Light-emissive compounds able to transfer protons, either intra- or intermolecularly in the excited state, have increasingly attracted attention, especially by structural diversification of ...recognized fluorophores. We report herein synthesis and structural characterization of novel 1,3,4-oxadiazole-based compounds functionalised by salicylaldehyde or o-vanillin moieties. Solution absorption and emission spectroscopy performed on the resulted compounds indicated the essential influence of the established (intra and/or intermolecular) hydrogen bonds onto the optical properties. Theoretical calculations positively contributed to the effort of understanding the emissive behaviour of the compounds and the calculated data correlated very well to experiments. Occurrence of hydrogen bond interactions has been also observed in solid state and we discuss their molecular structures and the effects on the luminescent behaviour. The phenol groups in close proximity of the oxadiazole core were further exploited in cocrystallization experiments with pyridine-based co-partners. Hydrogen bonding were also found responsible for the supramolecular recognition between the two components. One type of the resulted co-crystals preserved the luminescence of the starting compound.
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•Blue and green emissive 1,3,4-oxadiazoles able to transfer protons either intra- or intermolecularly were prepared.•DFT calculation confirms occurrence of ESIPT and/or ESPT.•The synthesized compounds emit blue and green light in solid state.•The synthesized compounds were exploited to prepare pyridine-based co-crystals.
Psoriasis is a chronic inflammatory, autoimmune-mediated disease that affects millions of individuals worldwide. Advances in treatment with biological agents represented by monoclonal antibodies, ...such as TNF-α inhibitors (TNFI), IL-17A and IL-12/23 antagonists have not only benefited from outstanding clinical efficacy with lower side effects compared to conventional systemic therapy, but also raised the standards towards therapeutic success, fact reflected in the greater Psoriasis Area and Severity Index (PASI) response rates. However, due to their relatively recent introduction in clinical practice, and despite their proven superior efficacy, further research is needed for monitoring the eventual changes in treatment-induced parameters, especially of metabolic origin. In this respect, initial reports stress on one particular comorbidity associated with psoriasis-obesity-which seems to be not only a risk and result of the disease, but also an adverse effect of long-term therapy with some biologics. The consequent drug-induced increase in body mass index (BMI) of patients suffering from psoriasis undergoing biological treatment appears to contribute to the progression of the disease, promote drug discontinuation and reduce overall clinical efficacy of monoclonal antibodies. Therefore, we review herein the impact of body weight (BMI) increase on the biological treatment of psoriasis, to further investigate on its relationship with the disease and aid on the management of treatment schemes that take into account individual characteristics of patients, such as body mass, for a more efficient and personalized therapy approach.
The feasibility of mixed-cation mixed-halogen perovskites of formula AxA’1−xPbXyX’zX”3−y−z is analyzed from the perspective of structural stability, opto-electronic properties and possible ...degradation mechanisms. Using density functional theory (DFT) calculations aided by machine-learning (ML) methods, the structurally stable compositions are further evaluated for the highest absorption and optimal stability. Here, the role of the halogen mixtures is demonstrated in tuning the contrasting trends of optical absorption and stability. Similarly, binary organic cation mixtures are found to significantly influence the degradation, while they have a lesser, but still visible effect on the opto-electronic properties. The combined framework of high-throughput calculations and ML techniques such as the linear regression methods, random forests and artificial neural networks offers the necessary grounds for an efficient exploration of multi-dimensional compositional spaces.
