ABSTRACT The objective of this study was to evaluate the effect of either a limited forage intake or concentrate supplementation prior to the adaptation to high-concentrate diets on dry matter intake, ruminal pH, bacteria, and protozoa of Nellore cattle. The experiment was designed as a two 3×3 Latin square, and six cannulated Nellore steers were used. Each experimental period was composed by three feeding phases: pre-adaptation (14 days), adaptation (12 days), and finishing (seven days) diet, in a total of 33 days per period. The steers were assigned to one of three pre-adaptation dietary treatments: control (Tifton hay fed ad libitum + mineral supplement), restriction (Tifton hay fed at 1.4% of BW + mineral supplement), and concentrate (Tifton hay fed ad libitum + 0.5% of BW of a mix of concentrate feedstuffs and mineral supplement). The adaptation period consisted of two adaptation diets, which contained 72 and 79% concentrate for six days each. The finishing diet contained 86% concentrate. During the pre-adaptation phase, restricted cattle had higher pH than concentrate-fed cattle. There was a reduction in M. elsdenii relative population in cattle from either restriction or concentrate groups. During adaptation and finishing phases, cattle from concentrate group had smaller F. succinogenes populations compared with the control group. The previous nutritional backgrounds impact ruminal microbiota during adaptation and finishing phases without causing any negative effect on ruminal pH. Feeding concentrate prior to the adaptation positively impacted the transition to high-concentrate diets and promoted increased dry matter intake.

In this paper a novel supramolecular strategy to improve the efficiency of a voltammetric sensor to determine two biologically relevant molecules (epinephrine (EP) and uric acid (UA)) is presented. The strategy is based on the use of a glassy carbon electrode modified with a copper(II) complex ([Cu(H2dimpy)Cl]PF6) adsorbed on multi-walled carbon nanotubes (MWCNTs). The [Cu(H2dimpy)Cl]PF6/MWCNT composite-supported electrode was characterized by electrochemical impedance spectroscopy, scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). The electrocatalytic oxidation of EP and UA using the sensor was investigated by cyclic voltammetry and square wave voltammetry. Under optimized conditions, voltammetric peak currents showed a linear response for the EP and UA concentrations in the ranges 0.5-159.2 and 0.2-58.5 µmol L−1, whereas the limits of detection were 0.2 and 0.05 µmol L−1, respectively. The sensor was successfully applied in the selective and simultaneous determination of EP and UA in human urine samples. Thus, our results showed that the supramolecular strategy was successful to build an efficient sensor for simultaneous detection of these molecules in biological samples.

The present work presents the development of a sensitive and selective amperometric sensor for the determination of hydrazine (HZ) in pharmaceutical formulations using a glassy carbon electrode (GCE) modified with a composite based on Co(Salophen), reduced graphene oxide (rGO) and deoxyribonucleic acid (DNA). The rGO/Co(Salophen)/DNA composite was characterized by using Fourier-transform infrared spectroscopy (FTIR), cyclic voltammetry, and amperometry. The proposed platform presented a well-defined voltammetric profile with a redox couple around 0.32 V vs. Ag/AgCl which showed excellent catalytic activity towards HZ oxidation. The peak current of HZ electrochemical oxidation on the proposed electrochemical platform have changed linearly with the HZ concentration in the range from 2 to 364 µmol L-1. The proposed platform presented sensitivity, limit of detection, and limit of quantification of 0.056 µA L µmol-1, 0.54 µmol L-1, and 1.64 µmol L-1 to HZ, respectively. The relative standard deviation for eight determinations using a solution of 50 µmol L-1 HZ was 0.85%. The proposed sensor was successfully applied for the determination of HZ in pharmaceutical formulations, and the recovery tests showed a good accuracy with recovery percentage between 99 and 101%.

