Amine-Rich Carbon Dots as Novel Nano-Aminocatalytic Platforms in Organic Synthesis

The development of novel and effective metal-free catalytic systems, which can drive value-added organic transformations in environmentally benign solvents (for instance, water), is highly desirable. Moreover, these new catalysts need to be harmless, easy-to-prepare, and potentially recyclable. In this context, amine-rich carbon dots (CDs) have recently emerged as promising nano-catalytic platforms. These nitrogen-doped nanoparticles, which show dimensions smaller than 10 nm, generally consist of carbon cores that are surrounded by shells containing numerous amino groups. In recent years, organic chemists have used these surface amines to guide the design of several synthetic methodologies under mild operative conditions. This Concept highlights the recent advances in the synthesis of amine-rich carbon dots and their applications in organic catalysis, including forward-looking opportunities within this research field

Advanced magnetic resonance imaging of cortical laminar necrosis in patients with stroke

Purpose: The aim of this study was to assess the novel advanced magnetic resonance imaging findings of acute stage cortical laminar necrosis developing after complicated cardiovascular or abdominal surgery. Materials and methods: This institutional review board-approved study included patients with postoperative stroke due to cortical laminar necrosis imaged with magnetic resonance in the acute stage. Brain magnetic resonance imaging examinations were obtained on a 3T magnetic resonance scanner within 48 hours of the neurological symptoms, including diffusion-weighted images (b value, 1000 s/mm2) and arterial spin labelling using a pseudo-continuous arterial spin labelling method in four patients. Conventional and advanced magnetic resonance images were analysed to assess the imaging features in acute stage cortical laminar necrosis. Results: The final population consisted of 14 patients (seven men and seven women, mean age 61 years, range 32–79 years) diagnosed with stroke and acute phase cortical laminar necrosis. All the patients presented with cortical lesions showing restricted diffusion on diffusion-weighted images and hypointensity on the apparent diffusion coefficient map. Cortical hyperintensity on T2-weighted or fluid-attenuated inversion recovery images was found in three (21%) and six (43%) patients, respectively. Reduced perfusion was noted in three out of four patients imaged with arterial spin labelling, while in one case no corresponding perfusion abnormality was noted on the arterial spin labelling maps. Arterial spin labelling abnormalities were much more extensive than diffusion restriction in two patients, and they were associated with a poor outcome. Conclusion: Cortical hyperintense abnormalities on diffusion-weighted imaging may be the only sign of developing cortical laminar necrosis injury. The acquisition of arterial spin labelling helps to identify perfusion alterations and the extension of the ischaemic injury

Proteomic and immunological characterization of a new food allergen from hazelnut (Corylus avellana).

Hazelnuts (Corylus avellana) are one of the most common sources of life-long IgE-mediated food allergies. In this study, we investigated the IgE-reactivity pattern of children with hazelnut allergy (N=15) from Regione Campania, located in Southern Italy, and addressed proteomic strategies for characterizing IgE-binding proteins. For all of the patients (15/15), the predominant IgE-reactive component was a minor ~55kDa protein not previously described. Similar to the hazelnut 11S globulin Cor a 9 allergen, the immunoreactive protein consisted of two subunits linked via a disulfide bridge. In contrast to Cor a 9, only the 20.7kDa alkaline subunit exhibited IgE-affinity. The immunogenic subunit was purified by a two-step chromatographic procedure, but peptide mass fingerprinting was unsuccessful in identifying it, due to the incompleteness of the annotated hazelnut genome. Several tryptic peptides were de novo sequenced by tandem mass spectrometry and showed a high degree of homology with the 11S globulin storage proteins from other seeds, some of which have already been reported as food allergens. The structural characterization suggests that the new putative allergen is a divergent isoform of the hazelnut 11S globulin. These results provide a new platform for developing innovative diagnostic and therapeutic intervention plans. BIOLOGICAL SIGNIFICANCE:Over the years, at least five proteins have been reported as potential food hazelnut allergens. The predominance of specific allergens appears to be strictly related to the geographical origin of the allergic subjects. The complex patterns of the IgE-reactivity of hazelnut storage proteins result in a poor diagnostic and prognostic accuracy. In the perspective of a component-resolved "molecular approach" to the hazelnut allergy we investigated the immune-reactivity patterns to hazelnuts of 15 patients (14 in the pediatric age range) from Region Campania, located in Southern Italy. For all the patients the predominant IgE-reactive component was a minor ~55kDa protein not previously annotated in either protein or genomic databases. The putative allergen was isolated, partially characterized by MS/MS de novo sequencing and appears to be an isoallergen of the hazelnut 11S globulin Cor a 9. Like this latter, the immunoreactive protein consisted of two subunits linked via a disulfide. In contrast to Cor a 9, only the 20.7kDa alkaline subunit exhibited IgE-affinity, in analogy to 11S allergens from other seeds (pistachio, cashew, soybean). We believe that the application of combined immunochemical and proteomic strategies to characterize the new food allergen could be of interest for the readers of Journal of Proteomics. In addition, the results of this study have functional worth in providing a new platform to plan innovative diagnostic and therapeutic intervention approaches to treat hazelnut allergy

