Chain walking copolymerization of ethylene with cyclopentene - Effect of ring incorporation on polymer chain topology

Chain walking ethylene copolymerizations with cyclopentene (CPE) as the ring-forming comonomer were carried out in this study to investigate the tuning of polyethylene chain topology via the unique strategy of ring incorporation. Four sets of polymers containing five-membered rings on the polymer backbone at various low contents (in the range of 0-7.5 mol%) were synthesized by controlling CPE feed concentration at four different ethylene pressure/temperature combinations (1 atm/15 °C, 1 atm/25 °C, 1 atm/35 °C, and 6 atm/25 °C, respectively) using a Pd-diimine catalyst, [(ArNC(Me)-(Me)CNAr)Pd(CH₃)(NCMe)]⁺SbF₆⁻ (Ar = 2,6-(iPr)₂C₆H₃). The polymers were characterized extensively using ¹³C nuclear magnetic resonance (NMR) spectroscopy, triple-detection gel permeation chromatography (GPC), and rheometry to elucidate the chain microstructures and study the effect of ring incorporation on polymer chain topology. It was found that CPE was incorporated in the copolymers primarily in the form of isolated cis-1,3 ring units, along with a small fraction in the form of isolated cis-1,2 ring units. Significant linearization of polymer chain topology was achieved with ring incorporation in each of the three sets of polymers synthesized at 1 atm on the basis of the incrementally raised intrinsic viscosity curves in the Mark-Houwink plot and the significantly enhanced zero-shear viscosity of the polymer melts with the increase of ring content despite the decreasing polymer molecular weight. For the set of polymers synthesized at 6 atm/25 °C, the effect of ring incorporation on polymer chain topology was negligible or weaker due to their linear chain topology resulting at this polymerization condition. The results obtained in this study support the proposed blocking effect of backbone-incorporated rings on catalyst chain walking, and demonstrate that effective tuning of polyethylene chain topology from hyperbranched to linear can be conveniently achieved via CPE incorporation while without changing ethylene pressure or polymerization temperature.     

Aberrant Expression of Posterior HOX Genes in Well Differentiated Histotypes of Thyroid Cancers

Molecular etiology of thyroid cancers has been widely studied, and several molecular alterations have been identified mainly associated with follicular and papillary histotypes. However, the molecular bases of the complex pathogenesis of thyroid carcinomas remain poorly understood. HOX genes regulate normal embryonic development, cell differentiation and other critical processes in eukaryotic cell life. Several studies have shown that HOX genes play a role in neoplastic transformation of several human tissues. In particular, the genes belonging to HOX paralogous group 13 seem to hold a relevant role in both tumor development and progression. We have identified a significant prognostic role of HOX D13 in pancreatic cancer and we have recently showed the strong and progressive over-expression of HOX C13 in melanoma metastases and deregulation of HOX B13 expression in bladder cancers. In this study we have investigated, by immunohistochemisty and quantitative Real Time PCR, the HOX paralogous group 13 genes/proteins expression in thyroid cancer evolution and progression, also evaluating its ability to discriminate between main histotypes. Our results showed an aberrant expression, both at gene and protein level, of all members belonging to paralogous group 13 (HOX A13, HOX B13, HOX C13 and HOX D13) in adenoma, papillary and follicular thyroid cancers samples. The data suggest a potential role of HOX paralogous group 13 genes in pathogenesis and differential diagnosis of thyroid cancers.     

A 3D Model for Optimizing Infrastructure Costs in Road Design

In this article, the optimal design of a road joining two terminals is investigated. A geometric model is proposed including horizontal transition curves and vertical curves, obtaining parameterizations for the central axis of the road as well as for its entire surface. These parameterizations allow to express and compute, with great simplicity, the major infrastructure costs, including land acquisition, clearance, pavement, maintenance, and earthwork, where multiple layers of materials with different costs can be handled. The road design problem is formulated as a smooth constrained optimization problem and a two‐stage algorithm is suggested for its numerical resolution. Finally, numerical results are presented in an academic test and in a case study that propose designing a bypass in a Spanish national road (N‐640) to avoid crossing Monterroso's town center.     

Magnetically triggered nanocomposite membranes: a versatile platform for triggered drug release

Drug delivery devices based on nanocomposite membranes containing thermoresponsive nanogels and superparamagnetic nanoparticles have been demonstrated to provide reversible, on-off drug release upon application (and removal) of an oscillating magnetic field. We show that the dose of drug delivered across the membrane can be tuned by engineering the phase transition temperature of the nanogel, the loading density of nanogels in the membrane, and the membrane thickness, allowing for on-state delivery of model drugs over at least 2 orders of magnitude (0.1-10 μg/h). The zero-order kinetics of drug release across the membranes permit drug doses from a specific device to be tuned according to the duration of the magnetic field. Drugs over a broad range of molecular weights (500-40000 Da) can be delivered by the same membrane device. Membrane-to-membrane and cycle-to-cycle reproducibility is demonstrated, suggesting the general utility of these membranes for drug delivery.     

