Rhodium‐Catalyzed Enantioselective Hydrogenation of (E)‐Enol Acetate Acids

The novel rhodium complex [Rh(S)‐Phanephos(cod)]‐catalyzed hydrogenation of disubstituted (E)‐enol acetate carboxylic acids is reported. The catalytic cycle works under 30 bar of hydrogen under conventional heating giving different 3‐acetoxy‐2,3‐disubstituted carboxylic acids with ee ≥90%. Hydrogenation occurred also under microwave dielectric heating without eroding the enantioselectivity but improving the overall efficiency of the process. With microwaves, hydrogen pressure and reaction time required for complete hydrogenation dropped to 5 bar and 30 min, respectively. The best performance of this catalyst under microwave irradiation was TON 100, TOF 196 h⁻¹ with ee 99% on a 6‐g scale.     

Amino acid composition of some Mexican foods

Knowledge of the amino acid composition of foods is essential to calculate their chemical score, which is used to predict protein quality of foods and diets. Though amino acid composition of many foods is reasonably well established, better knowledge is needed on native foods consumed in different regions and countries. This paper presents the amino acid composition of different presentations of raw and processed foods produced and consumed in Mexico. The amino acid composition was determined using Beckman amino acid analyzers (models 116 and 6300). Tryptophan was determined using the Spies and Chambers method. Of the different foods analyzed, some comments are made on native or basic foods in Mexico: Spirulin, where lysine is the limiting amino acid, with a chemical score of 67%, is a good source of tryptophan (1.16g/16 gN); amaranth contains high levels of sulphur amino acids (4.09 to 5.34 g/16gN), with a protein content of 15 g/100g; and pulque, a Pre-Hispanic beverage that contains high levels of tryptophan (2.58 g/16 gN) and sulphur amino acids (2.72 g/16 gN). Finally, insects are good sources of sulphur amino acids and lysine.     

New fluorinated poly(1,3,4-oxadiazole-ether-imide)s

New fluorinated poly(1,3,4-oxadiazole-ether-imide)s have been prepared by solution polycondensation reaction of different aromatic diamines having preformed 1,3,4-oxadiazole ring, such as 2,5-bis(p-aminophenyl)-1,3,4-oxadiazole, 2,5-bis[p-(4-aminophenoxy)phenyl]-1,3,4-oxadiazole, 2,5-bis[p-(3-aminophenoxy)phenyl]-1,3,4-oxadiazole, 2-(4-dimethylaminophenyl)-5-(3,5-diaminophenyl)-1,3,4-oxadiazole and 2-(4-fluorophenyl)-5-(3,5-diaminophenyl)-1,3,4-oxadiazole, with an aromatic dianhydride incorporating ether linkages and hexafluoroisopropylidene group, namely 1,1,1,3,3,3-hexafluoro-2,2-bis-[(3,4-dicarboxyphenoxy)phenyl]-propane dianhydride. The polymers were easily soluble in polar organic solvents, such as N-methylpyrrolidinone, N,N-dimethylformamide, and pyridine, as well as in certain low boiling-point organic solvents, such as tetrahydrofuran and chloroform. Very thin coatings deposited onto silicon wafers exhibited smooth, pinhole-free surface in atomic force microscopy. The polymers showed high thermal stability with decomposition temperature being above 410 °C. They exhibited a glass transition in the temperature range of 183-217 °C, with reasonable interval between glass transition and decomposition temperature. Solutions of some polymers in N,N-dimethylformamide exhibited blue fluorescence, having maximum emission wavelength in the range of 411-424 nm.     

Integration Concepts for the Fabrication of LTCC Structures

At the Keck Smart Materials Integration Laboratory at Penn State University, low-temperature co-fired ceramic (LTCC) material systems have been used to fabricate a number of devices for a variety of applications. This article presents an overview of the integration of the concepts and materials that we have used to achieve miniaturization and unique device function. Examples of microwave filters, metamaterial antennas, and a dielectrophoretic cell sorter will be presented, with emphasis on device modeling and design, prototype construction methods, and test results.     

Decreased benzo(a)pyrene concentration in rapeseed oil packed in polyethylene terephtalate

Commercially available rapeseed oil, the same oil additionally refined physically, and paraffin oil for comparison purposes were spiked with benzo(a)pyrene (BaP) at the level of 29.4, 34.3, and 50.4 µg kg^?1, respectively, filled into polyethylene terephtalate (PET) cylindrical‐shape receptacles, and the BaP concentrations were followed within 73 h by HPLC analysis. During this time, the BaP concentrations decreased to 22.9, 25.4, and 23.5 µg kg^?1 due to sorption of BaP onto PET. Using a modified kinetic equation, diffusion coefficients of BaP in all oils were calculated. The values of the diffusion coefficients and distribution coefficients indicated that other compounds present in the oils competed with BaP and affected the rate of BaP diffusion in the oils and the extent of adsorption onto PET. Moreover, the curves of BaP concentration vs. time, obtained experimentally, exhibited oscillations in BaP concentrations around the adsorption curves calculated by the kinetic equation. This was observed especially at the initial stages of the experiments, with the subsequent establishing of steady equilibrium BaP concentrations between liquid and solid phases at the end of the experiments, which does not correspond with known theory of adsorption.     

