Shedding Light on the Free Radical Nature of Sulfonated Melanins.

Melanin, an important class of natural pigment found in the human body, has stood out as a promising bioelectronic material due to its rather unique collection of electrical properties and biocompatibility. Among the available melanin derivatives, the sulfonated form has proven to not only be able to produce homogeneous device quality thin films with excellent adhesion, even on hydrophobic surfaces, but also to act as an ion to electron transducing element. It has recently been shown that the transport physics (and dominant carrier generation) may be related to a semiquinone free radical species in these materials. Hence, a better understanding of the paramagnetic properties of sulfonated derivatives could shed light on their charge transport behavior and thus enable improvement in regard to use in bioelectronics. Motivated by this question, in this work, different sulfonated melanin derivatives were investigated by hydration-controlled, continuous-wave X-band electron paramagnetic resonance spectroscopy and electronic structure calculations. Our results show that sulfonated melanin behaves similarly to non-functionalized melanin, but demonstrates a less pronounced response to humidity vis-à-vis standard melanin. We thus speculate on the structural and charge transport behavior in light of these differences with a view to further engineering structure-property relationships.

Study protocol to investigate biomolecular muscle profile as predictors of long-term urinary incontinence in women with gestational diabetes mellitus.

BACKGROUND: Pelvic floor muscles (PFM) and rectus abdominis muscles (RAM) of pregnant diabetic rats exhibit atrophy, co-localization of fast and slow fibers and an increased collagen type I/III ratio. However, the role of similar PFM or RAM hyperglycemic-related myopathy in women with gestational diabetes mellitus (GDM) remains poorly investigated. This study aims to assess the frequency of pelvic floor muscle disorders and pregnancy-specific urinary incontinence (PS-UI) 12 months after the Cesarean (C) section in women with GDM. Specifically, differences in PFM/RAM hyperglycemic myopathy will be evaluated. METHODS: The Diamater is an ongoing cohort study of four groups of 59 pregnant women each from the Perinatal Diabetes Research Centre (PDRC), Botucatu Medical School (FMB)-UNESP (São Paulo State University), Brazil. Diagnosis of GDM and PS-UI will be made at 24-26 weeks, with a follow-up at 34-38 weeks of gestation. Inclusion in the study will occur at the time of C-section, and patients will be followed at 24-48 h, 6 weeks and 6 and 12 months postpartum. Study groups will be classified as (1) GDM plus PS-UI; (2) GDM without PS-UI; (3) Non-GDM plus PS-UI; and (4) Non-GDM without PS-UI. We will analyze relationships between GDM, PS-UI and hyperglycemic myopathy at 12 months after C-section. The mediator variables to be evaluated include digital palpation, vaginal squeeze pressure, 3D pelvic floor ultrasound, and 3D RAM ultrasound. RAM samples obtained during C-section will be analyzed for ex-vivo contractility, morphological, molecular and OMICS profiles to further characterize the hyperglycemic myopathy. Additional variables to be evaluated include maternal age, socioeconomic status, educational level, ethnicity, body mass index, weight gain during pregnancy, quality of glycemic control and insulin therapy. DISCUSSION: To our knowledge, this will be the first study to provide data on the prevalence of PS-UI and RAM and PFM physical and biomolecular muscle profiles after C-section in mothers with GDM. The longitudinal design allows for the assessment of cause-effect relationships between GDM, PS-UI, and PFMs and RAMs myopathy. The findings may reveal previously undetermined consequences of GDM.

Light-Induced Structural Change in Iridium Complexes Studied by Electron Spin Resonance.

Iridium-based compounds are materials of great interest in the production of highly efficient organic light emitting diodes and several other applications. However, these organometallic compounds present relative low stability due to photodegradation processes still not well understood. In this work we investigated paramagnetic states induced by UV photoexcitation on iridium(III) bis[(4,6-fluorophenyl)-pyridinato-N,C2']picolinate (FIrpic) and iridium(III)-tris(2-phenylpyridine) (Ir(ppy)3) complexes dispersed in different polymeric matrices by electron spin resonance (ESR). Photogenerated charged states with relatively strong hyperfine interactions were observed and attributed to matrix/complex charge-transfer processes. Measurements of the signal amplitude decay after photoexcitation interruption were performed as a function of temperature. The photoinduced centers are thermally activated with energy barrier between 0.3 and 0.6 eV. Electronic structure calculations suggest that the signals observed by ESR are associated with metastable negatively charged Ir complexes distorted structures.

eNOS T-786C polymorphism affects atorvastatin-induced changes in erythrocyte membrane fluidity.

