Ultrafast Photo-Induced Charge Transfer Unveiled by Two-Dimensional Electronic Spectroscopy

The interaction of exciton and charge transfer (CT) states plays a central role in photo-induced CT processes in chemistry, biology and physics. In this work, we use a combination of two-dimensional electronic spectroscopy (2D-ES), pump-probe measurements and quantum chemistry to investigate the ultrafast CT dynamics in a lutetium bisphthalocyanine dimer in different oxidation states. It is found that in the anionic form, the combination of strong CT-exciton interaction and electronic asymmetry induced by a counter-ion enables CT between the two macrocycles of the complex on a 30 fs timescale. Following optical excitation, a chain of electron and hole transfer steps gives rise to characteristic cross-peak dynamics in the electronic 2D spectra, and we monitor how the excited state charge density ultimately localizes on the macrocycle closest to the counter-ion within 100 fs. A comparison with the dynamics in the radical species further elucidates how CT states modulate the electronic structure and tune fs-reaction dynamics. Our experiments demonstrate the unique capability of 2D-ES in combination with other methods to decipher ultrafast CT dynamics.Comment: 14 pages, 11 figures, and Supporting informatio

Rentabilidade econômica da produção de uva em louveira (sp) em diferentes sistemas de produção.

O presente trabalho foi desenvolvido junto aos produtores de uva do município de Louveira (SP) objetivando realizar uma análise de custo/benefício de três sistemas de produção aqui referidos por sistema tradicional, sistema alternativo 1 e sistema alternativo 2. Louveira é uma região com relevo ondulado e montanhoso com declives acentuados, e afloramentos rochosos. A fertilidade do solo varia de média a baixa e na maior parte do município os solos são muito susceptíveis à erosão. Embora a uva seja uma cultura que se adapta bem às condições edafoclimáticas de Louveira, para que o seu cultivo seja sustentável, dada as características citadas acima, o manejo da cultura deve utilizar técnicas que preservem a estrutura do recurso solo. No município ocorrem cerca de 3.500.000 pés de uva, distribuídos entre 397 produtores, 98% dos quais constituem agricultores familiares. Os produtores podem ser diferenciados quanto à tecnologia, uso de capital e práticas de cobertura no solo, no entanto, utilizam a mesma técnica de preparo do solo, tanto na implantação quanto na renovação da cultura, que ocorre a cada quinze anos. Foram analisadas três propriedades em áreas de LATOSSOLOS VERMELHO-AMARELOS argilosos, pouco profundos, bem drenados e de baixa fertilidade, derivados de filitos, gnaisses, xistos e granitos (Comissão de Solos, 1960; Oliveira et al., 1999). Os custos e benefícios foram avaliados sob a ótica da rentabilidade privada de uma atividade econômica, o que permite evidenciar a rentabilidade dos processos produtivos do ponto de vista privado ou do agricultor (NORONHA,1997). Os dados sobre custo, produtividade e preço foram levantados junto à Casa da Agricultura de Louveira para a produção de uva Niagara Rosada, no sistema latada. Esses parâmetros são concordantes com os publicados pela EMBRAPA (Maia e Mello, 2003). O Quadro 1 evidencia as diferenças de custo de produção, produtividade e preço da uva Niagara Rosada para os três sistemas de produção

Uso de diferentes doses de sêmen congelado/descongelado e fertilidade em cabras leiteiras na contra-estação: resultados preliminares.

Resumo: Para se obter a inseminação intrauterina de maneira rápida em cabras leiteiras, a EMBRAPA desenvolveu uma nova técnica de Inseminação Artificial (IA) (Fonseca et al. 2011, Embrapa Caprinos e Ovinos. Circular técnica, 43). Associada a ela, utiliza-se um novo protocolo de sincronização de cio usando dispositivos vaginais (60 mg MAP; Progespon®, Zoetis Indústria de Produtos Veterinários Ltda, Campinas, Brasil) por seis dias, além de 37,5 µg d-cloprostenol (Prolise®; ARSA S.R.L., Buenos Aires, Argentina) i.m. e 200 UI eCG (Novormon 5000®; Zoetis, Campinas, Brasil) i.m. 24 h antes da retirada do dispositivo. Todos os procedimentos são feitos entre 17:00 e 18:00h. Após a retirada do dispositivo o estro é monitorado duas vezes por dia por machos inteiros. Paralelo a isto, estudos relacionados a doses inseminantes de sêmen em associação a estas novas biotécnicas precisam ser realizados. A dose preconizada pelo CBRA é de 100 milhões de espermatozoides viáveis por palheta para congelação, com índice maior de 40% de espermatozoides com motilidade progressiva na hora da descongelação. Entretanto, com a nova técnica de IA e novos diluentes (Optixcell®, IMV), estas quantidades provavelmente poderiam ser reduzidas. O objetivo desse estudo foi testar o efeito de diferentes doses de sêmen congelado/descongelado sobre a taxa de gestação de cabras submetidas à indução de estro sincronizado. Os resultados obtidos preliminares sugerem que a dose mínima de sêmen necessária por palhetas seja a de 100 milhões de espermatozoides. Tanto a raça quanto as condições de manejo podem interferir nos resultados de gestação. Isto ressalta a importância de incluir um grupo com monta natural em estudos dessa natureza. A elevação do número de animais por grupo testado permitirá conclusões mais definitivas sobre a dose inseminante a ser utilizada. [Use of different doses of frozen / thawed semen and fertility in dairy goats in non-breeding season: Preliminary results].Edição dos resumos do XXIII Congresso Brasileiro de Reprodução Animal, Gramado, RS, Brasil, 15 a 17 de maio 2019