From Molecules to Behavior in Long-Term Inorganic Mercury Intoxication: Unraveling Proteomic Features in Cerebellar Neurodegeneration of Rats

Mercury is a severe environmental pollutant with neurotoxic effects, especially when exposed for long periods. Although there are several evidences regarding mercury toxicity, little is known about inorganic mercury (IHg) species and cerebellum, one of the main targets of mercury associated with the neurological symptomatology of mercurial poisoning. Besides that, the global proteomic profile assessment is a valuable tool to screen possible biomarkers and elucidate molecular targets of mercury neurotoxicity; however, the literature is still scarce. Thus, this study aimed to investigate the effects of long-term exposure to IHg in adult rats’ cerebellum and explore the modulation of the cerebellar proteome associated with biochemical and functional outcomes, providing evidence, in a translational perspective, of new mercury toxicity targets and possible biomarkers. Fifty-four adult rats were exposed to 0.375 mg/kg of HgCl₂ or distilled water for 45 days using intragastric gavage. Then, the motor functions were evaluated by rotarod and inclined plane. The cerebellum was collected to quantify mercury levels, to assess the antioxidant activity against peroxyl radicals (ACAPs), the lipid peroxidation (LPO), the proteomic profile, the cell death nature by cytotoxicity and apoptosis, and the Purkinje cells density. The IHg exposure increased mercury levels in the cerebellum, reducing ACAP and increasing LPO. The proteomic approach revealed a total 419 proteins with different statuses of regulation, associated with different biological processes, such as synaptic signaling, energy metabolism and nervous system development, e.g., all these molecular changes are associated with increased cytotoxicity and apoptosis, with a neurodegenerative pattern on Purkinje cells layer and poor motor coordination and balance. In conclusion, all these findings feature a neurodegenerative process triggered by IHg in the cerebellum that culminated into motor functions deficits, which are associated with several molecular features and may be related to the clinical outcomes of people exposed to the toxicant.     

AICAR Protects Vascular Endothelial Cells from Oxidative Injury Induced by the Long-Term Palmitate Excess

Hyperlipidemia manifested by high blood levels of free fatty acids (FFA) and lipoprotein triglycerides is critical for the progression of type 2 diabetes (T2D) and its cardiovascular complications via vascular endothelial dysfunction. However, attempts to assess high FFA effects in endothelial culture often result in early cell apoptosis that poorly recapitulates a much slower pace of vascular deterioration in vivo and does not provide for the longer-term studies of endothelial lipotoxicity in vitro. Here, we report that palmitate (PA), a typical FFA, does not impair, by itself, endothelial barrier and insulin signaling in human umbilical vein endothelial cells (HUVEC), but increases NO release, reactive oxygen species (ROS) generation, and protein labeling by malondialdehyde (MDA) hallmarking oxidative stress and increased lipid peroxidation. This PA-induced stress eventually resulted in the loss of cell viability coincident with loss of insulin signaling. Supplementation with 5-aminoimidazole-4-carboxamide-riboside (AICAR) increased endothelial AMP-activated protein kinase (AMPK) activity, supported insulin signaling, and prevented the PA-induced increases in NO, ROS, and MDA, thus allowing to maintain HUVEC viability and barrier, and providing the means to study the long-term effects of high FFA levels in endothelial cultures. An upgraded cell-based model reproduces FFA-induced insulin resistance by demonstrating decreased NO production by vascular endothelium.     

Inhibition of Neuronal Necroptosis Mediated by RIPK1 Provides Neuroprotective Effects on Hypoxia and Ischemia In Vitro and In Vivo

Ischemic brain injury is a widespread pathological condition, the main components of which are a deficiency of oxygen and energy substrates. In recent years, a number of new forms of cell death, including necroptosis, have been described. In necroptosis, a cascade of interactions between the kinases RIPK1 and RIPK3 and the MLKL protein leads to the formation of a specialized death complex called the necrosome, which triggers MLKL-mediated destruction of the cell membrane and necroptotic cell death. Necroptosis probably plays an important role in the development of ischemia/reperfusion injury and can be considered as a potential target for finding methods to correct the disruption of neural networks in ischemic damage. In the present study, we demonstrated that blockade of RIPK1 kinase by Necrostatin-1 preserved the viability of cells in primary hippocampal cultures in an in vitro model of glucose deprivation. The effect of RIPK1 blockade on the bioelectrical and metabolic calcium activity of neuron-glial networks in vitro using calcium imaging and multi-electrode arrays was assessed for the first time. RIPK1 blockade was shown to partially preserve both calcium and bioelectric activity of neuron-glial networks under ischemic factors. However, it should be noted that RIPK1 blockade does not preserve the network parameters of the collective calcium dynamics of neuron-glial networks, despite the maintenance of network bioelectrical activity (the number of bursts and the number of spikes in the bursts). To confirm the data obtained in vitro, we studied the effect of RIPK1 blockade on the resistance of small laboratory animals to in vivo modeling of hypoxia and cerebral ischemia. The use of Necrostatin-1 increases the survival rate of C57BL mice in modeling both acute hypobaric hypoxia and ischemic brain damage.     

Osteonecrosis of the Jaws in Patients with Hereditary Thrombophilia/Hypofibrinolysis—From Pathophysiology to Therapeutic Implications

Osteonecrosis of the jaws (ONJ) usually has a clear etiology. Local infection or trauma, radiotherapy and drugs that disrupt the vascular supply or bone turnover in the jaws are its major contributors. The thrombotic occlusion of the bone’s venous outflow that occurs in individuals with hereditary thrombophilia and/or hypofibrinolysis has a less known impact on jaw health and healing capability. Our research provides the most comprehensive, up-to-date and systematized information on the prevalence and significance of hereditary thrombophilia and/or hypofibrinolysis states in ONJ. We found that hereditary prothrombotic abnormalities are common in patients with ONJ refractory to conventional medical and dental treatments. Thrombophilia traits usually coexist with hypofibrinolysis traits. We also found that frequently acquired prothrombotic abnormalities coexist with hereditary ones and enhance their negative effect on the bone. Therefore, we recommend a personalized therapeutic approach that addresses, in particular, the modifiable risk factors of ONJ. Patients will have clear benefits, as they will be relieved of persistent pain and repeated dental procedures.