Objectives. The purpose of this study was to assess and compare the clinicopathological, molecular pathology, treatment and survival characteristics in patients with metachronous bilateral breast ...cancer (mBBC) and synchronous breast cancer (sBBC). Materials and methods. A cohort of 658 patients with breast cancer treated at the Coltea Clinical Hospital, Surgery Department, between January 2015 and December 2019 and followed-up until August 2020 was studied. Data pertaining to patients who were diagnosed as having bilateral breast cancer were retrospectively reviewed and collected. A 3-months interval was used to distinguish metachronous from synchronous tumors. Among patients with bilateral breast cancer, assessment parameters included patient characteristics, histological and molecular pathology features and the performed treatment that were statistically evaluated comparing the first and second tumor of each group and among groups. Survival analysis was performed comparing mBBC and sBBC patients. SPSS was used for data analysis. Outcomes. Of the 658 patients with primary breast cancer, 35 (5.3%) patients were diagnosed as having bilateral breast cancer (25 (3.8%) mBBC and 10 (1.5%) sBBC). When clinical and histopathological parameters were statistically evaluated, age, menopausal status, tumor size, number of invaded nodes and anatomic stage were found to be significant between the tumors of the metachronous group and tumor size, pathologic T(tumor) and stage between tumors of the synchronous group. Hormonal receptor (HR) status concordance was higher in the synchronous group (85.7%, p = 0.010), with a higher percentage of ER positive (71.4%) and PR positive (71.4%) concordance of the tumors. In terms of survival analysis, there was a difference in overall survival (OS, p = 0.005), disease-free survival (DFS, p = 0.011) and distant relapse-free survival (p = 0.003) between mBBC and sBBC. The mean disease-free survival for patients in whom metachronous tumor occurred within less than 5 years was 63.3 months, for sBBC patients was 39.6 months, whereas for patients with more than 5 years was 437.9 months (p = 0.012, Log Rank). Discordant biomarker defined subgroup (ER,HER2) patients were associated with better disease-free survival (p = 0.047, Log Rank) and better distant relapse-free survival (p = 0.015, Log Rank) in overall patients. In terms of loco-regional relapse-free survival, although mBBC and sBBC patients showed no statistical significant difference earlier in the time course (p = 0.088, Breslow; p = 0.054 Tarone-Ware), among mBBC patients was observed a better outcome (p = 0.027, Log Rank). Conclusions. Based on survival analysis, patients in whom metachronous tumor developed after more than 5 years, had a better distant relapse-free survival. Patients with synchronous bilateral breast cancer were associated with worse disease outcome based on overall survival analysis and disease free-survival rates with more frequent rates of distant metastasis. Outcome of patients in whom metachronous tumor was diagnosed within less than 5 years might be similar to synchronous tumors. Patients with discordant ER,HER2 status showed a better disease outcome. Although concordance in HR status and molecular subtype, did not show statistical significant differences, it is a subject which deserves further clinical observation.
Non-ischemic dilated cardiomyopathy encompasses a wide spectrum of myocardial disorders, characterized by left ventricular dilatation with systolic impairment and increased risk of sudden cardiac ...death. In spite of all the therapeutic progress that has been made in recent years, dilated cardiomyopathy continues to be an important cause of cardiac transplant, being associated with an enormous cost burden for health care systems worldwide. Predicting the prognosis of patients with dilated cardiomyopathy is essential to individualize treatment. Late gadolinium enhancement-cardiac magnetic resonance imaging, microvolt T-wave alternans, and genetic testing have emerged as powerful tools in predicting sudden cardiac death occurrence and maximizing patient’s selection. Despite all these new diagnostic modalities, additional tests to complement or replace current tools are required for better risk stratification. Therefore, biomarkers are an easy and important tool that can help to detect patients at risk of adverse cardiovascular events. Additionally, identifying potential biomarkers involved in dilated cardiomyopathy can provide us important information regarding the diagnostic, prognostic, risk stratification, and response to treatment for these patients. Many potential biomarkers have been studied in patients with dilated cardiomyopathy, but only a few have been adopted in current practice. Therefore, the aim of our review is to provide the clinicians with an update on the well-known and novel biomarkers that can be useful for risk stratification of patients with non-ischemic dilated cardiomyopathy.
This article presents a study on the development of tourism activities in Region 2 South East, especially in protected areas from the perspective of the national strategy for ecotourism development ...and with interferences of cultural tourism well supported by ethnic and cultural diversity, both in Dobrogea and in areas mountains located at the edge of the Carpathian arc. The fundamental arguments of this approach are provided by the large number of protected areas existing in the coastal area and the delta, as well as in Vrancea and Buzău counties where the maintenance of cultural traditions offers the possibility of a better capitalization of local resources. The main actors in these areas are also active factors in identifying the main lines of tourism development in the current particularly complex conditions,.
