From Coordination to π-Hole Chemistry of Transition Metals: Metalloporphyrins as a Case of Study.

Herein we have evidenced the formation of favorable π-hole Br···metal noncovalent interactions (NCIs) involving elements from groups 9, 11 and 12. More in detail, M (M = Co2+, Ni2+, Cu2+ and Zn2+) containing porphyrins have been synthesized and their supramolecular assemblies structurally characterized by means of single crystal X-ray diffraction and Hirshfeld surface analyses, revealing the formation of directional Br···M contacts in addition to ancillary hydrogen bond and lone pair-π bonds. Computations at the PBE0-D3/def2-TZVP level of theory revealed the π-hole nature of the Br···M interaction. In addition, the physical nature of these NCIs was studied using Quantum Chemistry methodologies, providing evidence of π-hole Spodium and Regium bonds in Zn2+ and Cu2+ porphyrins, in addition to unveiling the presence of  a π-hole for group 9 (Co2+). On the other hand, group 10 (Ni2+) acted as both electron donor and acceptor moiety without showing an electropositive π-hole. Owing to the underexplored potential of π-hole interactions in transition metal chemistry, we believe the results reported herein will be useful in supramolecular chemistry, organometallics, and solid-state chemistry by i) putting under the spotlight the π-hole chemistry involving first row transition metals and ii) unlocking a new tool to direct the self-assembly of metalloporphyrins.

Using Hybrid PDI-Fe3O4 Nanoparticles for Capturing Aliphatic Alcohols: Halogen Bonding vs. Lone Pair-π Interactions.

In this study, Fe3O4 nanoparticles (FeNPs) decorated with halogenated perylene diimides (PDIs) have been used for capturing VOCs (volatile organic compounds) through noncovalent binding. Concretely, we have used tetrachlorinated/brominated PDIs as well as a nonhalogenated PDI as a reference system. On the other hand, methanol, ethanol, propanol, and butanol were used as VOCs. Experimental studies along with theoretical calculations (the BP86-D3/def2-TZVPP level of theory) pointed to two possible and likely competitive binding modes (lone pair-π through the π-acidic surface of the PDI and a halogen bond via the σ-holes at the Cl/Br atoms). More in detail, thermal desorption (TD) experiments showed an increase in the VOC retention capacity upon increasing the length of the alkyl chain, suggesting a preference for the interaction with the PDI aromatic surface. In addition, the tetrachlorinated derivative showed larger VOC retention times compared to the tetrabrominated analog. These results were complemented by several state-of-the-art computational tools, such as the electrostatic surface potential analysis, the Quantum Theory of Atoms in Molecules (QTAIM), as well as the noncovalent interaction plot (NCIplot) visual index, which were helpful to rationalize the role of each interaction in the VOC···PDI recognition phenomena.

Comprehensive Genomic Studies on the Cell Blocks of Pancreatic Cancer.

Pancreatic cancer is one of the deadliest malignancies, characterized by late-stage diagnosis and limited treatment options. Comprehensive genomic profiling plays an important role in understanding the molecular mechanisms underlying the disease and identifying potential therapeutic targets. Cell blocks (CBs), derived from EUS-FNA, have become valuable resources for diagnosis and genomic analysis. We examine the molecular profile of pancreatic ductal adenocarcinoma (PDAC) using specimens obtained from CB EUS-FNA, across a large gene panel, within the framework of next-generation sequencing (NGS). Our findings revealed that over half (55%) of PDAC CB cases provided adequate nucleic acid for next-generation sequencing, with tumor cell percentages averaging above 30%. Despite challenges such as low DNA quantification and degraded DNA, sequencing reads showed satisfactory quality control statistics, demonstrating the detection of genomic alterations. Most cases (84.6%) harbored at least one gene variant, including clinically significant gene mutation variants such as KRAS, TP53, and CDKN2A. Even at minimal concentrations, as long as the extracted DNA is of high quality, performing comprehensive molecular profiling on PDAC samples from cell blocks has remained feasible. This strategy has yielded valuable information about the diagnosis, genetic landscape, and potential therapeutic targets, aligning closely with a precision cytopathology approach.

Agreement between a web collaborative dataset and an administrative dataset to assess the retail food environment in Mexico.

