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Although nowadays there is a renewed and growing interest in Mn-based contrast agents, there are only few studies dealing with Mn-based lipophilic nanoparticles and how they may be optimized as MRI contrast agents. Three amphiphilic paramagnetic Mn(II) complexes based on derivatives of EDTA and 1,4-DO2A were used for the preparation of lipidic nanoparticles. The length and position of the aliphatic chains were found to control whether either vesicular liposomes, nonvesicular bicelles, or a mixture of both was produced as well as the size and morphology of phospholipid-based self-assembling nanoaggregates. These differences determine whether hydrophilic Gd-based contrast agents or fluorescent dyes can be entrapped in the aqueous core of the nanoaggregate. Structural characterization was performed by cryo-TEM. Detailed 1H NMR relaxometric analyses were carried out on all systems. The effect of entrapping gadoteridol in the aqueous core (where present) was studied by preparing diamagnetic amphiphilic Zn(II) analogues. In the case of homogeneous systems, the data were also fitted to obtain the relaxometric parameters for comparison with literature data. The results of these studies demonstrate enhanced relaxivity of the nanoaggregates with respect to monomeric analogues. This work allowed us to understand how to control the formation of different types of nanovesicles (liposomes, bicelles, and micelles), optimize their MRI contrast, and provide different in vivo biodistribution characteristics.

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INTRODUCTION: Mass insect rearing is becoming increasingly pursued by food and feed industry due to its high sustainability and low environmental impact. Yellow mealworm larvae (Tenebrio molitor) are conventionally reared on wheat bran (WB), but alternative substrates, such as several by-products of the agri-food industry, have shown good prospects for insect rearing. OBJECTIVES: The objective of this study was to investigate on the metabolic and nutritional response of yellow mealworm larvae to dried brewer's spent grains (BSG) and WB used as rearing substrates. METHODS: Proximate, fibre and fatty acid compositions of durum WB and dried BSG were first characterized. Mealworm larvae were fed either WB (WB-L) or BSG (BSG-L) in a trial reproducing a scale rearing condition. Feed efficiency parameters together with proximate and FA composition were determined. Metabolic pathways affected by the dietary treatments were evaluated by means of a targeted metabolomics approach. Proton nuclear magnetic resonance (1H NMR) spectra were acquired on lipid and polar extracts of WB-L and BSG-L and then coupled to multivariate data analysis. Absolute quantitative 1H NMR data were carried out on selected metabolites. RESULTS: BSG-L exhibited better feed conversion ratio and efficiency in conversion of ingested food (P < 0.05) and almost half fat content (P < 0.001) than WB-L. BSG-L also showed higher ω-3 and ω-6 poliunsaturated fatty acids (P < 0.001) and lower content of monounsaturated fatty acids (P < 0.001) than WB-L. BSG-L mobilized body fat towards methylamine accumulation and led to enhanced trehalose catabolism. CONCLUSIONS: Our findings are useful to gain knowledge on the metabolic features that finally affect growth and body composition in reared yellow mealworm larvae.

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PURPOSE: To describe and quantify the different relaxation mechanisms operating in suspensions of liposomes that encapsulate paramagnetic lanthanide(III) complexes. THEORY AND METHODS: The transverse relaxation rate of lanthanide-loaded liposomes receives contribution from the exchange between intraliposomal and bulk water protons, and from magnetic susceptibility effects. Phospholipids vesicles encapsulating different Ln(III)-HPDO3A complexes (Ln = Eu, Gd, or Dy) were prepared using the conventional thin film rehydration method. Relaxation times (T1 , T2 , and T2*) were measured at 14 Tesla (T) and 25 °C. The effect of compartmentalization of the paramagnetic agent inside the liposomal cavity was evaluated by means of an IRON-modified MRI sequence. RESULTS: NMR measurements demonstrated that Curie spin relaxation is the dominant contribution (> 90%) to the observed transverse relaxation rate of paramagnetic liposomes. This was further confirmed by MRI that showed the ability of the liposome entrapped lanthanide complexes to generate IRON-MRI positive contrast in a size dependent manner. CONCLUSION: The Curie spin relaxation mechanism is by far the principal mechanism involved in the T2 shortening of the water protons in suspension of paramagnetic liposomes at 14T. The access to IRON contrast extends the potential of such nanosystems as MRI contrast agents.

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A new class of nanovesicles formed by the self-assembly of amphiphilic Janus dendrimers, dendrimersomes, loaded with hydrophilic or amphiphilic magnetic resonance imaging chelates shows promising properties as a novel, efficient and versatile nanoplatform for biomedical imaging.

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In this work, a quantitative characterisation of lipid (both triglycerides and phospholipids) rearrangements in the muscle of offshore-raised gilthead sea bream was carried out as a function of fish growth between April and September. Relative percentages of lipid classes and fatty acids/acyls composition of the commercial feeds and fish dorsal muscles were assessed by means of an interdisciplinary analytical approach. A combination of preparative chemistry and experimental results from NMR spectroscopy, GC, 3D-TLC as well as proximate analysis permitted the observed growth parameters in key metabolic events to be linked with fish fattening and lipid turnover. While defined effects of feed composition on fatty acid profiles of fillets were ascertained, the relative increase of fatty acyls in triglycerides and phospholipids were also estimated enabling detailed evaluation of TAG:PL ratio in adult offshore-farmed gilthead sea bream. NMR was also used to quantify PUFA regiospecific distribution in TAG and PL.

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The goal of this work was to study via NMR the unaltered metabolic profile of Sardinian Vermentino grape berry. Seven selections of Vermentino were harvested from the same vineyard. Berries were stored and extracted following an unbiased extraction protocol. Extracts were analyzed to investigate variability in metabolites concentration as a function of the clone, the position of berries in the bunch or growing area within the vineyard. Quantitative NMR and statistical analysis (PCA, correlation analysis, Anova) of the experimental data point out that, among the investigated sources of variation, the position of the berries within the bunch mainly influences the metabolic profile of berries, while the metabolic profile does not seem to be significantly influenced by growing area and clone. Significant variability of the amino acids such as arginine, proline, and organic acids (malic and citric) characterizes the rapid rearrangements of the metabolic profile in response to environmental stimuli. Finally, an application is described on the analysis of metabolite variation throughout the physiological development of berries.

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