Background and Objectives: SARS-CoV-2 has an extensive tissue tropism due to its ability to attach to the surfaces of cells through different receptors, leading to systemic complications. In this ...article, we aim to present the prevalence of pericardial effusions in patients with severe COVID-19, to identify the risk factors/predictors for pericardial involvement, and to evaluate its impact on overall mortality. Materials and Methods: We enrolled 100 patients with severe COVID-19 in our observational cohort study and divided them in two groups: Group A (27 patients with pericardial effusion) and Group B (73 patients without pericardial effusion). We recorded demographic and lifestyle parameters, anthropometric parameters, clinical parameters, inflammation markers, respiratory function parameters, complete blood count, coagulation parameters, and biochemical serum parameters. All patients were evaluated by computer tomography scans within 48 h of admission. Results: The median age was 61 years in both groups and the male/female ratio was 3.5 vs. 2.8 in Group A vs. Group B. We identified mild pericardial effusion (3–4 mm) in 62.9% patients and moderate pericardial effusion (5–9 mm) in 37.1% patients, with a median value of 4 3;6 mm. The patients with pericardial effusion presented with higher percentages of obesity, type-2 diabetes mellitus, arterial hypertension, and congestive heart failure, without statistical significance. Increased values in cardiac enzymes (myoglobin, CK, CK-MB) and LDH were statistically associated with pericardial effusion. The overall mortality among the participants of the study was 24% (24 patients), 33.3% in Group A and 20.8% in Group B. Conclusions: Pericardial effusion has a high prevalence (27%) among patients with severe forms of COVID-19 and was associated with higher mortality. Pericardial effusion in our study was not associated with the presence of comorbidities or the extent of lung involvement. Overall mortality was 60% higher in patients with pericardial effusion.
Buildings can become a significant contributor to an energy system’s resilience if they are operated in a coordinated manner to exploit their flexibility in multi-carrier energy networks. However, ...research and innovation activities are focused on single-carrier optimization (i.e., electricity), aiming to achieve Zero Energy Buildings, and miss the significant flexibility that buildings may offer through multi-energy coupling. In this paper, we propose to use blockchain technology and ERC-1155 tokens to digitize the heat and electrical energy flexibility of buildings, transforming them into active flexibility assets within integrated multi-energy grids, allowing them to trade both heat and electricity within community-level marketplaces. The solution increases the level of interoperability and integration of the buildings with community multi-energy grids and brings advantages from a transactive perspective. It permits digitizing multi-carrier energy using the same token and a single transaction to transfer both types of energy, processing transaction batches between the sender and receiver addresses, and holding both fungible and non-fungible tokens in smart contracts to support energy markets’ financial payments and energy transactions’ settlement. The results show the potential of our solution to support buildings in trading heat and electricity flexibility in the same market session, increasing their interoperability with energy markets while decreasing the transactional overhead and gas consumption.
Designing composites based on natural polymers has attracted attention for more than a decade due to the possibility to manufacture medical devices which are biocompatible with the human body. ...Herein, we present some biomaterials made up of collagen, polyurethane, and cellulose doped with lignin and lignin-metal complex, which served as transcutaneous drug delivery systems. Compared with base material, the compressive strength and the elastic modulus of biocomposites comprising lignin or lignin-metal complex were significantly enhanced; thus, the compressive strength increased from 61.37 to 186.5 kPa, while the elastic modulus increased from 0.828 to 1.928 MPa. The release of ketokonazole from the polymer matrix follows a Korsmeyer–Peppas type kinetics with a Fickian diffusion. All materials tested were shown to be active against pathogenic microorganisms. The mucoadhesiveness, bioadhesiveness, mechanical resistance, release kinetic, and antimicrobial activity make these biocomposites to be candidates as potential systems for controlled drug release.
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