Molecular Engineering of Metalloporphyrins for High‐Performance Energy Storage: Central Metal Matters

Porphyrin derivatives represent an emerging class of redox-active materials for sustainable electrochemical energy storage. However, their structure–performance relationship is poorly understood, which confines their rational design and thus limits access to their full potential. To gain such understanding, we here focus on the role of the metal ion within porphyrin molecules. The A$_2$B$_2$-type porphyrin 5,15-bis(ethynyl)-10,20-diphenylporphyrin and its first-row transition metal complexes from Co to Zn are used as models to investigate the relationships between structure and electrochemical performance. It turned out that the choice of central metal atom has a profound influence on the practical voltage window and discharge capacity. The results of DFT calculations suggest that the choice of central metal atom triggers the degree of planarity of the porphyrin. Single crystal diffraction studies illustrate the consequences on the intramolecular rearrangement and packing of metalloporphyrins. Besides the direct effect of the metal choice on the undesired solubility, efficient packing and crystallinity are found to dictate the rate capability and the ion diffusion along with the porosity. Such findings open up a vast space of compositions and morphologies to accelerate the practical application of resource-friendly cathode materials to satisfy the rapidly increasing need for efficient electrical energy storage

Shifting cancer care towards Multidisciplinarity: the cancer center certification program of the German cancer society

Background: Over the last decades numerous initiatives have been set up that aim at translating the best available medical knowledge and treatment into clinical practice. The inherent complexity of the programs and discrepancies in the terminology used make it difficult to appreciate each of them distinctly and compare their specific strengths and weaknesses. To allow comparison and stimulate dialogue between different programs, we in this paper provide an overview of the German Cancer Society certification program for multidisciplinary cancer centers that was established in 2003. Main body: In the early 2000s the German Cancer Society assessed the available information on quality of cancer care in Germany and concluded that there was a definite need for a comprehensive, transparent and evidence-based system of quality assessment and control. This prompted the development and implementation of a voluntary cancer center certification program that was promoted by scientific societies, health-care providers, and patient advocacy groups and based on guidelines of the highest quality level (S3). The certification system structures the entire process of care from prevention to screening and multidisciplinary treatment of cancer and places multidisciplinary teams at the heart of this program. Within each network of providers, the quality of care is documented using tumor-specific quality indicators. The system started with breast cancer centers in 2003 and colorectal cancer centers in 2006. In 2017, certification systems are established for the majority of cancers. Here we describe the rationale behind the certification program, its history, the development of the certification requirements, the process of data collection, and the certification process as an example for the successful implementation of a voluntary but powerful system to ensure and improve quality of cancer care. Conclusion: Since 2003, over 1 million patients had their primary tumors treated in a certified center. There are now over 1200 sites for different tumor entities in four countries that have been certified in accordance with the program and transparently report their results from multidisciplinary treatment for a substantial proportion of cancers. This led to a fundamental change in the structure of cancer care in Germany and neighboring countries within one decade

Robotic surgery in emergency setting : 2021 WSES position paper

Background Robotics represents the most technologically advanced approach in minimally invasive surgery (MIS). Its application in general surgery has increased progressively, with some early experience reported in emergency settings. The present position paper, supported by the World Society of Emergency Surgery (WSES), aims to provide a systematic review of the literature to develop consensus statements about the potential use of robotics in emergency general surgery. Methods This position paper was conducted according to the WSES methodology. A steering committee was constituted to draft the position paper according to the literature review. An international expert panel then critically revised the manuscript. Each statement was voted through a web survey to reach a consensus. Results Ten studies (3 case reports, 3 case series, and 4 retrospective comparative cohort studies) have been published regarding the applications of robotics for emergency general surgery procedures. Due to the paucity and overall low quality of evidence, 6 statements are proposed as expert opinions. In general, the experts claim for a strict patient selection while approaching emergent general surgery procedures with robotics, eventually considering it for hemodynamically stable patients only. An emergency setting should not be seen as an absolute contraindication for robotic surgery if an adequate training of the operating surgical team is available. In such conditions, robotic surgery can be considered safe, feasible, and associated with surgical outcomes related to an MIS approach. However, there are some concerns regarding the adoption of robotic surgery for emergency surgeries associated with the following: (i) the availability and accessibility of the robotic platform for emergency units and during night shifts, (ii) expected longer operative times, and (iii) increased costs. Further research is necessary to investigate the role of robotic surgery in emergency settings and to explore the possibility of performing telementoring and telesurgery, which are particularly valuable in emergency situations. Conclusions Many hospitals are currently equipped with a robotic surgical platform which needs to be implemented efficiently. The role of robotic surgery for emergency procedures remains under investigation. However, its use is expanding with a careful assessment of costs and timeliness of operations. The proposed statements should be seen as a preliminary guide for the surgical community stressing the need for reevaluation and update processes as evidence expands in the relevant literature.Peer reviewe

