Tetra dansylamides substituted cyclen and cyclam macrocycles as fluorescent sensing probes for metal ions and temperature-responsive materials in dopped polymers

PM003/2016). The financial support by the Bulgarian National Science Fund (BNSF) under grant – “Novel styryl and polymethine fluorophores as potential theranostic agents ”contract N◦ КП-06-М59/1 from November 15, 2021 is gratefully acknowledged by A.K. This work is also developed and acknowledged by A.K. as part of contract N◦: BGRRP-2.004-0002-C01, Laboratory of Organic Functional Materials (Project BiOrgaMCT), Procedure BG-RRP-2.004 „Establishing of a network of research higher education institutions in Bulgaria“, funded by BULGARIAN NATIONAL RECOVERY AND RESILIENCE PLAN“. G. D. thanks to the European Regional Development Fund within the Operational Programme Science and Education for Smart Growth 2014–2020 under the Project Center of Excellence: National center of mechatronics and clean technologies - BG05M2OP001-1.001-0008 for the financial support. © 2024 The Authors. Published by Elsevier Ltd.Two novel tetra-dansyl derivatives incorporating cyclen (1,4,7,10-tetraazacyclododecane) and cyclam (1,4,8,11-tetraazacyclotetradecane) macrocycles have been synthesized, thoroughly characterized, and their photophysical properties examined, both in solution and in the solid state. These compounds exhibit fluorescence emission with quantum yields up to 40 %, varying significantly with different solvents. They also display positive solvatofluorochromic behavior, with emissions ranging from green to yellow colours. Kamlet-Taft studies were conducted to better understand solute-solvent interactions. Furthermore, aggregation-induced emission was observed in solutions with high water content, confirmed via dynamic light scattering. Given the intrinsic properties of these compounds, their potential for environmental remediation was explored through metal ion sensing studies. Compounds L1 and L2 demonstrated high sensitivity to Cu2+ and Hg2+ ions, significantly modulating their emission, with L2 capable of detecting and quantifying Hg2+ concentrations as low as 2–3 μM. Additionally, the solid-state emission of these compounds encouraged an investigation into their potential as temperature sensors. Several doped polymer thin films were fabricated, establishing a linear relationship with temperature beyond their melting point. These findings suggest that these tetra-chromophoric compounds hold promise as molecular thermometers.publishersversionpublishe

A dual-responsive Dansyl–Naphthalimide system for Hg(II) CHEF detection and ligand-mediated Cu(II) reduction with catalytic relevance

PM003/2016. This work is also developed and acknowledged by A.K. as part of contract №: BG-RRP-2.004-0002-C01, Laboratory of Organic Functional Materials (Project BiOrgaMCT), Procedure BG-RRP-2.004 „Establishing of a network of research higher education institutions in Bulgaria“, funded by BULGARIAN NATIONAL RECOVERY AND RESILIENCE PLAN“. Publisher Copyright: © 2025 The AuthorsWe report a compelling structure–property relationship in a series of four naphthalimide-derived ligands, engineered for the selective and differential detection of Hg(II) and Cu(II) ions. By integrating a dansyl moiety, we induce intramolecular electron transfer that gives rise to two non-redox-innocent dyad systems. Notably, the detection of Hg(II) operates through a rare chelation-enhanced fluorescence (CHEF) mechanism, an unusual pathway considering the heavy atom effect typically associated with mercury. In contrast, the Cu(II) dyads reveal striking reduction of Cu(II) to Cu(I) in solution, driven by ligand-to-metal electron transfer, as conclusively demonstrated via EPR and XPS analysis. Furthermore, introducing a catalytic substrate probe highlights that this redox transformation is the bottleneck in catalytic efficiency. These findings provide deep mechanistic insights and position these ligands as versatile platforms for dual-mode ion sensing and redox-responsive catalysis.publishersversionpublishe

Synthesis, characterization and complex evaluation of antibacterial activity and cytotoxicity of new arylmethylidene ketones and pyrimidines with camphane skeletons