BACKGROUND: Latin American countries are often limited in the availability of food outlet data. There is a need to use online search engines that allow the identification of food outlets and assess their agreement with field observations. We aimed to assess the agreement in the density of food outlets provided by a web collaborative data (Google) against the density obtained from an administrative registry. We also determined whether the agreement differed by type of food outlet and by area-level socioeconomic deprivation. METHODS: In this cross-sectional study, we analyzed 1,693 census tracts from the municipalities of Hermosillo, Leon, Oaxaca de Juarez, and Tlalpan. The Google service was used to develop a tool for the automatic acquisition of food outlet data. To assess agreement, we compared food outlet densities obtained with Google against those registered in the National Statistical Directory of Economic Units (DENUE). Continuous densities were assessed using Bland-Altman plots and concordance correlation coefficient (CCC), while agreement across tertiles of density was estimated using weighted kappa. RESULTS: The CCC indicated a strong correlation between Google and DENUE in the overall sample (0.75); by food outlet, most of the correlations were from negligible (0.08) to moderate (0.58). The CCC showed a weaker correlation as deprivation increased. Weighted kappa indicated substantial agreement between Google and DENUE across all census tracts (0.64). By type of food outlet, the weighted kappa showed substantial agreement for restaurants (0.69) and specialty food stores (0.68); the agreement was moderate for convenience stores/small food retail stores (0.49) and fair for candy/ice cream stores (0.30). Weighted kappa indicated substantial agreement in low-deprivation areas (0.63); in very high-deprivation areas, the agreement was moderate (0.42). CONCLUSIONS: Google could be useful in assessing fixed food outlet densities as a categorical indicator, especially for some establishments, like specialty food stores and restaurants. The data could also be informative of the availability of fixed food outlets, particularly in less deprived areas.

Diphenylene Iodonium as a Prominent Halogen Bond Donor: The Case of Human Monoamine Oxidase B.

Herein we have investigated the formation and interplay of several noncovalent interactions (NCIs) involved in the inhibition of human monoamine oxidase B (MAO B). Concretely, an inspection of the Protein Data Bank (PDB) revealed the formation of a halogen bond (HlgB) between a diphenylene iodonium (DPI) inhibitor and a water molecule present in the active site, in addition to a noncovalent network of interactions (e. g. lone pair-π, hydrogen bonding, OH-π, CH-π and π-stacking interactions) with surrounding protein residues. Several theoretical models were built to understand the strength and directionality features of the HlgB in addition to the interplay with other NCIs present in the active site of the enzyme. Besides, a computational study was carried out using DPI as HlgB donor and several electron rich molecules (CO, H2O, CH2O, HCN, pyridine, OCN-, SCN-, Cl- and Br-) as HlgB acceptors. The results were analyzed using several state-of-the-art computational tools. We expect that our results will be useful for those scientists working in the fields of rational drug design, chemical biology as well as supramolecular chemistry.

Indocyanine green fluorescence imaging: an effective method to find inguinal sentinel lymph node in a case of vulvar carcinoma.

The aim was to demonstrate that the technique of near infrared range/indocyanine green (NIR/ICG) could aid the detection of inguinal sentinel lymph nodes in patients with vulvar cancer, in addition to technetium-99m (Tc-99m) scanning. We present a case report of sentinel lymph node detection in a patient with vulvar cancer with two methods: Tc-99m scan and NIR/ICG. The video showed that bilateral inguinal lymph nodes were detected both by Tc gamma probe and NIR/ICG. NIR/ICG may be a safe and effective alternative method for identifying sentinel lymph nodes in cases of early-stage vulvar cancer, although more evidence is required.

Vessel-Guided Mesohepatectomy for Liver Partition and Staged Major Parenchyma-Sparing Hepatectomies with Super-Selective Portal Vein Embolization or Enhanced ALPPS to Achieve R0 Resection for Colorectal Liver Metastases at the Hepatocaval Confluence.

Background. R0 minor parenchyma-sparing hepatectomy (PSH) is feasible for colorectal liver metastases (CRLM) in contact with hepatic veins (HV) at hepatocaval confluence since HV can be reconstructed, but in the case of contact with the first-order glissonean pedicle (GP), major hepatectomy is mandatory. To pursue an R0 parenchyma-sparing policy, we proposed vessel-guided mesohepatectomy for liver partition (MLP) and eventually combination with liver augmentation techniques for staged major PSH. Methods. We analyzed 15 consecutive vessel-guided MLPs for CRLM at the hepatocaval confluence. Patients had a median of 11 (range: 0-67) lesions with a median diameter of 3.5 cm (range: 0.0-8.0), bilateral in 73% of cases. Results. Grade IIIb or more complications occurred in 13%, median hospital stay was 14 (range: 6-62) days, 90-day mortality was 0%. After a median follow-up of 17.5 months, 1-year OS and RFS were 92% and 62%. In nine (64%) patients, MLP was combined with portal vein embolization (PVE) or ALPPS to perform staged R0 major PSH. Future liver remnant (FLR) volume increased from a median of 15% (range: 7-20%) up to 41% (range: 37-69%). Super-selective PVE was performed in three (33%) patients and enhanced ALPPS (e-ALPPS) in six (66%). In two e-ALPPS an intermediate stage of deportalized liver PSH was necessary to achieve adequate FLR volume. Conclusions. Vessel-guided MLP may transform the liver in a paired organ. In selected cases of multiple bilobar CRLM, to guarantee oncological radicality (R0), major PSH is feasible combining advanced surgical parenchyma sparing with liver augmentation techniques when FLR volume is insufficient.