Training curriculum in minimally invasive emergency digestive surgery : 2022 WSES position paper

Background Minimally invasive surgery (MIS), including laparoscopic and robotic approaches, is widely adopted in elective digestive surgery, but selectively used for surgical emergencies. The present position paper summarizes the available evidence concerning the learning curve to achieve proficiency in emergency MIS and provides five expert opinion statements, which may form the basis for developing standardized curricula and training programs in emergency MIS. Methods This position paper was conducted according to the World Society of Emergency Surgery methodology. A steering committee and an international expert panel were involved in the critical appraisal of the literature and the development of the consensus statements. Results Thirteen studies regarding the learning curve in emergency MIS were selected. All but one study considered laparoscopic appendectomy. Only one study reported on emergency robotic surgery. In most of the studies, proficiency was achieved after an average of 30 procedures (range: 20-107) depending on the initial surgeon's experience. High heterogeneity was noted in the way the learning curve was assessed. The experts claim that further studies investigating learning curve processes in emergency MIS are needed. The emergency surgeon curriculum should include a progressive and adequate training based on simulation, supervised clinical practice (proctoring), and surgical fellowships. The results should be evaluated by adopting a credentialing system to ensure quality standards. Surgical proficiency should be maintained with a minimum caseload and constantly evaluated. Moreover, the training process should involve the entire surgical team to facilitate the surgeon's proficiency. Conclusions Limited evidence exists concerning the learning process in laparoscopic and robotic emergency surgery. The proposed statements should be seen as a preliminary guide for the surgical community while stressing the need for further research.Peer reviewe

Characterization of a novel picornavirus isolate from a diseased European eel (Anguilla anguilla)

A novel picornavirus was isolated from specimens of a diseased European eel (Anguilla anguilla). This virus induced a cytopathic effect in eel embryonic kidney cells and high mortality in a controlled transmission study using elvers. Eel picornavirus has a genome of 7,496 nucleotides that encodes a polyprotein of 2,259 amino acids. It has a typical picornavirus genome layout, but its low similarity to known viral proteins suggests a novel species in the family Picornaviridae

Erythrocyte phenotyping and alloimmunization in patients with sickle cell anemia assisted at HEMOAL from Alagoas

