Tuning the Properties of Molecular Magnets and Conductors Based on Lanthanide and Transition Metal Ions Bridged by TCNQ Derivatives or Cyanometallate Ligands by Varying the Dimensionality of the Structure and Metal Ion Identity

Research in the fields of molecular conductors and magnets over the past four decades has involved collaborative efforts of chemists and physicists whose common goal is to design useful materials composed of molecular building blocks. Of particular interest are materials whose properties can be tuned by electronic or steric changes in the molecular sub-units. The research on TCNQ derivatives described in this thesis was inspired by the observation that, although a vast amount of research has been directed at understanding binary M(TCNQ•-) materials, analogous compounds based on substituted TCNQ acceptors are surprisingly scarce. Single crystals of a new structure type for the M+(TCNQ)•- binary family were isolated from reactions of two dihalogenated TCNQ derivatives with Cu(I) ions, namely Cu(TCNQX2) (X = Cl, Br). The new 3-D compound Cu(TCNQCl2) exhibits the highest conductivity of the M+(TCNQ)•- series to date, despite the greater separation of TCNQCl2 units as compared to other derivatives. Compounds of lower dimensionality were also obtained, namely the 2-D Cu(TCNQBr2)(CH3CN) and 1-D Cu(TCNQI2)(CH3CN)2 phases. Several 2p-3d heterospin molecular magnets were also synthesized. For example a “magnetic sponge” material based on a 2-D hexagonal framework of composition {[Mn2(TCNQF4)(CH3OH)7.5(H2O)0.5]-(TCNQF4)2•7.5CH3OH}∞, as well as molecular magnets based on first row metal ions and TCNQF4 ligands of composition MII(TCNQF4)-•(TCNQF42-)0.5(CH3CN) (M = Mn, Co) were prepared. In addition, unprecedented isostructural 2-D frameworks based on combinations of first row metal ions with TCNQBr2 radicals of composition [M(TCNQBr2)2(H2O)2]∞ (M = Mn, Zn) were synthesized. Lanthanide chemistry is also described in this dissertation. A series of mononuclear Ln-TCNQF4 heterospin complexes of composition {MIII[TCNQF4]2[H2O]x}(TCNQF4)(3H2O) (M = La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er and Yb) was also obtained which exhibit remarkable properties. In this family of compounds there exists an unprecedented subtle interplay between single molecule magnetic behavior and phonon bottleneck effect behavior for the Tb analogue. Magnetic ordering was observed for the Sm analogue. A homologous series of 1-D materials based on alternating lanthanide ions and hexacyanometallates of formula {[Ln(tptz)(H2O)4Fe(CN)6]•8H2O}∞ (Ln = Pr, Nd, Sm, Eu, Gd, Tb) was obtained and a detailed magnetic study provided incontrovertible evidence that the SmIII-[FeIII(CN)6]3- compound exhibits ferromagnetic and not antiferromagnetic coupling as had been reported for related 1-D chains

Power absorption measurements during NMR experiments

The heating produced by the absorption of radiofrequency (RF) has been considered a secondary undesirable effect during MRI procedures. In this work, we have measured the power absorbed by distilled water, glycerol and egg-albumin during NMR and non-NMR experiments. The samples are dielectric and examples of different biological materials. The samples were irradiated using the same RF pulse sequence, whilst the magnetic field strength was the variable to be changed in the experiments. The measurements show a smooth increase of the thermal power as the magnetic field grows due to the magnetoresistive effect in the copper antenna, a coil around the probe, which is directly heating the sample. However, in the cases when the magnetic field was the adequate for the NMR to take place, some anomalies in the expected thermal powers were observed: the thermal power was higher in the cases of water and glycerol, and lower in the case of albumin. An ANOVA test demonstrated that the observed differences between the measured power and the expected power are significant