This work reports a simple and low cost voltammetric approach comprising a boron-doped diamond electrode (BDDE) to determine the antibiotic ethionamide (ETO). Cyclic voltammetry studies revealed that ETO exhibits an irreversible reduction peak at -0.95 V and an irreversible oxidation peak at +1.4 V onto BDDE (vs. saturated Ag/AgCl reference electrode) in Britton-Robinson buffer solution (pH 5.0, 0.1 mol L-1). Different voltammetric scan rates (from 10 to 150 mV s-1) suggested that the reduction of ETO on the BDDE surface is a diffusion-controlled process. Square wave voltammetry (SWV) optimized conditions showed a linear response to ETO from 1.00 to 80.0 µmol L-1 (R2 = 0.998) with a limit of detection of 0.294 µmol L-1 and limit of quantification of 0.980 µmol L-1. The developed square wave voltammetric method was successfully used in the determination of ETO in human urine and pharmaceutical formulation. The ETO quantification results in pharmaceutical tablets obtained by SWV-BDDE were comparable to those found by official analytical protocols.

The [Ru(Spym)(bipy)(P–P)]PF6, [Spym = pyrimidine-2-thiolate anion; P–P = 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane and 1,1'-bis(diphenylphosphino)ferrocene] complexes were synthesized and characterized by spectroscopic, electrochemical and elemental analysis, and by X-ray crystallography. The minimal inhibitory concentration (MIC) of the compounds against Mycobacterium tuberculosis and the complex concentration causing 50% tumor cell growth inhibition (IC50) against breast cancer cells, MDA-MB-231, were determined. All three compounds gave promising values in both tests. It is interesting to mention that all three complexes display MICs against Mycobacteriumtuberculosis showing higher activity than cycloserine, a second line drug used in the treatment of the illness. The complexes interact weakly with the DNA.

Complexos de CoIII derivados da 2-acetilpiridina N(4)-R tiossemicarbazona (Hatc-R, R = alquil ou aril) foram caracterizados por análise elementar, espectroscopia na região do infravermelho, UV-Visível e ¹H RMN, voltametria cíclica (VC), medidas de condutividade e difração de raios X em monocristal. Os resultados obtidos são consistentes com a oxidação do centro de CoII para CoIII após a coordenação N,N,S-tridentada e monoaniônica dos ligantes tiossemicarbazonas, resultando em complexos octaédricos iônicos do tipo [Co(atc-R)2]Cl. Os estudos de eletroquímica mostram dois processos reversíveis, referentes aos pares redox CoIII/CoII e CoII/CoI, que são afetados pelo efeito indutivo dos grupos substituintes na posição N4 dos ligantes. Dois complexos de CoIII se mostraram satisfatoriamente ativos, com valores de concentração inibitória mínima abaixo de 10 µmol L- 1 e um deles apresentou muito baixa citotoxicidade contra células VERO e J774A.1 (IC50), conferindo-lhe altos índices de seletividade (SI > 10).

CoIII complexes derived from 2-acetylpyridine N(4)-R thiosemicarbazone (Hatc-R, R = alkyl, aryl) have been characterized by elemental analysis, FTIR, UV-Visible and ¹H NMR spectroscopies, cyclic voltammetry (CV), conductimetry measurements and single crystal X-ray diffractometry. The results obtained are consistent with the oxidation of the CoII center to CoIII upon coordination of the monoanionic N,N,S-tridentate thiosemicarbazone ligands, resulting in octahedral ionic complexes of the type [Co(atc-R)2]Cl. Electrochemistry studies show two reversible processes referring to the redox couples CoIII/CoII and CoII/CoI which can be modified by the inductive effects of the substituents groups at the N4 position of the ligands. Two CoIII complexes showed satisfactory activity with minimal inhibitory concentration value under 10 µmol L- 1 and one presented quite low cytotoxicity against VERO and J774A.1 cells (IC50), resulting in high selectivity index (SI > 10).

Paepalanthus spp., Eriocaulaceae, are native plants from Brazil known as "sempre-vivas" (everlasting flowers). In this work, we evaluated the potential anti-mycobacterial activity of two methoxylated flavonoids (flavonoid 7-methylquercetagetin and 7-methylquercetagetin-4'-O-β-D-glucopyranoside) isolated and identified from P. latipes and the naphthopyranone fractions from P. bromeliodes ethanolic extracts. The MIC value of 500 µg/mL was verified for all compounds tested against M. tuberculosis H37Rv. For M. avium, the MIC value ranged from 1000-2000 µg/mL excepting to naphthopyranone fractions with MIC of 500 µg/mL. This is the first report of activity determination of Paepalanthus spp. flavonoids activity against Mycobacterium tuberculosis and M. avium.

