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Metal-Assisted Synthesis of Extended Polyaromatic Nitrogen-Rich Ligands for Tunable Sensitization of Eu(III) Complexes
No full textWe report the metal-assisted synthesis of oligomeric nitrogen-rich DiL1 and PoL1 n sensitizers from the monomer L1 via acyclic diene metathesis (ADMET) polymerization for the tuning of the photoluminescence properties of europium-containing complexes by ligand design. The binding of [Eu(hfac)3 ] cargoes (H-hfac = 1,1,1,5,5,5-hexafluoropentane-2,4-dione) to monomer L1 to give [L1 Eu(hfac)3 ] during metathesis appeared to be essential (i) for protecting the Grubbs ruthenium catalyst to interact with the nitrogen atoms of L1 and (ii) to drive the Ru-catalyzed ADMET reaction toward dimeric {DiL1 [Eu(hfac)3 ]2 } and polymeric {PoL1 n [Eu(hfac)3 ] n } assemblies. Compared with the monomeric tridentate L1 -L4 ligands, significant electronic delocalization occurs through the π-conjugated benzimidazole-CH═CH-benzimidazole skeletons in the dimer DiL1 and polymers PoL1 n , which results in a stepwise red-shift of the excited levels in these extended polyaromatic ligands. As a consequence, the sensitization of bound [Eu(hfac)3 ] units reveals a decrease of the photoluminescence quantum yields along the [L4 Eu(hfac)3 ] > [L3 Eu(hfac)3 ] > [L2 Eu(hfac)3 ] ≈ [L1 Eu(hfac)3 ] > {DiL1 [Eu(hfac)3 ]2 } > {PoL1 18 [Eu(hfac)3 ]18 } series due to unfavorable europium-to-ligand back energy transfers
Gynécologie-obstétrique. Apport de l’évaluation hémodynamique pendant la grossesse
No full textPregnancy leads to a progressive adaptation of the maternal vascular and cardiac systems. Blood pressure is an imperfect indicator of this adaptation, as it reflects cardiac output, vascular resistance, and circulatory volume. Increasingly, studies show that poor hemodynamic adaptation can predict or accompany maternal and/or foetal complications. During pregnancy follow-up, assessing hemodynamic parameters could help identify patients at-risk and personalize their care. In obstetric emergencies, understanding the maternal hemodynamic status can improve clinical management.La grossesse entraîne une adaptation progressive des systèmes vasculaire et cardiaque maternels. La pression artérielle est un indicateur imparfait de cette adaptation, car elle dépend du débit cardiaque, des résistances vasculaires et du volume circulatoire De plus en plus d’études montrent que la mauvaise adaptation hémodynamique peut prédire ou accompagner des complications maternelles et/ou fœtales. Pendant le suivi de la grossesse, l’évaluation de certains paramètre hémodynamiques pourrait permettre d’identifier les femmes à risque de complications et de personnaliser leur suivi. En situation d’urgence obstétricale, comprendre le statut hémodynamique maternel peut améliorer la prise en charge
Intervention Planning for a Home Health-and-Social-Care Institute in Switzerland
No full textWe consider an intervention planning problem proposed by AVASAD, a home health-and-social-care institute in Switzerland. The main decisions are to assign interventions to caregivers, decide the start time of each intervention, and determine the caregiver routes. Various constraints are considered, including skills, working hours, patient availabilities, travel times, and imposed start times for some interventions. Six objective functions are ranked according to a strict priority im- posed by AVASAD (e.g., maximize the care continuity and the number of inter- ventions assigned to caregivers with the recommended skills, minimize the travel and idle times, maximize the assignment of interventions at the patient preferred times). Various insertion algorithms are proposed and combined, and their results are favorably compared to the schedules employed by AVASA
Navigating patients’ perceptions, experiences, and intentions towards their long-term medications in the Swiss ambulatory healthcare system
No full textManaging long-term medications is a complex and dynamic process that requires patients to adapt, organize, and sustain daily routines. Individuals living with chronic conditions regularly interact with multiple healthcare providers and access diverse sources of information, making care coordination challenging. At the same time, the shift toward patient-centered care underscores the importance of understanding how patients use medication-related information, make treatment decisions, and navigate the challenges inherent to long-term medication management.