ANÁLISE ECONÔMICA DO PLANALTO AO EXTREMO-OESTE CATARINENSE

Para entender a economia atual de Santa Catarina é fundamental conhecer a história desse Estado, já que ela reflete os acontecimentos atuais. Por diversos motivos, cada região desenvolveu sua economia de forma mais ou menos independente uma da outra, o que tornou a economia do Estado mais diversificada, com graus de desenvolvimento diferentes em cada região, tendo como característica marcante a presença de capital local, o que a torna forte e influente no cenário nacional. Atualmente, a indústria catarinense é formada por vários fatores, tendo destaque os setores agroindustrial, têxtil, madeireiro, metal-mecânico, carbonífero, entre outros. No interior do Estado, alguns aglomerados de indústrias formam Arranjos Produtivos Locais (APLs), como a produção de leite, no oeste, a indústria madeireira e metal-mecânica, no meio-oeste, móveis no planalto norte, entre outras, ligadas principalmente à agroindústria e à indústria da madeira. Esses tipos de aglomerados caracterizam os locais onde estão e contribuem para o seu desenvolvimento. No entanto, vários setores tornam esses ramos da indústria mais fortes ou mais fracos, e isso repercute no desenvolvimento das regiões onde se encontram.Palavras-chave: Economia. Arranjos produtivos locais. Desenvolvimento

Acute Seroconversion of Eastern Equine Encephalitis Coinfection With California Serogroup Encephalitis Virus

Eastern equine encephalitis (EEE) is a severe arboviral neuroinvasive disease with high mortality and neurological sequelae. Treatment for EEE is primarily supportive. Intravenous immunoglobulin (IVIg) and high-dose steroids have been used as empirical therapy for EEE with some case reports of benefit. We report a case of a patient who presented with encephalopathy with initial cerebrospinal spinal fluid (CSF) serology analysis showing California serogroup encephalitis virus IgG positivity. However, the rapid clinical deterioration of the patient into a comatose state prompted a second CSF serology analysis that showed seroconversion of high titer Eastern Equine Encephalitis virus IgM and positive titer of California serogroup encephalitis virus IgG. The patient completed a 5-day course of empiric IVIg without concurrent corticosteroid therapy but did not show significant clinical improvement

Educational sessions in pharmacovigilance: What do the doctors think?

Background: The aim of this study was to determine physicians"opinion regarding pharmacovigilance feedback sessions. A survey was conducted in a teaching hospital, and the physicians who attended the sessions were invited to participate by filling out a structured questionnaire. All sessions included a review of adverse drug reactions identified at the hospital and information on pharmacovigilance issues (news on warnings released by regulatory agencies or drug toxicity problems identified by recently published studies in medical journals). The survey questions were related to the interest, satisfaction, and belief in the utility of the sessions. A Likert scale (0-10 points) was used to assess physicians" opinions. Findings: A total of 159 physicians attended the sessions and 115 (72.3%) participated in the survey. The mean (SD) age was 38.9 (12.1) years, and 72 (62.6%) were men. The mean (SD) scores of interest, satisfaction with the information provided, and belief in the utility of these sessions were 7.52 (1.61), 7.58 (1.46), and 8.05 (1.38) respectively. Significant differences were observed among physicians according to medical category and speciality in terms of interest, satisfaction, and belief in the utility of those sessions. Conclusions: Educational activities for physicians, such as feedback sessions, can be integrated into the pharmacovigilance activities. Doctors who attend the sessions are interested in and satisfied with the information provided and consider the sessions to be useful. Additional studies on the development and effectiveness of educational activities in pharmacovigilance are necessary

Synthesis and characterization of a Bio-MOF based on mixed adeninate/tricarboxylate ligands and zinc ions

Artículo científicoIn this work, we present a new metal organic framework Zn7(Ad)4(BTC)4(DMF)O·4DMA·3DMF·4H2O which was synthesized under hydrothermal conditions with adenine and trimesic acid (BTC) linkers. The structure was determined by single-crystal (XRD) and the compound was further characterized by Scanning electron microscopy (SEM), infrared spectroscopy (IR), and thermogravimetric analysis. The 3D anionic framework includes adenine present in two-different coordination modes, with dimethylammonium balancing the framework charg