The synthesis of 20 arylidenecamphors and 15 pyrimidines with camphane skeleton is described in the current report. A modified method for preparation of sterically hindered 2- aminopyrimidines in two steps was demonstrated. The evaluation of their in vitro activity against Mycobacterium tuberculosis H37Rv showed different MIC values (up to 0.91 μM for ketone 39). Compound 35 demonstrated moderate (8.23 μM), but sustainable activity toward a collection of drug-resistant M. tuberculosis strains. Many of the compounds (especially among 2-aminopyridines 42–56) exhibited good to excellent activity against different strains of pathogenic bacteria and fungi (MIC up to 0.60 μM for compound 50), compared with reference antibiotics. Many of the newly designed compounds possess also in vitro cytotoxicity.This study was supported by: Bulgarian National Science Fund- project KP-06-H39/7 and Spanish Ministry of Science, Innovation and Universities- Grant RTI2018-094629-BI00. MEDINA’s authors disclosed the receipt of financial support from Fundación MEDINA, a public-private partnership of Merck Sharp and Dohme de EspañaS.A./Universidad de Granada/Junta de Andalucía

Early contact between late farming and pastoralist societies in southeastern Europe

Archaeogenetic studies have described two main genetic turnover events in prehistoric western Eurasia: one associated with the spread of farming and a sedentary lifestyle starting around 7000–6000 bc (refs. 1–3) and a second with the expansion of pastoralist groups from the Eurasian steppes starting around 3300 bc (refs. 4,5). The period between these events saw new economies emerging on the basis of key innovations, including metallurgy, wheel and wagon and horse domestication6–9. However, what happened between the demise of the Copper Age settlements around 4250 bc and the expansion of pastoralists remains poorly understood. To address this question, we analysed genome-wide data from 135 ancient individuals from the contact zone between southeastern Europe and the northwestern Black Sea region spanning this critical time period. While we observe genetic continuity between Neolithic and Copper Age groups from major sites in the same region, from around 4500 bc on, groups from the northwestern Black Sea region carried varying amounts of mixed ancestries derived from Copper Age groups and those from the forest/steppe zones, indicating genetic and cultural contact over a period of around 1,000 years earlier than anticipated. We propose that the transfer of critical innovations between farmers and transitional foragers/herders from different ecogeographic zones during this early contact was integral to the formation, rise and expansion of pastoralist groups around 3300 bc

The genomic history of southeastern Europe

Farming was first introduced to Europe in the mid-seventh millennium BC, and was associated with migrants from Anatolia who settled in the southeast before spreading throughout Europe. Here, to understand the dynamics of this process, we analysed genome-wide ancient DNA data from 225 individuals who lived in southeastern Europe and surrounding regions between 12000 and 500 BC. We document a west-east cline of ancestry in indigenous hunter-gatherers and, in eastern Europe, the early stages in the formation of Bronze Age steppe ancestry. We show that the first farmers of northern and western Europe dispersed through southeastern Europe with limited hunter-gatherer admixture, but that some early groups in the southeast mixed extensively with hunter-gatherers without the sex-biased admixture that prevailed later in the north and west. We also show that southeastern Europe continued to be a nexus between east and west after the arrival of farmers, with intermittent genetic contact with steppe populations occurring up to 2,000 years earlier than the migrations from the steppe that ultimately replaced much of the population of northern Europe

Diversity and ethics in trauma and acute care surgery teams: results from an international survey

Background: Investigating the context of trauma and acute care surgery, the article aims at understanding the factors that can enhance some ethical aspects, namely the importance of patient consent, the perceptiveness of the ethical role of the trauma leader, and the perceived importance of ethics as an educational subject. Methods: The article employs an international questionnaire promoted by the World Society of Emergency Surgery. Results: Through the analysis of 402 fully filled questionnaires by surgeons from 72 different countries, the three main ethical topics are investigated through the lens of gender, membership of an academic or non-academic institution, an official trauma team, and a diverse group. In general terms, results highlight greater attention paid by surgeons belonging to academic institutions, official trauma teams, and diverse groups. Conclusions: Our results underline that some organizational factors (e.g., the fact that the team belongs to a university context or is more diverse) might lead to the development of a higher sensibility on ethical matters. Embracing cultural diversity forces trauma teams to deal with different mindsets. Organizations should, therefore, consider those elements in defining their organizational procedures. Level of evidence: Trauma and acute care teams work under tremendous pressure and complex circumstances, with their members needing to make ethical decisions quickly. The international survey allowed to shed light on how team assembly decisions might represent an opportunity to coordinate team member actions and increase performance

