Tetra-anionic porphyrin loading onto ZnO nanoneedles: A hybrid covalent/non covalent approach

A stepwise surface functionalization procedure, based on hybrid covalent and non-covalent approach is herein proposed to anchor tetra-anionic meso-tetrakis(4-sulfonatophenyl)porphyrin on ZnO nanorods. Carboxyalkylphosphonic acids have been proven effective to form stable self-assembled monolayers through the surface grafting of –PO₃H₂ headgroups. The exposed carboxylic functionalities are suitable for the successful grafting of cationic poly-l-lysine that drives, in water, the non-covalent anchoring of the anionic porphyrin. A stepwise surface characterization, provided by X-ray photoelectron spectroscopy, elucidates the multilayers deposition and surface composition after each process step, thus, giving interesting insights on the chemical speciation of the exposed functionalities. UV–vis spectroscopy confirms the role of ZnO morphology to increase the porphyrin loading onto the investigated surfaces. The proposed approach is effective to achieve deposition of anionic porphyrins on ZnO nanostructures and combines the robustness of covalent functionalization with the versatility and full reversibility of the non-covalent strategies.     

Effect of hemodiafiltration with endogenous reinfusion on overt idiopathic chronic inflammation in maintenance hemodialysis patients: A multicenter longitudinal study

Chronic inflammation is widely diffuse in maintenance hemodialysis (MHD) patients and is associated with poor survival. Hemodiafiltration with endogenous reinfusion (HFR) is a dialysis technique, highly biocompatible, able to adsorb proinflammatory cytokines and to decrease amino acids and antioxidants loss. These features could be helpful in MHD patients affected by idiopathic chronic inflammation, but this issue remains to be elucidated. We performed a multicenter longitudinal study to assess the effect of the switching from bicarbonate HD to HFR in patients with serum C‐reactive Protein (CRP) > 5 mg/L coupled with albumin <4.0 g/dL in the last 6 months. We enrolled 24/176 (14%) patients, of which 20 patients were assessed at 4 months and 18 completed the study. We excluded 11 patients with evident causes of inflammation. At baseline, serum levels of CRP (18.7[7.0–39.4] mg/L) and albumin (3.5[3.3–3.7] g/dL) were significantly correlated (r = ?0.49; P = 0.028). The effect on CRP and albumin was almost evident in the first 4 months and remained stable until to eighth month. A strict correlation (R = ?0.49; 0.040) between percentage change of CRP (?35%) and albumin (+14%) after 8 months of HFR. These effects were associated with the reduction of IL‐6, IL‐1β, and TNF‐α and the increment of pre‐albumin and leptin, whereas the serum levels of Branched Chain Amino Acid (BCAA) remained unchanged. In MHD patients affected by idiopathic chronic inflammation the switching from BHD to HFR is associated with improvement of inflammation. Whether these favorable effects may modify the outcomes of these high‐risk patients needs to be confirmed by studies ad hoc.     

Thermoluminescence solid-state nanodosimetry--the peak 5A/5 dosemeter

The shape of composite peak 5 in the glow curve of LiF:Mg,Ti (TLD-100) following (90)Sr/(90)Y beta irradiation, previously demonstrated to be dependent on the cooling rate used in the 400°C pre-irradiation anneal, is shown to be dependent on ionisation density in both naturally cooled and slow-cooled samples. Following heavy-charged particle high-ionisation density (HID) irradiation, the temperature of composite peak 5 decreases by ～5°C and the peak becomes broader. This behaviour is attributed to an increase in the relative intensity of peak 5a (a low-temperature satellite of peak 5). The relative intensity of peak 5a is estimated using a computerised glow curve deconvolution code based on first-order kinetics. The analysis uses kinetic parameters for peaks 4 and 5 determined from ancillary measurements resulting in nearly 'single-glow peak' curves for both the peaks. In the slow-cooled samples, owing to the increased relative intensity of peak 5a compared with the naturally cooled samples, the precision of the measurement of the 5a/5 intensity ratio is found to be ～15% (1 SD) compared with ～25% for the naturally cooled samples. The ratio of peak 5a/5 in the slow-cooled samples is found to increase systematically and gradually through a variety of radiation fields from a minimum value of 0.13±0.02 for (90)Sr/(90)Y low-ionisation density irradiations to a maximum value of ～0.8 for 20 MeV Cu and I ion HID irradiations. Irradiation by low-energy electrons of energy 0.1-1.5 keV results in values between 1.27 and 0.95, respectively. The increasing values of the ratio of peak 5a/5 with increasing ionisation density demonstrate the viability of the concept of the peak 5a/5 nanodosemeter and its potential in the measurement of average ionisation density in a 'nanoscopic' mass containing the trapping centre/luminescent centre spatially correlated molecule giving rise to composite peak 5.     

Self‐Assembled Conjugated Thiophene‐Based Rotaxane Architectures: Structural,Computational, and Spectroscopic Insights into Molecular Aggregation

A comparative study of the self‐assembly at a variety of surfaces of a dithiophene rotaxane 1 ?β‐CD and its corresponding dumbbell, 1, by means of atomic force microscopy (AFM) imaging and scanning tunneling microscopy (STM) imaging on the micrometer and nanometer scale, respectively. The dumbbell is found to have a greater propensity to form ordered supramolecular assemblies, as a result of π–π interactions between dithiophenes belonging to adjacent molecules, which are hindered in the rotaxane. The fine molecular structure determined by STM was compared to that obtained by molecular modelling. The optical properties of both rotaxane and dumbbell in the solid state were investigated by steady‐state and time‐resolved photoluminescence (PL) experiments on spin‐cast films and diluted solutions. The comparison between the optical features of the threaded and unthreaded systems reveals an effective role of encapsulation in reducing aggregation and exciton migration for the rotaxanes with respect to the dumbbells, thus leading to higher PL quantum efficiency and preserved single‐molecule photophysics for longer times after excitation in the threaded oligomers.     

