Nitric oxide releasing metal-diazeniumdiolate complexes strongly induce vasorelaxation and endothelial cell proliferation

The preparation, characterization, and NO-releasing properties of metal complexes derived from N-aminoethylpiperazine-N-diazeniumdiolate (HPipNONO), [Cu(PipNONO)Cl] and [Ni(PipNONO)Cl], and the Ni(II) complex derived from the Schiff base between HPipNONO and salicylaldehyde, [Ni(SalPipNONO)], are described. Compounds [Cu(PipNONO)Cl] and [Ni(SalPipNONO)] release NO at a much slower rate than HPipNONO in aqueous buffer in the pH range between 6.8 and 8.0. The kinetics of NO release by [Ni(SalPipNONO)] is complex, with an apparent stepwise release of NO molecules. Both [Cu(PipNONO)Cl] and [Ni(SalPipNONO)] are effective vasorelaxant agents of precontracted rabbit aorta rings, and are active in the nM concentration range. In addition, these complexes promote the proliferation of endothelial cells. Both vascular activities were inhibited by a specific inhibitor of guanylate cyclase, suggesting the involvement of the cGMP pathway. In all biological assays, the reference agent sodium nitroprusside was shown to be 10-1000-fold less potent than the two metal-NONOates.     

Oxidative Alkoxycarbonylation of Alkynes by Means of Aryl α‐Diimine Palladium(II) Complexes as Catalysts

The straightforward in situ synthesized bis(2,6‐diisopropyl)acenaphthenequinonediimine palladium triflate catalyst was generally employed for both the mono‐alkoxycarbonylation of terminal alkynes, and the bis‐alkoxycarbonylation of 1,2‐disubstituted alkynes by using mild reaction conditions [carbon monoxide pressure (P_CO)=4 bar, temperature=20 °C]. Utilizing low catalyst loading (down to 0.5 mol%), a variety of propiolic esters were synthesized with good to excellent isolated yields. Most importantly the system was very efficient not only with methanol but also with a range of different alcohols, starting from the less hindered benzyl alcohol to the most hindered ones, such as isopropyl alcohol and tert‐butyl alcohol. In addition, aromatic and aliphatic 1,2‐disubstituted alkynes were converted into maleic acid derivatives, together with an acid‐catalyzed isomerization reaction, showing modest to good selectivity and excellent combined yields. In particular 3‐hexyne showed a satisfactory degree of selectivity for the maleic diesters of methanol and benzyl alcohol, obtaining the corresponding products with good isolated yields.

     

Taxonomic structure of the yeasts and lactic acid bacteria microbiota of pineapple (Ananas comosus L. Merr.) and use of autochthonous starters for minimally processing

Pichia guilliermondii was the only identified yeast in pineapple fruits. Lactobacillus plantarum and Lactobacillus rossiae were the main identified species of lactic acid bacteria. Typing of lactic acid bacteria differentiated isolates depending on the layers. L. plantarum 1OR12 and L. rossiae 2MR10 were selected within the lactic acid bacteria isolates based on the kinetics of growth and acidification. Five technological options, including minimal processing, were considered for pineapple: heating at 72 °C for 15 s (HP); spontaneous fermentation without (FP) or followed by heating (FHP), and fermentation by selected autochthonous L. plantarum 1OR12 and L. rossiae 2MR10 without (SP) or preceded by heating (HSP). After 30 days of storage at 4 °C, HSP and SP had a number of lactic acid bacteria 1000 to 1,000,000 times higher than the other processed pineapples. The number of yeasts was the lowest in HSP and SP. The Community Level Catabolic Profiles of processed pineapples indirectly confirmed the capacity of autochthonous starters to dominate during fermentation. HSP and SP also showed the highest antioxidant activity and firmness, the better preservation of the natural colours and were preferred for odour and overall acceptability.     

Invited review: Dairy proteins and bioactive peptides: Modeling digestion and the intestinal barrier

Dairy products are one of the most important sources of biologically active proteins and peptides. The health-promoting functions of these peptides are related to their primary structure, which depends on the parent protein composition. A crucial issue in this field is the demonstration of a cause-effect relationship from the ingested protein form to the bioactive form in vivo. Intervention studies represent the gold standard in nutritional research; however, attention has increasingly been focused on the development of sophisticated in vitro models of digestion to elucidate the mechanism of action of dairy nutrients in a mechanistic way and significantly reduce the number of in vivo trials. On the other hand, the epithelial intestinal barrier is the first gate that actively interacts with digestion metabolites, making the intestinal cells the first target tissue of dairy nutrients and respective metabolites. An evolution of the in vitro digestion approach in the study of dairy proteins and derived bioactive compounds is the setup of combined in vitro digestion and cell culture models taking into consideration the endpoint to measure the target organism (e.g., animal, human) and the key concepts of bioaccessibility, bioavailability, and bioactivity. This review discusses the relevance and challenges of modeling digestion and the intestinal barrier, focusing on the implications for the modeling of dairy protein digestion for bioactivity evaluation.     

