Effect Of Zinc Cations On The Kinetics Of Supramolecular Assembly And The Chirality Of Porphyrin J-Aggregates

Dilute aqueous solutions of anionic meso-4-sulfonatophenyl-porphyrin (TPPS) extract zinc(ii) ions from glass or quartz surfaces at room temperature and efficiently form the corresponding metal complex (ZnTPPS). The partial or complete formation of ZnTPPS has been probed by UV/Vis spectroscopy and both static and time-resolved fluorescence. The source of zinc(ii) ions has been clearly identified through inductively coupled plasma optical emission spectrometry. The presence of increasing amounts of ZnTPPS slows down the rate of TPPS J-aggregate formation in acid solution. This influences the nucleation step and has a profound impact on the onset of chirality in these species. This evidence indicates the important role of this adventitious metal ion in the interpretation of various spectroscopic and kinetic data for the self-assembly of the TPPS porphyrin and provides some insights into controversial findings on their chirality. The use of this metal derivative as the starting compound for in situ formation of monomeric TPPS is suggested

Hardware limitations to secure C-ITS: experimental evaluation and solutions

Cooperative Intelligent Transportation Systems (C-ITS) improve driving experience and safety through secure Vehicular Ad-hoc NETworks (VANETs) that satisfy strict security and performance constraints. Relevant standards, such as the IEEE 1609.2, prescribe network-efficient cryptographic protocols to reduce communication latencies through a combination of the Elliptic Curve Qu-Vanstone (ECQV) implicit certificate scheme and the Elliptic Curve Digital Signature Algorithm (ECDSA). However, literature lacks open implementations and performance evaluations for vehicular systems. This paper assesses the applicability of IEEE 1609.2 and of ECQV and ECDSA schemes to C-ITSs. We release an open implementation of the standard ECQV scheme to benchmark its execution time on automotive-grade hardware. Moreover, we evaluate its performance in real road and traffic scenarios and show that compliance with strict latency requirements defined for C-ITS requires computational resources that are not met by many automotive-grade embedded hardware platforms. As a final contribution, we propose and evaluate novel heuristics to reduce the number of signatures to be verified in real C-ITS scenarios

A Dip Into a Deep Well: Online Political Advertisements, Valence, and European Electoral Campaigning

Online political advertisements have become an important element in electoral campaigning throughout the world. At the same time, concepts such as disinformation and manipulation have emerged as a global concern. Although these concepts are distinct from online political ads and data-driven electoral campaigning, they tend to share a similar trait related to valence, the intrinsic attractiveness or averseness of a message. Given this background, the paper examines online political ads by using a dataset collected from Google's transparency reports. The examination is framed to the mid-2019 situation in Europe, including the European Parliament elections in particular. According to the results based on sentiment analysis of the textual ads displayed via Google's advertisement machinery, (i) most of the political ads have expressed positive sentiments, although these vary greatly between (ii) European countries as well as across (iii) European political parties. In addition to these results, the paper contributes to the timely discussion about data-driven electoral campaigning and its relation to politics and democracy

Protein profiling in hepatocellular carcinoma by label-free quantitative proteomics in two west african populations.

Background Hepatocellular Carcinoma is the third most common cause of cancer related death worldwide, often diagnosed by measuring serum AFP; a poor performance stand-alone biomarker. With the aim of improving on this, our study focuses on plasma proteins identified by Mass Spectrometry in order to investigate and validate differences seen in the respective proteomes of controls and subjects with LC and HCC. Methods Mass Spectrometry analysis using liquid chromatography electro spray ionization quadrupole time-of-flight was conducted on 339 subjects using a pooled expression profiling approach. ELISA assays were performed on four significantly differentially expressed proteins to validate their expression profiles in subjects from the Gambia and a pilot group from Nigeria. Results from this were collated for statistical multiplexing using logistic regression analysis. Results Twenty-six proteins were identified as differentially expressed between the three subject groups. Direct measurements of four; hemopexin, alpha-1-antitrypsin, apolipoprotein A1 and complement component 3 confirmed their change in abundance in LC and HCC versus control patients. These trends were independently replicated in the pilot validation subjects from Nigeria. The statistical multiplexing of these proteins demonstrated performance comparable to or greater than ALT in identifying liver cirrhosis or carcinogenesis. This exercise also proposed preliminary cut offs with achievable sensitivity, specificity and AUC statistics greater than reported AFP averages. Conclusions The validated changes of expression in these proteins have the potential for development into high-performance tests usable in the diagnosis and or monitoring of HCC and LC patients. The identification of sustained expression trends strengthens the suggestion of these four proteins as worthy candidates for further investigation in the context of liver disease. The statistical combinations also provide a novel inroad of analyses able to propose definitive cut-offs and combinations for evaluation of performance

Trends in chronic hepatitis B virus infection in Italy over a 10-year period: Clues from the nationwide PITER and MASTER cohorts toward elimination

Objectives: The study measures trends in the profile of patients with chronic hepatitis B virus linked to care in Italy. Methods: A cross-sectional, multicenter, observational cohort (PITER cohort) of consecutive patients with hepatitis B surface antigen (HBsAg) over the period 2019-2021 from 46 centers was evaluated. The reference was the MASTER cohort collected over the years 2012-2015. Standard statistical methods were used. Results: The PITER cohort enrolled 4583 patients, of whom 21.8% were non-Italian natives. Compared with those in MASTER, the patients were older and more often female. The prevalence of hepatitis B e antigen (HBeAg) declined (7.2% vs 12.3; P <0.0001) and that of anti-hepatitis D virus (HDV) remained stable (9.3% vs 8.3%). In both cohorts, about 25% of the patients had cirrhosis, and those in the PITER cohort were older. HBeAg-positive was 5.0% vs 12.6% (P <0.0001) and anti-HDV positive 24.8% vs 17.5% (P <0.0017). In the logistic model, the variables associated with cirrhosis were anti-HDV-positive (odds ratio = 10.08; confidence interval 7.63-13.43), age, sex, and body mass index; the likelihood of cirrhosis was reduced by 40% in the PITER cohort. Among non-Italians, 12.3% were HBeAg-positive (vs 23.4% in the MASTER cohort; P <0.0001), and 12.3% were anti-HDV-positive (vs 11.1%). Overall, the adherence to the European Association for the Study of the Liver recommendations for antiviral treatment increased over time. Conclusion: Chronic hepatitis B virus infection appears to be in the process of becoming under control in Italy; however, HDV infection is still a health concern in patients with cirrhosis and in migrants