Electron Holes in G-Quadruplexes: The Role of Adenine Ending Groups

The study deals with four-stranded DNA structures (G-Quadruplexes), known to undergo ionization upon direct absorption of low-energy UV photons. Combining quantum chemistry calculations and time-resolved absorption spectroscopy with 266 nm excitation, it focuses on the electron holes generated in tetramolecular systems with adenine groups at the ends. Our computations show that the electron hole is placed in a single guanine site, whose location depends on the position of the adenines at the 3′ or 5′ ends. This position also affects significantly the electronic absorption spectrum of (G⁺)^● radical cations. Their decay is highly anisotropic, composed of a fast process (<2 µs), followed by a slower one occurring in ~20 µs. On the one hand, they undergo deprotonation to (G-H2)^● radicals and, on the other, they give rise to a reaction product absorbing in the 300–500 nm spectral domain.     

Preparation and thermal behavior of random poly(butylene terephthalate/azelate) copolyesters

Poly(butylene terephthalate), poly(butylene azelate), and poly(butylene terephthalate/butylene azelate) random copolymers of various compositions were synthesized in bulk using the well‐known two‐stage polycondensation procedure, and characterized in terms of chemical structure and molecular weight. The thermal behavior was examined by thermogravimetric analysis and differential scanning calorimetry. As far as the thermal stability is concerned, it was found to be rather similar for all copolymers and homopolymers investigated. All the copolymers were found to be partially crystalline, and the main effect of copolymerization was a lowering in the amount of crystallinity and a decrease of melting temperature with respect to pure homopolymers. Flory's equation was found to describe the T_m–composition data and permitted to calculate the melting temperatures (T^°_m ) and the heats of fusion (ΔH_u) of both the completely crystalline homopolymers. Owing to the high crystallization rate, the glass transition was observable only for the copolymers containing from 30 to 70 mol % of the terephthalate units; even though the samples cannot be frozen in a completely amorphous state, the data obtained confirmed that the introduction of the aromatic units gave rise to an increase of T_g, due to a chain stiffening. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2694–2702, 1999     

Macro-counterions in a precursor to poly(phenylene vinylene): Toward defect-free luminescent films

Thermal elimination of a water soluble poly(xylylidene) precursor to poly(phenylene vinylene) (PPV) was accomplished in air at 80 °C using the macro-counterion poly(ethylene glycol)-4-nonylphenyl-3-sulfopropyl ether (PEGNOPS). The high relative photoluminescence efficiency was ascribed to the low carbonyl content, with a possible contribution from PPV chain separation, which minimizes radiationless interchain exciton formation. In addition, the PEGNOPS precursor showed no carbonyl formation on long term storage, in contrast to the precursors with dodecylbenzene sulfonate and chloride counterions.     

Target Score—A Proteomics Data Selection Tool Applied to Esophageal Cancer Identifies GLUT1-Sialyl Tn Glycoforms as Biomarkers of Cancer Aggressiveness

Esophageal cancer (EC) is a life-threatening disease, demanding the discovery of new biomarkers and molecular targets for precision oncology. Aberrantly glycosylated proteins hold tremendous potential towards this objective. In the current study, a series of esophageal squamous cell carcinomas (ESCC) and EC-derived circulating tumor cells (CTCs) were screened by immunoassays for the sialyl-Tn (STn) antigen, a glycan rarely expressed in healthy tissues and widely observed in aggressive gastrointestinal cancers. An ESCC cell model was glycoengineered to express STn and characterized in relation to cell proliferation and invasion in vitro. STn was found to be widely present in ESCC (70% of tumors) and in CTCs in 20% of patients, being associated with general recurrence and reduced survival. Furthermore, STn expression in ESCC cells increased invasion in vitro, while reducing cancer cells proliferation. In parallel, an ESCC mass spectrometry-based proteomics dataset, obtained from the PRIDE database, was comprehensively interrogated for abnormally glycosylated proteins. Data integration with the Target Score, an algorithm developed in-house, pinpointed the glucose transporter type 1 (GLUT1) as a biomarker of poor prognosis. GLUT1-STn glycoproteoforms were latter identified in tumor tissues in patients facing worst prognosis. Furthermore, healthy human tissues analysis suggested that STn glycosylation provided cancer specificity to GLUT1. In conclusion, STn is a biomarker of worst prognosis in EC and GLUT1-STn glycoforms may be used to increase its specificity on the stratification and targeting of aggressive ESCC forms.     