Resting-State Functional Connectome in Patients with Brain Tumors Before and After Surgical Resection

Purpose: High-grade glioma surgery has evolved around the principal belief that a safe maximal tumor resection improves symptoms, quality of life, and survival. Mapping brain function has been recently improved by resting-state functional magnetic resonance imaging (rest-fMRI), a novel imaging technique that explores networks connectivity at “rest.” Methods: This prospective study analyzed 10 patients with high-grade glioma in whom rest-fMRI connectivity was assessed both in single-subject and in group analysis before and after surgery. Seed-based functional connectivity analysis was performed with CONN toolbox. Network identification focused on 8 major functional connectivity networks. A voxel-wise region of interest (ROI) to ROI correlation map to assess functional connectivity throughout the whole brain was computed from a priori seeds ROI in specific resting-state networks before and after surgical resection in each patient. Results: Reliable topography of all 8 resting-state networks was successfully identified in each participant before surgical resection. Single-subject functional connectivity analysis showed functional disconnection for dorsal attention and salience networks, whereas the language network demonstrated functional connection either in the case of left temporal glioblastoma. Functional connectivity in group analysis showed wide variations of functional connectivity in the default mode, salience, and sensorimotor networks. However, salience and language networks, salience and default mode networks, and salience and sensorimotor networks showed a significant correlation (P uncorrected <0.0025; P false discovery rate <0.077) in comparison before and after surgery confirming non-disconnection of these networks. Conclusions: Resting-state fMRI can reliably detect common functional connectivity networks in patients with glioma and has the potential to anticipate network alterations after surgical resection

Comparative analysis of eliciting capacity of raw and roasted peanuts: the role of gastrointestinal digestion

This study investigated the simultaneous impact of food matrix and processing on the food allergy eliciting capacity of peanuts in a physiologically relevant context. Whole raw and roasted peanuts were subjected to in vitro digestion combining the harmonized oral-gastric-duodenal digestion models with brush border membrane enzymes (BBM) to simulate the jejunal degradation of peptides. SDS-PAGE and HPLC analysis showed that roasting increased digestibility of peanuts and this trend was even more evident after BBM degradation. The eliciting properties of raw and roasted peanuts were assessed by Rat Basophil Leukemia assay in the presence of sera from peanut-allergic patients. As general features, the BBM digestion reduced allergenicity of roasted peanuts compared to the raw counterpart, suggesting that intestinal peptidases effectively contribute to further destroy specific domains of peanut allergens. These findings provide new and more realistic insights in the stability of peanut allergens within their natural matrix

Proteomic study of muscle sarcoplasmic proteins using AUT-PAGE/SDS-PAGE as two-dimensional gel electrophoresis