Cascade Reactions: Sequential Homobimetallic Catalysis Leading to Benzofurans and β,γ‐Unsaturated Esters

The concatenation between a Pd(0)‐promoted deallylation catalytic cycle and a Pd(II)‐promoted heterocyclization catalytic cycle (an example of what we have named “sequential homobimetallic catalysis”) has been shown to occur starting from 1‐(2‐allyloxyphenyl)‐2‐yn‐1‐ols 1 to afford 2‐benzofuran‐2‐ylacetic esters 2 and β,γ‐unsaturated esters in high yields under carbonylative conditions. In view of the conceptual as well as the synthetic importance of the process, the mechanistic aspects and the synthetic scope of the reaction have been investigated in detail. All the experimental evidence is in agreement with the sequential homobimetallic mechanism, and the reaction has proven to be of general synthetic applicability.     

Effects of flour storage and heat generated during milling on starch,dietary fibre and polyphenols in stoneground flours from two durum‐type wheats

In the perspective of cereal‐based functional food development, the research compared stone watermill and stone mill which differed in the heating generated during grinding (30 and 60 °C) and the effects of storage on the preservation of phytochemicals. After 6‐month storage of flour, a decrease in soluble dietary fibre (loss of 1.9–2.5 g 100 g^?1) and bound polyphenols (loss of 6.2–8.5%) was observed, while other wheat grain components remained unvaried. Comparing the milling techniques, stoneground wheat grains (60 °C) showed the highest amylose (34.7–36.9% of total starch) and resistant starch amounts (0.85–1.16% of total starch), which could be of interest for lowering Glycaemic Index. Stoneground KAMUT^® starch had higher tendency to be converted into resistant starch and it also showed the higher degree of starch damage, as compared to the durum wheat variety Claudio. The study provided suggestions for modulating the production chain with the aim of supplying added value to wheat‐based products.     

Reliability and accuracy of embedded fiber Bragg grating sensors for strain monitoring in advanced composite structures

This work investigated issues for an efficient and reliable embedding and use of Fiber Bragg Grating (FBG) sensors for strain monitoring of composite structures with particular regard to the manufacturing process of components in the nautical field by means of the vacuum bag technique in autoclave. CFRP material laminates with embedded FBGs were produced and the effect of the curing process parameters on the light transmission characteristics of the optical fibers was initially investigated. Two different types of coating, namely polyimide and acrylate, were tested by measuring the light attenuation by an Optical Time Domain Reflectometer. Tensile specimens were subsequently extracted from the laminas and instrumented also with a surface-mounted conventional electrical strain gage (SG). Comparison between the FBG and SG measurements during static tensile tests allowed the evaluation of the strain monitoring capability of the FBGs, in particular of their sensitivity (i.e., gage factor) when embedded.     

In Vitro and In Vivo Effects of the Urokinase Plasminogen Activator Inhibitor WX-340 on Anaplastic Thyroid Cancer Cell Lines

Increased expression of the urokinase-type plasminogen activator (uPA) system is associated with tumor invasion, neo-angiogenesis, and metastatic spread, and has been shown to positively correlate with a poor prognosis in several cancer types, including thyroid carcinomas. In recent years, several uPA inhibitors were found to have anticancer effects in preclinical studies and in some phase II clinical trials, which prompted us to evaluate uPA as a potential therapeutic target for the treatment of patients affected by the most aggressive form of thyroid cancer, the anaplastic thyroid carcinoma (ATC). In this study, we evaluated the in vitro and in vivo effects of WX-340, a highly specific and selective uPA inhibitor, on two ATC-derived cell lines, CAL-62 and BHT-101. The results obtained indicated that WX-340 was able to reduce cell adhesion and invasiveness in a dose-dependent manner in both cell lines. In addition, WX-340 increased uPA receptor (uPAR) protein levels without affecting its plasma membrane concentration. However, this compound was unable to significantly reduce ATC growth in a xenograft model, indicating that uPA inhibition alone may not have the expected therapeutic effects.     

Investigation of the Effects of Virgin Olive Oil Cleaning Systems on the Secoiridoid Aglycone Content Using High Performance Liquid Chromatography–Mass Spectrometry

Phenolic compounds are useful markers to control olive oil technological processes, including the virgin olive oil (VOO)/water separation after olive oil extraction. In this investigation, VOO extracted from olives of cv. Coratina using a mild oil/water separator called the hydrocyclone sedimentation system (Hydroil) was compared with VOO obtained using a conventional vertical centrifuge separator (Cenoil), which is mostly used in the modern olive oil industry. Secoiridoid aglycones were selected, among phenolic compounds, as markers and analyzed using reversed‐phase liquid chromatography coupled to linear quadrupole ion‐trap mass spectrometry with electrospray ionization in the negative mode. VOO samples obtained using the Hydroil system were found to contain significantly higher levels of secoiridoid aglycones, compared to the Cenoyl‐type samples. In particular, the total content of the aglycones of decarboxymethyl oleuropein, decarboxymethyl ligstroside, ligstroside, and oleuropein, expressed in terms of oleuropein, was estimated as 35.40 ± 0.80 mg kg^?1, compared to 8.06 ± 0.41 mg kg^?1 in the Cenoil samples (n = 3). Since no significant difference in residual water (P < 0.05) was found between the two types of VOO samples, the higher amount of secoiridoids obtained for Hydroil‐type ones was explained by the lower extent of oxidation occurring during the mild oil/water separation achieved using the Hydroil system.