HPLC separation,NMR and QTOF/MS/MS structure elucidation of a prominent nitric oxide donor agent based on an isomeric composition of a nitrosyl ruthenium complex

A new and promising nitrosyl ruthenium complex, [Ru(NO)(bdqi-COOH)(terpy)](PF₆)₃, bdqi-COOH is 3,4-diiminebenzoic acid and terpy is 2,2′-terpyridine, has been synthesized as a NO donor agent. The procedure used for [Ru(NO)(bdqi-COOH)(terpy)](PF₆)₃ synthesis has, apparently, yielded the formation of two isomers in which the ligand bdqi-COOH appears to be coordinated in its reduced form (bdcat-COOH), which could have differences in their pharmacological properties. Therefore, it was intended to separate the two possible isomers by high-performance liquid chromatography (HPLC) and to characterize them by high resolution mass spectrometry (QTOF MS) and by magnetic nuclear resonance spectroscopy (NMR). The results obtained by MS showed that the ESI-MS mass spectra of both HPLC column fractions, e.g. peak 1 and peak 2, are essentially equal, showing that both isomers display nearly identical gas-phase behavior with clusters of isotopologue ions centered at m/z 573, m/z 543 and m/z 513. Regarding the NMR analysis, the results showed that the positional isomerism is located in the bdqi-COOH ligand. From the observed results it can be concluded that the synthesis procedure that has been used results in the formation of two [Ru(terpy)(bdqi-COOH)NO](PF₆)₃ isomers.     

Factors associated with adiposity in normal weight female adolescents with adequate and high percent body fat: elaborating a risk model

Factors associated with adiposity in normal weight female adolescents with adequate and high percent body fat: elaborating a risk model. This study was carried out to evaluate the factors associated with adiposity in normal weight adolescents presenting appropriate or high percent body fat, who attended the public schools in Vi?osa county-Minas Gerais/Brazil. A total of 118 female adolescents at age range from 14 to 19 years and have already presented the menarche were evaluated. The adolescents were divided into 2 groups: G1 with high percent body fat and G2 with appropriate percent body fat. The following variables were evaluated: anthropometric, body composition, lifestyle and the family history of non-communicable chronic diseases. In subsample, the basal energy consumption was determined by indirect calorimetry. The G1-grouped adolescents showed higher values for most anthropometric and body composition variables (p < 0.001). No differences were observed (p > 0.05) for basal metabolism and metabolism of lean body mass, smoking habit, total energy consumption and protein and lipid as well between groups. When comparing the physical activity level, the G1 adolescents spent more time with 1-level sedentary activities whereas the G2 ones showed higher total caloric consumption with daily activities (p < 0.001). According to risk factors under analysis, the variables related to lifestyle, as distinguishing the use of sweeteners (OR = 13.47), provided higher contribution to excessive adiposity in the normal weight adolescents. The detailed analysis of the body composition as well as the risk factors associated with excessive body fat makes possible the early diagnosis and the development of more appropriate intervention means.     

Prolonged Activation of Brain CB2 Signaling Modulates Hypothalamic Microgliosis and Astrogliosis in High Fat Diet-Fed Mice

Low-grade inflammation of the hypothalamus is associated with the disturbance of energy balance. The endocannabinoid system has been implicated in the development and maintenance of obesity as well as in the control of immune responses. The type 2 cannabinoid receptor (CB2) signaling has been associated with anti-inflammatory effects. Therefore, in high fat diet (HFD)-induced obese mice, we modulated CB2 signaling and investigated its effects on energy homeostasis and hypothalamic microgliosis/astrogliosis. We observed no effect on caloric intake and body weight gain in control diet-fed animals that received prolonged icv infusion of the CB2 receptor agonist HU308. Interestingly, we observed a decrease in glucose tolerance in HFD-fed animals treated with HU308. Prolonged icv infusion of HU308 increases astrogliosis in the ventromedial nucleus (VMH) of obese animals and reduced HFD-induced microgliosis in the hypothalamic arcuate (ARC) but not in the paraventricular (PVN) or VMH nuclei. These data indicate that central CB2 signaling modulates glucose homeostasis and glial reactivity in obesogenic conditions, irrespective of changes in body weight.     

Synthesis and self‐assembly study of zwitterionic amphiphilic derivatives of chitosan

New zwitterionic derivatives of chitosan (CH) were synthesized through the Michael addition reaction of 1‐(3‐sulfopropyl)‐2‐vinylpyridine hydroxide (SPP) with primary amines of deacetylated CHs (with weight‐average molecular weights of 46 and 216 kDa) to obtain SPP‐substituted CHs. The hydrophilic derivatives were subsequently modified with 2.1, 4.6, and 9.7% of dodecyl groups [degree of substitution by dodecyl groups (DS_Dod)]. The SPP‐substituted CH derivatives were characterized by ¹H‐NMR, Fourier transform infrared spectroscopy, and gel permeation chromatography. Aqueous solutions of SPP‐substituted CH samples remained clear, independently of the pH (3.0 < pH < 12.0). The self‐association study of the amphiphilic derivatives was performed in aqueous buffered solution at pH 5.0 and 7.4, and the critical aggregation concentration values varied from 5.6 × 10^?3 to 0.02 g/L. The measurements of dynamic light scattering and ζ potentials showed that the self‐assembly behavior was dependent on the pH and DS_Dod. At pH 7.4, the measured ζ potentials were near zero, and colloidal stability was provided by the hydrated zwitterionic shell of the aggregates. Transmission electron microscopy revealed spherelike microsized particles of broad distribution. The amphiphilic SPP‐substituted CH samples were shown to be nontoxic with a 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide assay performed with HeLa cells. The remarkable water solubility and nontoxicity displayed by the new SPP‐substituted CH derivatives showed promising properties for the design of CH‐based biomaterials and nanoparticles. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44176.     

Innovative Cooking Techniques for Improving the Overall Quality of a Kailan-Hybrid Broccoli

The microbial, physical, sensory and nutritional quality of boiled (vacuum and conventional), steamed, pressure cooked, sous vide, microwaved (sous vide and conventional), deep-fried (vacuum and conventional) and grilled kailan-hybrid broccoli (Bimi®) after cooking was studied. Sous vide microwaving greatly decreased microbial counts, achieving very low psychrophilic and enterobacteria counts (1.1 and 0.2 log CFU g^?1, respectively). Vacuum boiling and sous vide reduced the stem broccoli firmness by approximately 54–58 %, reaching a pleasant and moderate softening. Sous vide, grilling and steaming induced the lowest stem colour changes. Generally, all cooking treatments showed a good overall sensory quality. The total phenolic content (1,148 mg CAE kg^?1 fw) usually increased after cooking, with microwave and grilled treatments registering the highest increases up to 2-fold. Commonly, the total antioxidant capacity (296.6 mg AAE kg^?1 fw) increased after cooking by sous vide, microwaving and frying treatments registering the highest increments, by approximately 3.6-fold. Generally, the cooking process reduced the initial vitamin C content, with vacuum and conventional boiling showing the lowest and highest losses with 27 and 62 %, respectively, while vacuum deep frying preserved the initial value (1,737 mg kg^?1 fw). As a main conclusion, the studied grilling and vacuum-based cooking treatments resulted in better microbial quality, colour, stem firmness and sensory quality than the remaining ones. This maintained or even improved the total antioxidant content of the new kailan-hybrid broccoli studied.