Nanoparticle-based cerebral drug-delivery systems and antiangiogenic approach in gliomas treatment

The efficacy of current anti-cancer multimodal therapeutic strategies in gliomas is limited by the lack of specific therapies against malignant cells and the prognosis in patients affected by cerebral gliomas remains very unfavorable. Glial tumors seem to be able to create a favorable environment for the invasion of neoplastic cells when they combine with the extracellular matrix through the up-regulation of crucial pathways such as angiogenesis and invasion. The major problem in brain drug delivery is the presence of the blood brain barrier which limits the delivery of many chemotherapeutic agents and other kinds of therapeutic molecules. This event often contributes to the failure of the treatment. Nanoparticle systems can represent ideal devices for delivery of specific compounds to brain tumors across the blood brain barrier. The specificity of hybridization makes antisense method an interesting strategy to selectively modulate the expression of genes involved in tumorigenesis. In this review we will focus on the mechanisms of angiogenesis into gliomas, their importance into tumor progression and the possibilities to block these mechanisms with new nanoparticle-based therapeutic strategies. We will also report the results of preclinical and/or clinical studies that adopt nanoparticle-based antiangiogenic therapeutic approach in cerebral gliomas, considering also some patents deal with antiangiogenic strategy.     

Main aspects of geothermal energy in Mexico

With an installed geothermal electric capacity of 853 MW_e, Mexico is currently the third largest producer of geothermal power worldwide, after the USA and the Philippines. There are four geothermal fields now under exploitation: Cerro Prieto, Los Azufres, Los Humeros and Las Tres Vírgenes. Cerro Prieto is the second largest field in the world, with 720 MW_e and 138 production wells in operation; sedimentary (sandstone) rocks host its geothermal fluids. Los Azufres (88 MW_e), Los Humeros (35 MW_e) and Las Tres Vírgenes (10 MW_e) are volcanic fields, with fluids hosted by volcanic (andesites) and intrusive (granodiorite) rocks. Four additional units, 25 MW_e each, are under construction in Los Azufres and due to go into operation in April 2003. One small (300 kW) binary-cycle unit is operating in Maguarichi, a small village in an isolated area with no link to the national grid. The geothermal power installed in Mexico represents 2% of the total installed electric capacity, but the electricity generated from geothermal accounts for almost 3% of the national total.     

Effect of CeO2 on the Glass Structure of Sodium Germanate Glasses

Germanate glasses have potential applications as optical fibers. Materials doped with rare earth ions are good candidates for optical, lasing, and magnetic applications. Based on the ternary system, CeO₂–Na₂O–GeO₂ a series of six glasses were fabricated using powder fusion, and varying the Na₂O content from 0 to 45 mol%, and a CeO₂ content constant at 3 mol%. The glasses were analyzed by FT‐IR, Raman and X‐ray photoelectron (XPS) spectroscopies to obtain information about the glass structure, cerium oxidation's state and how it is introduced in the glass network. FT‐IR and Raman spectra revealed the presence of GeO₆ and GeO₄ groups as well as Q² and Q³ units in the glasses with alkali low content. XPS spectra analysis revealed that the cerium ions were reduced from Ce⁴⁺ to Ce³⁺. The nonbonding to total oxygen ratio was estimated from the curve fitting of the O 1s core level spectra. Density and elastic parameters showed a nonlineal tendency in the change of the physical properties as a function of Na₂O content. Finally, photoluminescence spectroscopy confirmed the presence of Ce³⁺ ions. The characteristic 4f → 5d electronic transitions at 360 nm were detected, when a 280 nm excitation line of pulsed laser was used as excitation source.     

Interaction of noise with excitable dynamics

In this paper, the interaction of noise with excitable dynamics of a three-electrode electrochemical cell is examined. Different scenarios involving both external and internal noise sources are considered. In the case of external noise, aperiodic stochastic resonance and regulation of the noise-induced spiking behaviour are investigated. In the case of internal noise, the interaction of intrinsic electrochemical noise with autonomous nonlinear dynamics is studied. The amplitude of this internal noise, determined by the concentration of chloride ions, is monotonically increased and the provoked dynamics are analysed. Our results indicate that internal noise, similar to its external counterpart, is able to induce regularity in the system response.     

Analytical investigation of elastic period of infilled RC MRF buildings

Fundamental period of vibration, dependent on mass and stiffness structure characteristics, is a key parameter in assessing seismic demand. The period can be evaluated both by means of empirical formulas and modal analysis carried out on a structure numerical model. The presence of external or internal infill elements, usually considered as “non-structural” elements, is generally not taken into account in structural modelling, although these elements can significantly increase the lateral stiffness of a Reinforced Concrete (RC) Moment Resisting Frame (MRF) building leading to a modification in dynamic properties.In this study, results of modal analyses carried out on 3D numerical RC MRF building models are presented, varying structure morphology (height, surface area, ratio between plan dimensions) and infill characteristics. Simplified formulas based on regression analysis of obtained numerical data are presented and discussed. These relationships are also compared with similar literature numerical expressions and empirical data from experimental measurements on existing buildings.