Objective: To determine the erythrocyte phenotyping in blood donors and patients with sickle cell anemia (SS) assisted at Hemocentro of Alagoas and also the frequency and factors associated with erythrocyte alloimmunization. Methods: Cross-sectional study with 102 patients with sickle cell anemia (SS) and 100 blood donors. This study was approved by the Ethical Committee of the Federal University of São Paulo and by the Ethical Committee of the University of Science of Health of Alagoas. Patients and blood donors were requested to sign an informed consent form prior to enrolment. The following tests were performed: erythrocyte phenotyping by gel centrifugation, Direct antiglobulin test, Indirect antiglobulin test, and detection of irregular antibodies by panels of phenotyped red blood cells. Variables were compared by Mann-Whitney test and c 2 test or exact Fisher test. Factors associate with alloimmunization was analyzed by univariate and multiple logistic regression analysis. Differences were considered significant if p<0.002. Results: The most frequent antigens found in patients and blood donors were: c (93.1% vs. 83.0%), and (96.1% vs. 94.0%), M (82.4% vs. 82.0%), s (92.2% vs. 79.0%), JK(a) (88.2% vs. 82.0), respectively. Significant differences were observed between the frequency of the phenotype of patients and donors in regard to antigens s, FY(a) and JK(b). From 79 transfused patients, 10 (12.7%) presented positive Indirect Coombs. Thirteen alloantibodies were found, 7 from Rh system, 2 from Kell and 4 were not identified. Factors associated with alloimmunization were the period of time between the last transfusion and the data of the test and being submitted to more than 10 red blood cell transfusions. Patients who received more than 10 transfusions presented a likelihood of presenting alloimmunization 16.39 (2.23-120.59) times higher than who received less than 10 transfusions. All patients presented a negative Direct antiglobulin test. Conclusion: The prevalence of alloimmunization in patients with sickle cell anemia was 12.7% with 70% of antibodies belonging to Rh and Kell systems. This study shows the importance of performing erythrocyte phenotyping in blood donors and receptors in order to decrease the risk of alloimmunization.Objetivo: Determinar a imunofenotipagem eritrocitária em doadores de sangue e em pacientes com anemia falciforme (SS) atendidos no Hemocentro de Alagoas, além de descrever a frequência e os fatores associados à aloimunização eritrocitária. Método: Estudo transversal realizado com 102 pacientes com anemia falciforme (SS) e 100 doadores de sangue. Estudo aprovado pelos Comitês de Ética em Pesquisa da Universidade Federal de São Paulo e da Universidade de Ciências da Saúde de Alagoas. Foi solicitada a assinatura do Termo de Consentimento Livre e Esclarecido antes da inclusão no estudo. Realizou-se a fenotipagem eritrocitária pelo método de gel centrifugação, teste de Coombs Direto (CD), Coombs Indireto (CI) e detecção de anticorpos irregulares por painéis de hemácias fenotipadas. Os dados coletados foram comparados por meio do teste de Mann- Whitney e qui-quadrado ou teste exato de Fisher. Para análise dos fatores associados à aloimunização foi utilizada a regressão logística univariada e múltipla. Considerou-se nível de significância estatística p<0,05. Resultados: Os antígenos mais frequentes entre os pacientes e os doadores foram, c (93,1% vs. 83,0%), e (96,1% vs. 94,0%), M (82,4% vs. 82,0%), s (92,2% vs. 79,0%), JK(a) (88,2% vs. 82,0), respectivamente. Observaram-se diferenças estatísticas significantes entre as frequências dos fenótipos dos pacientes e dos doadores em relação aos antígenos s, FY(a) e JK(b). Dos 79 pacientes transfundidos, 10 (12,7%) apresentaram CI positivo. Foram detectados 13 aloanticorpos, sete do sistema Rh, dois do Kell e quatro não foram identificados. Os fatores associados à aloimunização foram o intervalo de tempo entre a última transfusão e a data do exame e ter recebido mais de 10 transfusões de hemácias. O paciente que recebeu mais de 10 transfusões apresentou uma chance 16,39 (IC95%: 2,23- 120,59) vezes maior de ser aloimunizado, comparado àqueles que receberam menos de 10 transfusões. Todos os pacientes apresentaram CD negativo. Conclusão: A prevalência de aloimunização nos pacientes portadores de anemia falciforme foi 12,7%, sendo 70% dos anticorpos encontrados pertencente a grupos sanguíneos Rh e Kell. Esse estudo mostra a importância de realizar a fenotipagem eritrocitária em doadores e receptores para diminuir o risco de aloimunização.TEDEBV UNIFESP: Teses e dissertaçõe

Does Forest Continuity Enhance the Resilience of Trees to Environmental Change?

<div><p>There is ample evidence that continuously existing forests and afforestations on previously agricultural land differ with regard to ecosystem functions and services such as carbon sequestration, nutrient cycling and biodiversity. However, no studies have so far been conducted on possible long-term (>100 years) impacts on tree growth caused by differences in the ecological continuity of forest stands. In the present study we analysed the variation in tree-ring width of sessile oak (<i>Quercus petraea</i> (Matt.) Liebl.) trees (mean age 115–136 years) due to different land-use histories (continuously existing forests, afforestations both on arable land and on heathland). We also analysed the relation of growth patterns to soil nutrient stores and to climatic parameters (temperature, precipitation). Tree rings formed between 1896 and 2005 were widest in trees afforested on arable land. This can be attributed to higher nitrogen and phosphorous availability and indicates that former fertilisation may continue to affect the nutritional status of forest soils for more than one century after those activities have ceased. Moreover, these trees responded more strongly to environmental changes – as shown by a higher mean sensitivity of the tree-ring widths – than trees of continuously existing forests. However, the impact of climatic parameters on the variability in tree-ring width was generally small, but trees on former arable land showed the highest susceptibility to annually changing climatic conditions. We assume that incompletely developed humus horizons as well as differences in the edaphon are responsible for the more sensitive response of oak trees of recent forests (former arable land and former heathland) to variation in environmental conditions. We conclude that forests characterised by a long ecological continuity may be better adapted to global change than recent forest ecosystems.</p></div

Variation of radial growth of sessile oak (<i>Quercus petraea</i>) among historical land-use types between 1896 and 2005.

<p>Data represent site chronologies based on 10 trees per sample site; a) former arable land (10 sites), (b) former heathland (8 sites), and (c) continuously existing forests (7 sites).</p