On the Importance of Halogen and Chalcogen Bonds in the Solid State of Nucleic Acids: A Combined Crystallographic and Theoretical Perspective.

In this work, intra- and intermolecular halogen and chalcogen bonds (HlgBs and ChBs, respectively) present in the solid state of nucleic acids (NAs) have been studied at the RI-MP2/def2-TZVP level of theory. To achieve this, a Protein Data Bank (PDB) survey was carried out, revealing a series of structures in which Br/I or S/Se/Te atoms belonging to nucleobases or pentose rings were involved in noncovalent interactions (NCIs) with electron-rich species. The energetics and directionality of these NCIs were rationalized through a computational study, which included the use of Molecular Electrostatic Potential (MEP) surfaces, the Quantum Theory of Atoms in Molecules (QTAIM), and Non Covalent Interaction plot (NCIplot) and Natural Bonding Orbital (NBO) techniques.

[Spatial analysis of maternal morbidity and mortality in users of the Brazilian Unified National Health System in the city of Rio de Janeiro, Brazil, 2014-2016]. / Análise espacial da morbimortalidade materna em usuárias do Sistema Único de Saúde no Município do Rio de Janeiro, Brasil, 2014-2016.

The objective of this study is to analyze the maternal morbidity and mortality of women treated in hospitals of the Brazilian Unified National Health System (SUS) in the city of Rio de Janeiro in the period 2014-2016. An ecological study was conducted using data from the Brazilian Information System on Live Birth (SINASC), the Brazilian Mortality Information System (SIM), and the Brazilian Hospital Information System (SIH/SUS). For the analysis of the maternal mortality ratio (MMR), data from the SIM were used. For the analysis of maternal morbidity, World Health Organization criteria were used to estimate the ratios of maternal near miss and potentially life-threatening conditions. SINASC was used to retrieve data on the number of live births, for demographic characterization, social aspects, and access to prenatal care. To evaluate the spatial association between the indicators MMR, ratios of maternal near miss, and potentially life-threatening conditions and the demographic, social, obstetric, and access indicators, obtained from SINASC, the bivariate Moran Index was estimated with a significance level of 0.05, using the GeoDa program. In the period analyzed, the MMR in the Rio de Janeiro was 94.16/100,000 live births, the ratio of maternal near miss was 28.21/1,000 live births, and the potentially life-threatening conditions was 34.31/1,000 live births. Cases of potentially life-threatening conditions were used for the first time in this study and presented diagnoses and procedures during hospitalization more consistent with the maternal mortality profile in the city of Rio de Janeiro. There was a significant association between MMR and percentage of live births in SUS, potentially life-threatening conditions and percentage of live births in SUS, and potentially life-threatening conditions and being single.

O objetivo deste estudo é analisar a morbimortalidade materna de mulheres atendidas em hospitais do Sistema Único de Saúde (SUS) no Município do Rio de Janeiro, Brasil, no período de 2014 a 2016. Foi realizado estudo ecológico, por meio da coleta de dados do Sistema de Informações sobre Nascidos Vivos (SINASC), Sistema de Informação sobre Mortalidade (SIM) e Sistema de Informações Hospitalares (SIH/SUS). Para analisar a razão de mortalidade materna (RMM), foram utilizados dados do SIM. Para investigar a morbidade materna, adotaram-se critérios da Organização Mundial da Saúde para estimar as razões de near miss materno e de condições potencialmente ameaçadoras à vida. Dados do SINASC foram usados para número de nascidos vivos e caracterização demográfica, social e de acesso a serviço de pré-natal. Para avaliar a associação espacial entre os indicadores RMM, razões de near miss materno e condições potencialmente ameaçadoras à vida e os indicadores demográficos, sociais, obstétricos e de acesso obtidos no SINASC, foi calculado o índice de Moran bivariado com nível de 0,05 de significância, por meio do programa GeoDa. No período analisado, a RMM no Município do Rio de Janeiro foi de 94,16/100 mil nascidos vivos, a razão de near miss materno de 28,21/1.000 nascidos vivos e a razão de condições potencialmente ameaçadoras à vida de 34,31/1.000 nascidos vivos. Casos de condições potencialmente ameaçadoras à vida foram utilizados pela primeira vez neste estudo e apresentaram diagnósticos de internação e procedimentos realizados mais condizentes com o perfil de mortalidade materna no Município do Rio de Janeiro. Houve associação significativa entre RMM e percentual de nascidos vivos no SUS, razão de condições potencialmente ameaçadoras à vida e percentual de nascidos vivos no SUS e razão de condições potencialmente ameaçadoras à vida e ser solteira.