PURPOSE: Statins have pleiotropic effects, including endothelial nitric oxide synthase (eNOS) upregulation and increased nitric oxide formation, which can be modulated by a genetic polymorphism in the promoter region of the eNOS gene (T-786C). Here, we report our investigation of whether this polymorphism modulates the effects of atorvastatin on the fluidity of erythrocyte membranes. METHODS: We genotyped 200 healthy subjects (males, 18-60 years of age) and then randomly selected 15 of these with the TT genotype and 15 with the CC genotype to receive placebo or atorvastatin (10 mg/day oral administration) for 14 days. Cell membrane fluidity was evaluated by electron paramagnetic resonance (EPR) and spin-labeling method. The EPR spectra were registered on a VARIAN-E4 spectrometer. Thiobarbituric acid-reactive species (TBA-RS) and plasma membrane cholesterol were determined in the erythrocytes. RESULTS: Atorvastatin reduced membrane fluidity in CC subjects (P < 0.05) but not in those with the TT genotype (P > 0.05). While no significant differences were found in plasma membrane cholesterol concentrations, higher TBA-RS concentrations were found in the CC subjects than in the TT subjects (P < 0.05). CONCLUSIONS: These findings suggest that a short treatment with atorvastatin is disadvantageous to subjects with the CC genotype for the T-786C polymorphism compared to those with TT genotype, at least in terms of the hemorheological properties of erythrocytes.

Magnetic properties of synthetic eumelanin--preliminary results.

We report an experimental and theoretical study of magnetic properties of synthetic eumelanin. The magnetization curves are determined by using both a vibrating sample magnetometer and a superconducting quantum interferometer device in an extended range of magnetic fields ranging from -10 kOe to 10 kOe at different temperatures. We find that the eumelanin magnetization can be qualitatively explained in terms of a simple model of dipolar spheres with an intrinsic magnetic moment. The latter one is experimentally measured by using X-band electron paramagnetic resonance. Our findings indicate that synthetic melanins are superparamagnetic.

Hirsch's index: a case study conducted atthe Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto, Universidade de São Paulo

An analysis of scientific bibliographic productivity using the Hirsch h-index, information from the Institute of Scientific Information database and the Curriculum Lattes (CNPq, Brazil) was performed at the Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto, Universidade de São Paulo (FFCLRP-USP) that has four departments in natural, biological and social sciences. Bibliometric evaluations of undergraduate programs showed a better performance of the departments of Chemistry (P < 0.001) and Biology (P < 0.001) when compared to the departments of Physics and Mathematics and Psychology and Education. We also analyzed the scientific output of the six graduate programs of FFCLRP: Psychology, Psychobiology, Chemistry, Physics Applied to Medicine and Biology, Comparative Biology, and Entomology. The graduate program in Psychology presented a lower h-index (P < 0.001) and had fewer papers indexed by the ISI web of science (P < 0.001) when compared to the other graduate programs. The poorer performance of the Psychology program may be associated with the limited coverage by the Thompson Institute of Scientific Information database.

Hirsch's index: a case study conducted atthe Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto, Universidade de São Paulo.

An analysis of scientific bibliographic productivity using the Hirsch h-index, information from the Institute of Scientific Information database and the Curriculum Lattes (CNPq, Brazil) was performed at the Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto, Universidade de São Paulo (FFCLRP-USP) that has four departments in natural, biological and social sciences. Bibliometric evaluations of undergraduate programs showed a better performance of the departments of Chemistry (P < 0.001) and Biology (P < 0.001) when compared to the departments of Physics and Mathematics and Psychology and Education. We also analyzed the scientific output of the six graduate programs of FFCLRP: Psychology, Psychobiology, Chemistry, Physics Applied to Medicine and Biology, Comparative Biology, and Entomology. The graduate program in Psychology presented a lower h-index (P < 0.001) and had fewer papers indexed by the ISI web of science (P < 0.001) when compared to the other graduate programs. The poorer performance of the Psychology program may be associated with the limited coverage by the Thompson Institute of Scientific Information database.

Transport and recombination in organic light-emitting diodes studied by electrically detected magnetic resonance.

We have used electrically detected magnetic resonance (EDMR) to study a series of multilayer organic devices based on aluminum (III) 8-hydroxyquinoline (Alq3). These devices were designed to identify the microscopic origin of different spin-dependent processes, i.e. hopping and exciton formation. The EDMR signal in organic light-emitting diodes (OLEDs) based on Alq3 is only observed when the device is electroluminescent and is assigned to spin-dependent exciton formation. It can be decomposed in at least two Gaussians: one with peak-to-peak line (deltaH(PP)) of 1.6 mT and another with deltaH(PP) of 2.0 to 3.4 mT, depending on bias and temperature. The g-factors of the two components are barely distinguishable and close to 2.003. The broad line is attributed to the resonance in Alq3 anions, while the other line is attributed to cationic states. These attributions are supported by line shape and its electrical-field dependence of unipolar Alq3-based diodes, where hopping process related to dication and dianion formation is observed. In these unipolar devices, it is shown that the signal coming from spin-dependent hopping occurs close to organic semiconductor/metal interfaces. The sign of the magnetic-resonance-induced conductivity change is dominated by charge injection rather than charge mobility. Our results indicate that the probability of singlet exciton formation in our OLEDs is smaller than 25%.