Canagliflozin and Renal Outcomes in Type 2 Diabetes and Nephropathy

BACKGROUND Type 2 diabetes mellitus is the leading cause of kidney failure worldwide, but few effective long-term treatments are available. In cardiovascular trials of inhibitors of sodium–glucose cotransporter 2 (SGLT2), exploratory results have suggested that such drugs may improve renal outcomes in patients with type 2 diabetes. METHODS In this double-blind, randomized trial, we assigned patients with type 2 diabetes and albuminuric chronic kidney disease to receive canagliflozin, an oral SGLT2 inhibitor, at a dose of 100 mg daily or placebo. All the patients had an estimated glomerular filtration rate (GFR) of 30 to 300 to 5000) and were treated with renin–angiotensin system blockade. The primary outcome was a composite of end-stage kidney disease (dialysis, transplantation, or a sustained estimated GFR of <15 ml per minute per 1.73 m 2), a doubling of the serum creatinine level, or death from renal or cardiovascular causes. Prespecified secondary outcomes were tested hierarchically. RESULTS The trial was stopped early after a planned interim analysis on the recommendation of the data and safety monitoring committee. At that time, 4401 patients had undergone randomization, with a median follow-up of 2.62 years. The relative risk of the primary outcome was 30% lower in the canagliflozin group than in the placebo group, with event rates of 43.2 and 61.2 per 1000 patient-years, respectively (hazard ratio, 0.70; 95% confidence interval [CI], 0.59 to 0.82; P=0.00001). The relative risk of the renal-specific composite of end-stage kidney disease, a doubling of the creatinine level, or death from renal causes was lower by 34% (hazard ratio, 0.66; 95% CI, 0.53 to 0.81; P<0.001), and the relative risk of end-stage kidney disease was lower by 32% (hazard ratio, 0.68; 95% CI, 0.54 to 0.86; P=0.002). The canagliflozin group also had a lower risk of cardiovascular death, myocardial infarction, or stroke (hazard ratio, 0.80; 95% CI, 0.67 to 0.95; P=0.01) and hospitalization for heart failure (hazard ratio, 0.61; 95% CI, 0.47 to 0.80; P<0.001). There were no significant differences in rates of amputation or fracture. CONCLUSIONS In patients with type 2 diabetes and kidney disease, the risk of kidney failure and cardiovascular events was lower in the canagliflozin group than in the placebo group at a median follow-up of 2.62 years

Supramolecular dynamics: Synthesis, structure and novel properties of silver(I) benzamido pyridine complexes and copper(II) cubane assemblies

The synthesis and characterization of 17 crystal structures containing a new molecular scaffolds based on bis[L] silver (I), namely [Ag(L)2]X, where L = N-(4-pyridyl)benzamide (NPBA) and N-Phenyl-isonicotinamide (NPI), X = NO3−, PF6−, BF4−, ClO4−, CF3SO3 −, and p-toluenesulfonate was studied that result in molecular solids with 1-, 2- and 3-D non-covalent networks. These molecular solids provided a library from which one was discovered to exhibit single-crystal to single-crystal transformations and revealed information about supramolecular dynamics in the solid-state. We demonstrated that crystal systems that do not maximize their supramolecular contacts in the solid-state may exhibit reversible phase change behavior at higher temperatures. We proposed that this results will have an impact in the area of crystal polymorphism that procures the generation of new crystal systems with higher stability in order to increase % yield in the bulk manufacture of fine chemicals. We also report the synthesis and structural characterization of molecular magnets based on copper(II) cubane clusters. They magnetic properties were studied from 300 to 4 K. We observed that a set of hydrogen bonds stabilized the cubane structure. We designed experiments that showed that this supramolecular stabilization was key to the isolation and characterization of the Cu system