Housing Conditions and a Challenge with Lipopolysaccharide on the Day of Estrus Can Influence Gene Expression of the Corpus Luteum in Gilts.

Abstract: The corpus luteum (CL) is a temporary endocrine gland that plays a decisive role in the reproductive physiology of gilts. Recently, it has been suggested that exogenous factors may compromise the normal functioning of the CL. In the present study, we aimed to understand to what extent an acute and systemic challenge with lipopolysaccharide (LPS) on the day of estrus could compromise gene expression of gilts' CLs housed in different welfare conditions. For this, we housed 42 gilts in three different housing systems: crates, indoor group pens, and outdoor housing. Then, we challenged six females from each group with LPS and eight with saline (SAL) on the day of estrus. After slaughtering the gilts on the fifth day after the challenge, ovaries were collected for gene expression analysis by RT-qPCR. Housing system and LPS challenge did not have a significant interaction for any genes evaluated; thus, their effects were studied separately. We identified significant (p < 0.05) downregulation of the angiogenic genes VEGF and FTL1 among LPS-challenged animals. Meanwhile, we also observed upregulation of HSD3B1 gene among LPS-challenged animals. We found that STAR and LHCGR genes were differentially expressed depending on the housing system, which indicates that the environment may affect adaptation capabilities. Our results indicate that an acute health challenge on the estrus day alters CL gene expression; however, the role of the housing system remains uncertain

The role of proestrus on fertility and postovulatory uterine function in the cow

Abstract Modern protocols to synchronize ovulations for timed artificial insemination and timed embryo transfer that include manipulations in the proestrus period (i.e., between luteolysis and estrus) affect fertility in cattle. Specifically, stimulating pre-ovulatory follicle growth and exposure to estrogens after CL regression increase the proportion of cows pregnant and decrease late embryo mortality. Such effects may be due to both preovulatory actions of estrogens and post-ovulatory actions of progesterone, as concentrations of the later hormone may be changed in response to manipulations conducted during proestrus. In the first portion of this paper we describe strategies used recently to manipulate the proestrus period in protocols for synchronization of ovulation, and to present evidence of their effects on fertility. Manipulations of timing and prominence of sex steroids during the proestrus and early diestrus that affect fertility may act on targets such as the endometrium. This tissue expresses receptors for both estrogens and progesterone and these hormones change endometrial function to support conceptus growth and pregnancy maintenance. However, specific cellular and molecular mechanisms through which fertility is affected via manipulations of the proestrus are poorly understood. In the second portion of this paper we describe a welldefined animal model to study changes in endometrial function induced by manipulations conducted during the proestrus. Such manipulations induced endometrial changes on sex steroid receptors expression, cell proliferation, oxidative metabolism and eicosanoid synthesis in the uterus, but not on glucose transport to uterine lumen. In summary, evidence is accumulating to support a positive role of increasing duration and estrogen availability during the proestrus on fertility to synchronization protocols. Such positive effects may be through changes in endometrial function to stimulate conceptus growth and survival

Antimicrobial resistance among migrants in Europe: a systematic review and meta-analysis