Through four complementary studies, using both quantitative and qualitative methodologies, this thesis explores patients’ experiences with long-term medications to deepen the understanding of medication management from the patient perspective. The Contradictions study examined whether individuals with chronic conditions perceive conflicting medication information, assessed its prevalence and sources, and investigated its impact on patients’ navigation in the healthcare system. The Adjustments study explored how and why patients make self-initiated changes to their long-term medications without prior consultation with a healthcare professional, including the types of adjustments, underlying motivations, perceived consequences, and the decision-making tools they rely on. The Specchio-Adherence study assessed the impact of the COVID-19 pandemic on long-term medication adherence and access to care. Finally, the Nirmatrelvir/r study investigated patients’ self-management of nirmatrelvir/ritonavir prescribed for COVID-19, its influence on the management of concomitant long-term medications, and their experiences with the information delivered by pharmacists and physicians.
This thesis underscores the importance of understanding how patients self-manage long-term medications, taking into account their lived experiences, perceived needs, and daily routines. Patients frequently self-adjust their medications without professional support, revealing gaps in collaboration and a reluctance to discuss medication management with healthcare providers. This highlights the need for new strategies that promote consistent patient-centered communication and strengthen interprofessional collaboration in community settings. Clear definitions of the roles and responsibilities of patients, physicians, pharmacists, and nurses—as well as enhanced training in communication skills—are essential to support medication self-management. Strengthening the link between research and clinical practice, in close partnership with patients, will be crucial to better integrate their experiences and ensure the best possible use of healthcare services.</p
Hepatectomy alters adjuvant anti-PD-1 action in a mouse model of HCC but does not compromise neoadjuvant efficacy
No full textBackground aims: Immune checkpoint inhibitors (ICI) have transformed the management of advanced hepatocellular carcinoma (HCC), yet their integration in the perioperative setting remains insufficiently explored. This study aims to investigate the effect of hepatectomy on the tumor microenvironment and assess whether neoadjuvant or adjuvant anti-PD-1 therapy offers improved therapeutic outcomes.
Methods: Using a murine orthotopic HCC model, a non-curative partial hepatectomy was performed, removing a non-tumor-bearing lobe with anti-PD-1 administered as neoadjuvant or adjuvant therapy. In a separate experiment, curative hepatectomy (resection of the tumor-bearing lobe) was performed to evaluate recurrence and survival.
Results: Anti-PD-1 therapy significantly reduced tumor growth in non-surgical settings (p=0.0094), but its efficacy was lost in the adjuvant setting. This loss correlates with reduced infiltration of effector memory CD103⁺CD8⁺ T cells, increased expression of exhaustion markers (TIM-3, LAG-3), and accumulation of myeloid-derived suppressor cells (MDSC). MDSC depletion at the time of surgery improved adjuvant efficacy (p=0.0084), and delaying adjuvant ICI partially rescued responses, indicating a temporary postoperative immunosuppressive window. By contrast, neoadjuvant anti-PD-1 therapy significantly reduced tumor burden (p=0.0005), enhanced immune cell infiltration, and increased the expression of key activation markers on CD8+ cells (Tbx21, Gzma, Cxcr6, Cd69). Moreover, neoadjuvant treatment significantly reduced recurrence rates compared to sham treatment (35% vs. 68%, p=0.0405) and improved survival (p=0.0373), which was not achieved with adjuvant therapy.
Conclusions: Partial hepatectomy disrupts antitumor immunity and limits adjuvant ICI efficacy. Neoadjuvant anti-PD-1 immunotherapy offers a superior strategy compared to adjuvant immunotherapy in enhancing immune responses and reducing HCC recurrence.</p
Broadband and long-duration optical memory in <sup>171</sup>Yb<sup>3+</sup>:Y<sub>2</sub>SiO<sub>5</sub>
No full textOptical quantum memories are essential components for realizing the full potential of quantum networks. Among these, rare-earth-doped crystal memories stand out due to their large multimode storage capabilities. To maximize the multimode capacity in the time domain, it is key to simultaneously achieve large memory bandwidth and long optical storage time. Here, we demonstrate an atomic frequency comb optical memory in 171Yb3+:Y2SiO5 , with a memory bandwidth of 250 MHz and a storage time of up to 125 µs. The efficiency reaches 20% at short storage times, and 5% at 125 µs. These results were enabled by an optimized optical pumping scheme, guided by numerical modelling. Our approach is specifically designed for future spin-wave storage experiments, with the theoretical bandwidth limit set at 288 MHz by the hyperfine structure of 171Yb3+:Y2SiO5 . Additionally, we introduce an efficient method for synthesizing the optical pumping waveforms required for generating combs with tens of thousands of teeth, as well as a simple yet frequency-agile laser setup for optical pumping across a 10 GHz bandwidth
Techniques and Gender
No full textThis chapter examines the links between gender and technology in the history of contemporary Western societies. It offers an interpretation of the production of gender identities and the socialisation of technology in different contexts: from industry to consumption, from material cultures to digital cultures, from innovation to use, from mobilisation to protest.
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