Up-Regulation of mRNA Ventricular PRNP Prion Protein Gene Expression in Air Pollution Highly Exposed Young Urbanites: Endoplasmic Reticulum Stress,Glucose Regulated Protein 78, and Nanosized Particles

Mexico City Metropolitan Area children and young adults exposed to high concentrations of air pollutants including fine and ultrafine particulate matter (PM) vs. clean air controls, exhibit myocardial inflammation and inflammasome activation with a differential right and left ventricular expression of key inflammatory genes and inflammasomes. We investigated the mRNA expression levels of the prion protein gene PRNP, which plays an important role in the protection against oxidative stress and metal toxicity, and the glucose regulated protein 78, a key protein in endoplasmic reticulum (ER) stress signaling, in ventricular autopsy samples from 30 children and young adults age 19.97 ± 6.8 years with a lifetime of low (n:4) vs. high (n:26) air pollution exposures. Light microscopy and transmission electron microscopy studies were carried out in human ventricles, and electron microscopy studies were also done in 5 young, highly exposed Mexico City dogs. There was significant left ventricular PRNP and bi-ventricular GRP78 mRNA up-regulation in Mexico City young urbanites vs. controls. PRNP up-regulation in the left ventricle was significantly different from the right, p < 0.0001, and there was a strong left ventricular PRNP and GRP78 correlation (p = 0.0005). Marked abnormalities in capillary endothelial cells, numerous nanosized particles in myocardial ER and in abnormal mitochondria characterized the highly exposed ventricles. Early and sustained cardiac ER stress could result in detrimental irreversible consequences in urban children, and while highly complex systems maintain myocardial homeostasis, failure to compensate for chronic myocardial inflammation, oxidative and ER stress, and particles damaging myocardial organelles may prime the development of pathophysiological cardiovascular states in young urbanites. Nanosized PM could play a key cardiac myocyte toxicity role.     

<Emphasis Type="Italic">Arabidopsis thaliana:</Emphasis> A New Test Species for Phytotoxic Bioassays

Lettuce seeds (Lactuca sativa L.) and other crop species are often used in phytotoxic bioassays that are designed to detect allelochemicals. The seeds of these species are considered ideal because they are readily available, germinate rapidly and uniformly, and are routinely used in laboratories around the world. Despite their common use, however, the seeds of these species are often not as sensitive or responsive to some phytotoxic chemicals as are the seeds of other species. While searching for a more sensitive test species for phytotoxic bioassays, the Columbia ecotype of Arabidopsis thaliana exhibited greater sensitivity to seven potent allelochemicals than did lettuce seeds, which, in some cases, did not respond at all to those substances. Sensitivity satisfies one of the criteria for selecting a test species for bioassays. We now report on the results of our study and offer additional reasons for using A. thaliana seeds.     

Dibenzothiophene HDS Over Sulphided CoMo on High‐Silica USY Zeolites

USY faujasites (SiO₂/Al₂O₃ = 12, 30 and 80) were used as hydrodesulphurization (HDS) catalyst supports. Mo, Co and P were impregnated at two concentrations: ～12.5, ～3 and ～1.6 mass %; ～18, ～5.5 and ～2.2 mass % (CL and HL series, respectively). Surface acidity decreased after Co‐Mo‐P deposition. Sulphided catalysts were tested in dibenzothiophene (DBT) HDS (320°C, 5.59 MPa). The HDS rate slightly increased with both SiO₂ content and Co‐Mo‐P loading. High selectivity to hydrogenated products suggested deficient Mo promotion in CL solids. Improved Mo promotion by Co (HL series) could be responsible for higher activity and marked selectivity to desulphurization to biphenyl.     

Control of Polymer Composition in Pd‐Catalyzed CO/Olefin Terpolymerization Reactions

The CO/tert‐butylstyrene/ethylene terpolymerization catalyzed by Pd‐(N‐N′) complexes was studied. The results evidence that the olefin preferentially inserted in the terpolymer chain is strictly related to the nature of the nitrogen ligand, mainly to its steric constraints, and not to the kind of ligand. Indeed, slight variations in the backbone of the nitrogen ligands coordinated to palladium allow for the synthesis of terpolymers with a controlled composition.     

Melting behavior,crystallization kinetics and morphology of random copolyesters of poly(2‐hydroxyethoxybenzoate) with ε‐caprolactone

The melting behavior after isothermal crystallization and the crystallization kinetics of random poly(2‐hydroxyethoxybenzoate/ε‐caprolactone) copolymers rich in 2hydroxyethoxybenzoate units were investigated by means of differential scanning calorimetry and hot‐stage optical microscopy. The observed multiple endotherms, which are commonly displayed by polyesters, were found to be influenced both by crystallization temperature and composition. By applying the Hoffman‐Weeks method to the melting temperatures of isothermally crystallized samples, the equilibrium melting temperatures of the copolymers were obtained. Furthermore, isothemal crystallization kinetics was analyzed according to the Avrami treatment. Values of the exponent n close to 3 were obtained, independently of crystallization temperature and composition, in agreement with a crystallization process originating from predeterminated nuclei and characterized by three‐dimensional spherulitic growth. Space‐filling banded spherulites were observed by hot‐stage optical polarizing microscopy at all the crystallization temperatures explored, the band spacing being affected by both crystallization temperature and composition. As expected, the introduction of ε‐caprolactone comonomeric units in the polymer chain of PHEBA was found to decrease its crystallization rate.