Three-dimensional modeling using x-ray shape-from-silhouette

We present the application of the shape-from-silhouette technique to reconstruct the three-dimensional profile of ancient handworks from their x-ray absorption images. The acquisition technique is similar to tomography, since the images are taken all around the object while it is rotated. Some reference points are placed on a small and light structure corotating with the object, and are acquired on the images for calibration and registration. The reconstruction algorithm gives finally the three-dimensional appearance of the handwork. We present the analysis of a bronze pendant of VI-VII century B.C. (Venetic area, Italy) completely hidden by corrosion products. The three-dimensional reconstruction shows that the pendant is a very elaborated piece, with two embraced figures that were completely invisible at the excavation.     

Automatic on-line monitoring of atmospheric volatile organic compounds: gas chromatography-mass spectrometry and gas chromatography-flame ionization detection as complementary systems

Traditionally air quality networks have been carrying out the continuous, on-line measurement of volatile organic compounds (VOC) in ambient air with GC-FID. In this paper some identification and coelution problems observed while using this technique in long-term measurement campaigns are described. In order to solve these problems a GC-MS was set up and operated simultaneously with a GC-FID for C₂-C₁₁ VOCs measurement.There are few on-line, unattended, long term measurements of atmospheric VOCs performed with GC-MS. In this work such a system has been optimized for that purpose, achieving good repeatability, linearity, and detection limits of the order of the GC-FID ones, even smaller in some cases. VOC quantification has been made by using response factors, which is not frequent in on-line GC-MS. That way, the identification and coelution problems detected in the GC-FID, which may led to reporting erroneous data, could be corrected.The combination of GC-FID and GC-MS as complementary techniques for the measurement of speciated VOCs in ambient air at sub-ppbv levels is proposed. Some results of the measurements are presented, including concentration values for some compounds not found until now on public ambient air VOC databases, which were identified and quantified combining both techniques. Results may also help to correct previously published VOC data with wrongly identified compounds by reprocessing raw chromatographic data.     

Rapid Evaporative Ionization Mass Spectrometry-Based Lipidomics for Identification of Canine Mammary Pathology

The present work proposes the use of a fast analytical platform for the mass spectrometric (MS) profiling of canine mammary tissues in their native form for the building of a predictive statistical model. The latter could be used as a novel diagnostic tool for the real-time identification of different cellular alterations in order to improve tissue resection during veterinary surgery, as previously validated in human oncology. Specifically, Rapid Evaporative Ionization Mass Spectrometry (REIMS) coupled with surgical electrocautery (intelligent knife—iKnife) was used to collect MS data from histologically processed mammary samples, classified into healthy, hyperplastic/dysplastic, mastitis and tumors. Differences in the lipid composition enabled tissue discrimination with an accuracy greater than 90%. The recognition capability of REIMS was tested on unknown mammary samples, and all of them were correctly identified with a correctness score of 98–100%. Triglyceride identification was increased in healthy mammary tissues, while the abundance of phospholipids was observed in altered tissues, reflecting morpho-functional changes in cell membranes, and oxidized species were also tentatively identified as discriminant features. The obtained lipidomic profiles represented unique fingerprints of the samples, suggesting that the iKnife technique is capable of differentiating mammary tissues following chemical changes in cellular metabolism.     

Evaluation of lipid oxidation in spaghetti pasta enriched with long chain n−3 polyunsaturated fatty acids under different storage conditions

This study investigated lipid oxidation in spaghetti enriched in long chain n−3 polyunsaturated fatty acids (LC n−3 PUFA) by the addition to semolina of an integrator containing eicosapentaenoic acid and docosahexaenoic acid. Two oxidative parameters were evaluated: peroxide value (PV), to assess primary oxidation and oxidised fatty acids to quantify secondary oxidation products. Functional spaghetti had a shelf life comparable to control pasta. LC n−3 PUFA were not significantly implicated in the onset of oxidation in spaghetti stored under daylight and accelerated oxidation in a laboratory heater. Storage decidedly affected shelf life: PV in functional spaghetti increased from 7.1 to 43.4 meq O₂/kg of fat under light exposure over 12 months, and from 7.1 to 16.2 meq O₂/kg under accelerated ageing at 55 °C for 27 days, reproducing about 18 months at room temperature. Oxidised fatty acids increased in fortified spaghetti from 4.8 to 13.8 g/100 g of fat under light exposure over 12 months and from 4.8 to 7.8 g/100 g of fat at 55 °C in 27 days. The high sensitivity of spectrophotometric and chromatographic analytical methods permitted the evaluation of primary and secondary oxidative derivatives in small amounts of fat.     

Design and test of a real-time shelf out-of-stock detector system

Microsystem Technologies - The&nbsp;shelf out-of-stock (SOOS) problem is relevant for retailers and producers since the absence of products on the shelf can lead to a significant reduction of...