Vanadium diaminebis(phenolate) complexes of the general formulas [LVCl(THF)] (L = Me(2)NCH(2)CH(R)N(CH(2)-2-O-3,5-C(6)H(2)(t)Bu(2))(2), where R = H, Me) and [LV(O)X] [X = Cl; R = H (2), Me (3), O(i)Pr (4), (mu-O)V(O)L (5)] are described. All compounds display octahedral geometry and trans-O(Ph) coordination. For compounds 2, 3, and 5, only one isomer, presenting the V=O ligand trans to the tripodal nitrogen, was formed, while for 4, two isomers were observed by NMR in solution. The UV-vis and circular dichroism spectra of 2 and 3 display very intense charge-transfer transition bands from the phenolate donors to the vanadium, which are in agreement with the (51)V low-field shifts observed. All vanadium(V) complexes were tested as thioanisole sulfoxidation catalysts, revealing very high selectivity when H(2)O(2) was used as the oxidant. However, no enantioselectivity was observed even when enantiopure 3 was used as the catalyst precursor. (1)H and (51)V NMR studies were conducted for the reactions of 2 with aqueous solutions of H(2)O(2) in methanol-d(4) and in acetonitrile-d(3); 2 reacts with the solvents, leading to [LV(O)OMe], by replacement of Cl by MeO in methanol, and to a new vanadium aminebis(phenolate) complex, where the dimethylamine fragment of the original ligand L was replaced by CH(3)CN. In either case, (51)V NMR spectra suggest the formation of peroxovanadium species upon the addition of a H(2)O(2) solution. The subsequent addition of thioanisole to the methanol-d(4) solution leads to regeneration of the original complex.

An important factor in consumers’ acceptability, beyond visual appearance and taste, is food texture. The elderly and people with dysphagia are more likely to present malnourishment due to visually and texturally unappealing food. Three-dimensional Printing is an additive manufacturing technology that can aid the food industry in developing novel and more complex food products and has the potential to produce tailored foods for specific needs. As a technology that builds food products layer by layer, 3D Printing can present a new methodology to design realistic food textures by the precise placement of texturing elements in the food, printing of multi-material products, and design of complex internal structures. This paper intends to review the existing work on 3D food printing and discuss the recent developments concerning food texture design. Advantages and limitations of 3D Printing in the food industry, the material-based printability and model-based texture, and the future trends in 3D Printing, including numerical simulations, incorporation of cooking technology to the printing, and 4D modifications are discussed. Key challenges for the mainstream adoption of 3D Printing are also elaborated on.

Fish is a very perishable food and therefore several storage strategies need to be employed to increase its shelf-life, guaranteeing its safety and quality from catch to consumption. Despite the advances in modern fish storage technologies, chilling and freezing are still the most common preservation methods used onboard. The present review aims to summarize strategies to increase the shelf-life of fresh (chilled) and frozen fish, as whole, gutted, or fillet, involving the assessment of different traditional cooling and freezing conditions of different fish species caught in different locations. Although there are other factors that influence the fish shelf-life, such as the fish species and the stress suffered during catch, storage time and temperature and the amount of ice are some of the most important. In addition, the way that fish is stored (whole, fillet, or gutted) also contributes to the final quality of the product. In most studies, whole chilled and frozen fish present longer shelf-life than those preserved as gutted and filleted. However, it should be noted that other factors related to the organism, capture method, and transport to the preparation/processing industry should be considered for shelf-life extension.

Type 2 Diabetes Mellitus (T2DM) is a chronic disease which corresponds to 90% of the worldwide cases of diabetes, mainly due to epigenetic factors such as unhealthy lifestyles. First line therapeutic approaches are based on lifestyle changes, most of the time complemented with medication mostly associated with several side effects and high costs. As a result, the scientific community is constantly working for the discovery and development of natural therapeutic strategies that provide lower financial impact and minimize side effects. This review focus on these nature-based therapeutic strategies for prevention and control of T2DM, with a special emphasis on natural compounds that present pharmacological activity as dipeptidyl peptidase-4 (DPP4), alpha-amylase, alpha-glucosidase, lipase, and protein tyrosine phosphatase 1B (PTP1B) inhibitors.

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Reactions of titanium and yttrium trichlorides with 1 equiv of the sodium or potassium salts of the diamine bis(phenolate) H2 tBu2O2NN′ (Me2NCH2CH2-(CH2-2-HO-3,5-C6H2 tBu2)2) led to formation of [TiCl(tBu2O2NN′)(L)] (L = THF, 1; py, 2) and [YCl(tBu2O2NN′)(DME)], 3. Reactions of 1 or 3 with MCH2-(2-NMe2)C6H4 and with M[2-(CH2NMe2)C6H4] (M = Li, K) led to [Ti(tBu2O2NN′)(κ2-(CH2C6H4NMe2))], 5, [Y(tBu2O2NN′)(κ2-(CH2C6H4NMe2))], 6, and [Y(tBu2O2NN′)(κ2-(C6H4CH2NMe2))], 7. [Y(tBu2O2NN′)N(SiMe3)2], 4, was obtained from 3 and KN(SiMe3)2, whereas [(Y(tBu2O2NN′)(CH2SiMe3))2(μ4-O)(μ3-Li)2], 8, formed from reaction of 3 and LiCH2SiMe3. The reaction of 7 with 1 equiv of CH3CN gave [Y(tBu2O2NN′)(NC(CH3)C6H4CH2NMe2)], 10, which displays a chelating ketimide ligand formed by nitrile insertion in the Y−Ph bond. Further reaction with CH3CN led to [Y(tBu2O2NN′)(κ2-(N(H)C(CH3)C(H)C(C6H4CH2NMe2)N(H)], 9, the formation of which involves an imine−enamine tautomerism followed by a second nitrile insertion and 1,3-hydrogen shift. The reaction of 1 with CH3CN gave [TiCl(tBu2O2NN′)(NCCH3)], which upon heating converts to a new paramagnetic species that is likely a chloride-bridged Ti(III) dimer. The EPR study performed reveals that bis(phenolate) Ti(III) complexes do not promote nitrile coupling reactions by electron transfer. The solid state molecular structures of 1−9 revealed that in all the complexes the bis(phenolate) ligand is coordinated to the metal center by the two oxygen atoms and the two nitrogen atoms with trans phenolate arrangement.

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