The conversion of muscle to meat in pig involves mainly proteolysis of myofibrillar proteins, which undergo notable changes since early stage of rigor mortis, even after 48 h post mortem. The tenderness of meat has been thoroughly investigated to understand the biochemical mechanisms, which influence texture and flavour development as well as the technological parameters and hence meat quality. Cytoplasmic proteolytic calcium dependent enzymes, named -and m-calpains, which act in the early stages of rigor mortis, significantly contribute to tenderization weakening myofibrils. These enzymes, however, act for fewdays because they are specifically inhibited by calpastatin and by pH lowering. However, when pH falls to about 5.0, proteolytic activity on muscle proteins is continued by longer acting lysosomal proteinase, cathepsins [3,7–9]. Post mortem proteolysis also causes relevant changes in sarcoplamic protein fraction, which represent the water soluble fraction (quantitatively about 30–35%) of meat total protein, and the involved proteins has already been identified by proteomic-based studies. Recent investigations have demonstrated that the most commonly found Lactobacillus species in dry fermented meats are able to hydrolyse myofibrillar and sarcoplasmic muscle proteins in vitro.The most abundant sarcoplasmic proteins, as mixture of basic polypeptides with a narrow spread range of molecular masses, represented an excellent model to test our analytical technique and to delineate its capabilities. In the present study, we compared 2D AUT-PAGE/SDSPAGE maps of water-soluble proteins extracted from fresh meat and from dry-cured ham, a non fermented product, from “Naples-type” salami, a microbiologically fermented product, and from “Coppa”, a typical semi-fermented product. Electrophoretically separated proteins have been identified by MALDI-ToF mass fingerprinting

Photodynamic therapy of cutaneous T-cell lymphoma cell lines mediated by 5-aminolevulinic acid and derivatives

The delta-amino acid 5-aminolevulinic acid (ALA), is the precursor of the endogenous photosensitiser Protoporphyrin IX (PpIX), and is currently approved for Photodynamic Therapy (PDT) of certain superficial cancers. However, ALA-PDT is not very effective in diseases in which T-cells play a significant role. Cutaneous T-cell lymphomas (CTCL) is a group of non-Hodgkin malignant diseases, which includes mycosis fungoides (MF) and Sézary syndrome (SS). In previous work, we have designed new ALA esters synthesised by three-component Passerini reactions, and some of them showed higher performance as compared to ALA. This work aimed to determine the efficacy as pro-photosensitisers of five new ALA esters of 2-hydroxy-N-arylacetamides (1f, 1 g, 1 h, 1i and 1 k) of higher lipophilicity than ALA in Myla cells of MF and HuT-78 cells of SS. We have also tested its effectiveness against ALA and the already marketed ALA methyl ester (Me-ALA) and ALA hexyl ester (He-ALA). Both cell Myla and SS cells were effectively and equally photoinactivated by ALA-PDT. Besides, the concentration of ALA required to induce half the maximal porphyrin synthesis was 209 μM for Myla and 169 μM for HuT-78 cells. As a criterion of efficacy, we calculated the concentration of the ALA derivatives necessary to induce half the plateau porphyrin values obtained from ALA. These values were achieved at concentrations 4 and 12 times lower compared to ALA, according to the derivative used. For He-ALA, concentrations were 24 to 25 times lower than required for ALA for inducing comparable porphyrin synthesis in both CTCL cells. The light doses for inducing 50% of cell death (LD50) for He-ALA, 1f, 1 g, 1 h and 1i were around 18 and 25 J/cm2 for Myla and HuT-78 cells respectively, after exposure to 0.05 mM concentrations of the compounds. On the other hand, the LD50s for the compound 1 k were 40 and 57 J/cm2 for Myla and HuT-78, respectively. In contrast, 0.05 mM of ALA and Me-ALA did not provoke photokilling since the concentration employed was far below the porphyrin saturation point for these compounds. Our results suggest the potential use of ALA derivatives for topical application in PDT treatment of MF and extracorporeal PDT for the depletion of activated T-cells in SS