BACKGROUND: Rates of antimicrobial resistance (AMR) are rising globally and there is concern that increased migration is contributing to the burden of antibiotic resistance in Europe. However, the effect of migration on the burden of AMR in Europe has not yet been comprehensively examined. Therefore, we did a systematic review and meta-analysis to identify and synthesise data for AMR carriage or infection in migrants to Europe to examine differences in patterns of AMR across migrant groups and in different settings. METHODS: For this systematic review and meta-analysis, we searched MEDLINE, Embase, PubMed, and Scopus with no language restrictions from Jan 1, 2000, to Jan 18, 2017, for primary data from observational studies reporting antibacterial resistance in common bacterial pathogens among migrants to 21 European Union-15 and European Economic Area countries. To be eligible for inclusion, studies had to report data on carriage or infection with laboratory-confirmed antibiotic-resistant organisms in migrant populations. We extracted data from eligible studies and assessed quality using piloted, standardised forms. We did not examine drug resistance in tuberculosis and excluded articles solely reporting on this parameter. We also excluded articles in which migrant status was determined by ethnicity, country of birth of participants' parents, or was not defined, and articles in which data were not disaggregated by migrant status. Outcomes were carriage of or infection with antibiotic-resistant organisms. We used random-effects models to calculate the pooled prevalence of each outcome. The study protocol is registered with PROSPERO, number CRD42016043681. FINDINGS: We identified 2274 articles, of which 23 observational studies reporting on antibiotic resistance in 2319 migrants were included. The pooled prevalence of any AMR carriage or AMR infection in migrants was 25·4% (95% CI 19·1-31·8; I2 =98%), including meticillin-resistant Staphylococcus aureus (7·8%, 4·8-10·7; I2 =92%) and antibiotic-resistant Gram-negative bacteria (27·2%, 17·6-36·8; I2 =94%). The pooled prevalence of any AMR carriage or infection was higher in refugees and asylum seekers (33·0%, 18·3-47·6; I2 =98%) than in other migrant groups (6·6%, 1·8-11·3; I2 =92%). The pooled prevalence of antibiotic-resistant organisms was slightly higher in high-migrant community settings (33·1%, 11·1-55·1; I2 =96%) than in migrants in hospitals (24·3%, 16·1-32·6; I2 =98%). We did not find evidence of high rates of transmission of AMR from migrant to host populations. INTERPRETATION: Migrants are exposed to conditions favouring the emergence of drug resistance during transit and in host countries in Europe. Increased antibiotic resistance among refugees and asylum seekers and in high-migrant community settings (such as refugee camps and detention facilities) highlights the need for improved living conditions, access to health care, and initiatives to facilitate detection of and appropriate high-quality treatment for antibiotic-resistant infections during transit and in host countries. Protocols for the prevention and control of infection and for antibiotic surveillance need to be integrated in all aspects of health care, which should be accessible for all migrant groups, and should target determinants of AMR before, during, and after migration. FUNDING: UK National Institute for Health Research Imperial Biomedical Research Centre, Imperial College Healthcare Charity, the Wellcome Trust, and UK National Institute for Health Research Health Protection Research Unit in Healthcare-associated Infections and Antimictobial Resistance at Imperial College London

Global economic burden of unmet surgical need for appendicitis

Background: There is a substantial gap in provision of adequate surgical care in many low-and middle-income countries. This study aimed to identify the economic burden of unmet surgical need for the common condition of appendicitis. Methods: Data on the incidence of appendicitis from 170 countries and two different approaches were used to estimate numbers of patients who do not receive surgery: as a fixed proportion of the total unmet surgical need per country (approach 1); and based on country income status (approach 2). Indirect costs with current levels of access and local quality, and those if quality were at the standards of high-income countries, were estimated. A human capital approach was applied, focusing on the economic burden resulting from premature death and absenteeism. Results: Excess mortality was 4185 per 100 000 cases of appendicitis using approach 1 and 3448 per 100 000 using approach 2. The economic burden of continuing current levels of access and local quality was US $92 492 million using approach 1 and$73 141 million using approach 2. The economic burden of not providing surgical care to the standards of high-income countries was $95 004 million using approach 1 and$75 666 million using approach 2. The largest share of these costs resulted from premature death (97.7 per cent) and lack of access (97.0 per cent) in contrast to lack of quality. Conclusion: For a comparatively non-complex emergency condition such as appendicitis, increasing access to care should be prioritized. Although improving quality of care should not be neglected, increasing provision of care at current standards could reduce societal costs substantially

Pooled analysis of WHO Surgical Safety Checklist use and mortality after emergency laparotomy

Background The World Health Organization (WHO) Surgical Safety Checklist has fostered safe practice for 10 years, yet its place in emergency surgery has not been assessed on a global scale. The aim of this study was to evaluate reported checklist use in emergency settings and examine the relationship with perioperative mortality in patients who had emergency laparotomy. Methods In two multinational cohort studies, adults undergoing emergency laparotomy were compared with those having elective gastrointestinal surgery. Relationships between reported checklist use and mortality were determined using multivariable logistic regression and bootstrapped simulation. Results Of 12 296 patients included from 76 countries, 4843 underwent emergency laparotomy. After adjusting for patient and disease factors, checklist use before emergency laparotomy was more common in countries with a high Human Development Index (HDI) (2455 of 2741, 89.6 per cent) compared with that in countries with a middle (753 of 1242, 60.6 per cent; odds ratio (OR) 0.17, 95 per cent c.i. 0.14 to 0.21, P <0001) or low (363 of 860, 422 per cent; OR 008, 007 to 010, P <0.001) HDI. Checklist use was less common in elective surgery than for emergency laparotomy in high-HDI countries (risk difference -94 (95 per cent c.i. -11.9 to -6.9) per cent; P <0001), but the relationship was reversed in low-HDI countries (+121 (+7.0 to +173) per cent; P <0001). In multivariable models, checklist use was associated with a lower 30-day perioperative mortality (OR 0.60, 0.50 to 073; P <0.001). The greatest absolute benefit was seen for emergency surgery in low- and middle-HDI countries. Conclusion Checklist use in emergency laparotomy was associated with a significantly lower perioperative mortality rate. Checklist use in low-HDI countries was half that in high-HDI countries.Peer reviewe