journal. 113:98-106. https://doi.org/10.1016/j.eurpolymj.2019.01.001S9810611

Effect of graphene nanoplatelets on the dielectric permittivity and segmental motions of electrospun poly(ethylene-co-vinyl alcohol) nanofibers

The influence of the addition of graphene nanoplatelets (GNPs) on the intra/inter – molecular segmental motions of poly(ethylene-co-vinyl alcohol) (EVOH) was assessed by means of dielectric thermal analysis (DETA). The relaxation spectra were studied in terms of the dielectric permittivity (ε′) and the dielectric loss tangent (tan δ) at wide ranges of frequency (from 10−2 to 107 Hz) and temperature (from -150 to 140 °C). Two relaxation zones were disthinguished. Below the glass transition temperature (Tg), two β-relaxations were observed, which are characteristic local modes of mobility of the EVOH side groups, and related to the influence of the different surroundings of ethylene or vinyl alcohol units. At higher temperatures, the dielectric α-relaxation in the vicinities of the glass transition of EVOH was determined. The thermal activation of the β-relaxations was explained by an Arrhenius model, and showed activation energies (Ea) around 55 and 80 kJ·mol−1. The α-relaxation was explained by the Vogel-Fulcher-Tammann-Hesse (VFTH) model. The study of the segmental dynamics showed an increase in the dynamic fragility parameters with the addition of GNPs. The permittivity was increased at preferential concentrations of GNPs. In particular, the addition of GNPs up to 0.5 wt% increased the dielectric permittivity of the electrospun EVOH/GNPs nanocomposite fibers, specially at low frequencies.The authors would like to thank the European Regional Development Funds (ERDF) and the Spanish Ministry of Science, Innovation, and Universities (MICIU) for the concession of the Research Projects ENE2017-86711-C3-1-R and RTI2018-097249-B-C21. The UPV authors would also like to thank the Chilean Economic Development Agency (CORFO) the economic support in the frame of the project 13CEI2-21839. This research was also funded by the EU H2020 YPACK (773872) and USABLE (BBI-JTI-2018-836884) projects. Torres-Giner is a recipient of a Juan de la Cierva—Incorporación contract (IJCI-2016-29675) from MICIU. Universitat Politècnica de València is acknowledged for the post-doctoral aid for R. Teruel-Juanes, under the PAID-10-19 SUB.1 SP20190049 scholarship.Peer reviewe