OBJECTIVE: Obstructive sleep apnea is frequent during the acute phase of stroke, and it is associated with poorer outcomes. A well-established relationship between supine sleep and obstructive sleep apnea severity exists in non-stroke patients. This study investigated the frequency of supine sleep and positional obstructive sleep apnea in patients with ischemic or hemorrhagic stroke. METHODS: Patients who suffered their first acute stroke, either ischemic or hemorrhagic, were subjected to a full polysomnography, including the continuous monitoring of sleep positions, during the first night after symptom onset. Obstructive sleep apnea severity was measured using the apnea-hypopnea index, and the NIHSS measured stroke severity. RESULTS: We prospectively studied 66 stroke patients. The mean age was 57.6±11.5 years, and the mean body mass index was 26.5±4.9. Obstructive sleep apnea (apnea-hypopnea index >5) was present in 78.8% of patients, and the mean apnea-hypopnea index was 29.7±26.6. The majority of subjects (66.7%) spent the entire sleep time in a supine position, and positional obstructive sleep apnea was clearly present in the other 23.1% of cases. A positive correlation was observed between the NIHSS and sleep time in the supine position (r s = 0.5; p<0.001). CONCLUSIONS: Prolonged supine positioning during sleep was highly frequent after stroke, and it was related to stroke severity. Positional sleep apnea was observed in one quarter of stroke patients, which was likely underestimated during the acute phase of stroke. The adequate positioning of patients during sleep during the acute phase of stroke may decrease obstructive respiratory events, regardless of the stroke subtype.

Our purpose was to determine the anti-Mycobacterium tuberculosis activity of the metabolites produced by the endophitic fungus Phomopsis stipata (Lib.) B. Sutton, (Diaporthaceae), cultivated in different media. The antimycobacterial activity was assessed through the Resazurin Microtiter Assay (REMA) and the cytotoxicity test performed on macrophage cell line. The extracts derived from fungi grown on Corn Medium and Potato Dextrose Broth presented the smallest values of Minimum Inhibitory Concentration (MIC) and low cytotoxicity, which implies a high selectivity index. This is the first report on the chemical composition and antitubercular activity of metabolites of P. stipata, as well as the influence of culture medium on these properties.

O sistema de plantio direto é uma alternativa viável para o uso sustentável dos solos. O objetivo do presente trabalho foi avaliar a influência do sistema plantio direto com diferentes tempos de implantação e do plantio convencional sobre os atributos químicos e os estoques de C de um Latossolo Vermelho-Amarelo do cerrado piauiense. Amostras de solo foram coletadas nas camadas de 0-5, 5-10, 10-20 e 20-40 cm em sistema de plantio convencional (PC) e plantio direto (PD) com 2 (PD2), 4 (PD4) e 6 (PD6) anos de implantação, além de uma área sob floresta nativa de cerrado (FNC). Foram determinados o pH em água, P extraível (Pext), bases trocáveis, Al, acidez potencial (H+Al), carbono orgânico total (COT) e carbono da biomassa microbiana (Cmic). A adoção do sistema plantio direto aumentou o pH, os teores de P e de bases trocáveis do solo, em comparação com o PC. Em relação ao PC, os estoques de COT e Cmic aumentaram 34 e 99% no PD2, 47 e 92% no PD4 e 61 e 108% no PD6, respectivamente, na camada superficial de 0-20 cm. A implantação do sistema plantio direto melhora os atributos químicos e aumenta os estoques de carbono orgânico total e microbiano do solo e seu uso contínuo contribui para a qualidade do solo em áreas do cerrado piauiense.