COVID-19 and the Global Impact on Colorectal Practice and Surgery

Background: The novel severe acute respiratory syndrome coronavirus 2 virus that emerged in December 2019 causing coronavirus disease 2019 (COVID-19) has led to the sudden national reorganization of health care systems and changes in the delivery of health care globally. The purpose of our study was to use a survey to assess the global effects of COVID-19 on colorectal practice and surgery. Materials and Methods: A panel of International Society of University Colon and Rectal Surgeons (ISUCRS) selected 22 questions, which were included in the questionnaire. The questionnaire was distributed electronically to ISUCRS fellows and other surgeons included in the ISUCRS database and was advertised on social media sites. The questionnaire remained open from April 16 to 28, 2020. Results: A total of 287 surgeons completed the survey. Of the 287 respondents, 90% were colorectal specialists or general surgeons with an interest in colorectal disease. COVID-19 had affected the practice of 96% of the surgeons, and 52% were now using telemedicine. Also, 66% reported that elective colorectal cancer surgery could proceed but with perioperative precautions. Of the 287 respondents, 19.5% reported that the use of personal protective equipment was the most important perioperative precaution. However, personal protective equipment was only provided by 9.1% of hospitals. In addition, 64% of surgeons were offering minimally invasive surgery. However, 44% reported that enough information was not available regarding the safety of the loss of intra-abdominal carbon dioxide gas during the COVID-19 pandemic. Finally, 61% of the surgeons were prepared to defer elective colorectal cancer surgery, with 29% willing to defer for ≤ 8 weeks. Conclusion: The results from our survey have demonstrated that, globally, COVID-19 has affected the ability of colorectal surgeons to offer care to their patients. We have also discussed suggestions for various practical adaptation strategies for use during the recovery period. We have presented the results of a survey used to assess the global impact of coronavirus disease 2019 (COVID-19) on the delivery of colorectal surgery. Despite accessible guidance information, our results have demonstrated that COVID-19 has significantly affected the ability of colorectal surgeons to offer care to patients. We have also discussed practical adaptation strategies for use during the recovery phase

Time for a paradigm shift in shared decision-making in trauma and emergency surgery? Results from an international survey

Background: Shared decision-making (SDM) between clinicians and patients is one of the pillars of the modern patient-centric philosophy of care. This study aims to explore SDM in the discipline of trauma and emergency surgery, investigating its interpretation as well as the barriers and facilitators for its implementation among surgeons. Methods: Grounding on the literature on the topics of the understanding, barriers, and facilitators of SDM in trauma and emergency surgery, a survey was created by a multidisciplinary committee and endorsed by the World Society of Emergency Surgery (WSES). The survey was sent to all 917 WSES members, advertised through the society’s website, and shared on the society’s Twitter profile. Results: A total of 650 trauma and emergency surgeons from 71 countries in five continents participated in the initiative. Less than half of the surgeons understood SDM, and 30% still saw the value in exclusively engaging multidisciplinary provider teams without involving the patient. Several barriers to effectively partnering with the patient in the decision-making process were identified, such as the lack of time and the need to concentrate on making medical teams work smoothly. Discussion: Our investigation underlines how only a minority of trauma and emergency surgeons understand SDM, and perhaps, the value of SDM is not fully accepted in trauma and emergency situations. The inclusion of SDM practices in clinical guidelines may represent the most feasible and advocated solutions

COVID-19 infection is a significant risk factor for death in patients presenting with acute cholecystitis: a secondary analysis of the ChoCO-W cohort study

Background: During the coronavirus disease (COVID-19) pandemic, there has been a surge in cases of acute cholecystitis. The ChoCO-W global prospective study reported a higher incidence of gangrenous cholecystitis and adverse outcomes in COVID-19 patients. Through this secondary analysis of the ChoCO-W study data, we aim to identify significant risk factors for mortality in patients with acute cholecystitis during the COVID-19 pandemic, emphasizing the role of COVID-19 infection in patient outcomes and treatment efficacy.” Methods: The ChoCO-W global prospective study reported data from 2546 patients collected at 218 centers from 42 countries admitted with acute cholecystitis during the COVID-19 pandemic, from October 1, 2020, to October 31, 2021. Sixty-four of them died. Nonparametric statistical univariate analysis was performed to compare patients who died and patients who survived. Significant factors were then entered into a logistic regression model to define factors predicting mortality. Results: The significant independent factors that predicted death in the logistic regression model with were COVID-19 infection (p < 0.001), postoperative complications (p < 0.001), and type (open/laparoscopic) of surgical intervention (p = 0.003). The odds of death increased 5 times with the COVID-19 infection, 6 times in the presence of complications, and it was reduced by 86% with adequate source control. Survivors predominantly underwent urgent laparoscopic cholecystectomy (52.3% vs. 23.4%). Conclusions: COVID-19 was an independent risk factor for death in patients with acute cholecystitis. Early laparoscopic cholecystectomy has emerged as the cornerstone of treatment for hemodynamically stable patients