No-tillage adoption has been considered a viable alternative for sustainable soil use. This work aimed to evaluate the influence of no-tillage system with different times of adoption and conventional tillage on chemical attributes and carbon stocks in an Oxisol of the savannah of Piauí in Northeastern Brazil. Soil samples in the 0-5, 5-10, 10-20 and 20-40 cm layers were collected in conventional tillage (CT) no-tillage (NT) with 2 (NT2), 4 (NT4) and 6 (NT6) years of adoption and native forest (NF). The following chemical properties were evaluated: pH, extractable P, exchangeable cations, Al, potential acidity (H+Al), total organic carbon (TOC) and microbial biomass carbon (Cmic). NT adoption increased pH, extractable P and exchangeable cations contents. Compared to conventional tillage, TOC and Cmic stocks increased 34 and 99% (NT2), 47 and 92% (NT4) and 61 and 108% (NT6), respectively, in the superficial layer (0-20 cm). No-tillage adoption improves chemical attributes and increases total organic carbon and microbial carbon and its continuous use contributes to soil quality in savannah soils of Piaui state.

Três complexos de PdII com tiossemicarbazonas N(4)-substituídas foram preparados: [Pd(aptsc)(PPh3)](NO3)•H2O, 1, [Pd(apmtsc)(PPh3)](NO3), 2, e [Pd(apptsc)(PPh3)](NO3)•H2O, 3, sendo PPh3 = trifenilfosfina; Haptsc = 2-acetilpyridina-tiossemicarbazona; Hapmtsc = 2-acetilpiridina-N(4)-metil-tiossemicarbazona e Happtsc = 2-acetilpiridina-N(4)-fenil-tiossemicarbazona. Os complexos foram caracterizados por análise elementar, IR, UV-Vis, ¹H e 31P{¹H} NMR e tiveram suas estruturas cristalinas determinadas por difratometria de raios X em monocristal. Os ligantes tiossemicarbazonatos monoaniônicos atuam de modo tridentado, ligando-se ao metal pelos átomos de nitrogênio piridínico, nitrogênio azometínico e enxofre. A atividade citotóxica frente à linhagem de células tumorais MDA-MB231 (tumor de mama) e a atividade anti-Mycobacterium tuberculosis H37Rv ATCC 27294 dos compostos foram investigadas. Os complexos de PdII mostraram-se altamente ativos contra as células tumorais, com valores de IC50 em torno de 5 µmol L-1, enquanto o agente antitumoral em uso clínico cisplatina mostrou-se inativo. Os compostos apresentaram atividade anti-M. tuberculosis significante, com valores de CIM comparáveis ou melhores que aqueles referentes a alguns fármacos usados clinicamente contra tuberculose.

Three PdII complexes were prepared from N(4)-substituted thiosemicarbazones: [Pd(aptsc)(PPh3)](NO3)•H2O, 1, [Pd(apmtsc)(PPh3)](NO3), 2, and [Pd(apptsc)(PPh3)](NO3)•H2O, 3, where PPh3 = triphenylphosphine; Haptsc = 2-acetylpyridine-thiosemicarbazone; Hapmtsc = 2-acetylpyridine-N(4)-methyl-thiosemicarbazone and Happtsc = 2-acetylpyridine-N(4)-phenyl-thiosemicarbazone. All complexes were characterized by elemental analysis, IR, UV-Vis, ¹H and 31P{¹H} NMR spectroscopies, and had their crystalline structures determined by X-ray diffractometry from single crystals. The monoanionic thiosemicarbazonate ligands act in a tridentate mode, binding to the metal through the pyridine nitrogen, the azomethine nitrogen and the sulfur atoms. The cytotoxic activity against the breast cancer cell line MDA-MB231 and the anti-Mycobacterium tuberculosis H37Rv ATCC 27294 activity were evaluated for the compounds. All PdII complexes were highly active against the studied cell line, presenting similar values of IC50, around 5 µmol L-1, while the clinically applied antitumor agent cisplatin was inactive. The compounds show remarkable anti-M. tuberculosis activities, presenting MIC values comparable or better than some commercial anti-M tuberculosis drugs.