El objetivo de este estudio es analizar la morbimortalidad materna de las mujeres atendidas en hospitales del Sistema Único de Salud (SUS) del municipio de Rio de Janeiro, Brasil, en el período 2014-2016. Fue realizado un estudio ecológico, por medio del uso de datos del Sistema de Información sobre Nacidos Vivos (SINASC), Sistema de Información sobre Mortalidad (SIM) y del Sistema de Información Hospitalaria (SIH/SUS). Para el análisis de la razón de mortalidad materna (RMM) se utilizaron los datos SIM. Para el análisis de la morbilidad materna se utilizaron los criterios de la Organización Mundial de la Salud para estimar las razón de near miss materno y de condiciones potencialmente amenazantes a la vida. Para el número de nacidos vivos y la información demográfica, social y de acceso al servicio de atención prenatal fueron utilizados datos del SINASC. Para evaluar la asociación espacial entre los indicadores RMM, razon de near miss materno y razon de condiciones potencialmente amenazantes a la vida y los indicadores demográficos, sociales, obstétricos y de accesos obtenidos en el SINASC fue calculado el Índice de Moran bivariado con nivel de 0,05 de significación, usando el programa GeoDa. En el período analizado, la RMM en el municipio de Rio de Janeiro fue de 94,16/100.000 nascidos vivos, la razón de near miss materno de 28,21/1.000 nascidos vivos y la razón de condiciones potencialmente amenazantes a la vida de 34,31/1.000 nascidos vivos. Los casos de condiciones potencialmente amenazantes a la vida se utilizaron por primera vez en este estudio y presentaron diagnósticos de hospitalización y procedimientos realizados más acordes con el perfil de mortalidad materna en el Municipio de Rio de Janeiro Hubo una asociación significativa entre RMM y el porcentaje de nacidos vivos en el SUS, razón de condiciones potencialmente amenazantes a la vida y el porcentaje de nacidos vivos en el SUS y razón de condiciones potencialmente amenazantes a la vida y ser soltera.

On-chip monitoring of toxic gases: capture and label-free SERS detection with plasmonic mesoporous sorbents.

The detection of the spread of toxic gas molecules in the air at low concentration in the field requires a robust miniaturized system combined with an analytical technique that is portable and able to detect and identify the molecules, as is the case with surface enhanced Raman scattering (SERS). This work aims to address capability gaps faced by first responders in real-time detection, identification and monitoring of neurotoxic gases by developing robust, reliable and reusable SERS microfluidic chips. Thus, the key performance attributes of a portable SERS detection system that must be addressed in detail are its limit of detection, response time and reusability. To this purpose, we integrate a 3D plasmonic architecture based on closely packed mesoporous silica (MCM48) nanospheres decorated with Au nanoparticle arrays, denoted as MCM48@Au, into a Si microfluidic chip designed and used for preconcentration and label-free detection of gases at a trace concentration level. The SERS performance of the plasmonic platform is thoroughly analyzed using DMMP as a model neurotoxic simulant over a 1 cm2 SERS active area and over a range of concentrations from 100 ppbV to 2.5 ppmV. The preconcentration-based SERS signal amplification by the mesoporous silica moieties is evaluated against dense silica counterparts, denoted as Stöber@Au. To assess the potential for applications in the field, the microfluidic SERS chip has been interrogated with a portable Raman spectrometer, evaluated with temporal and spatial resolution and subjected to several gas detection/regeneration cycles. The reusable SERS chip shows exceptional performance for the label-free monitoring of 2.5 ppmV gaseous DMMP.

Exploring the Outcome of Disappearance or Small Remnants of Colorectal Liver Metastases during First-Line Chemotherapy on Hepatobiliary Contrast-Enhanced and Diffusion-Weighted MR Imaging.

We aimed to evaluate the outcome of the disappearance or small remnants of colorectal liver metastases during first-line chemotherapy assessed by hepatobiliary contrast-enhanced and diffusion-weighted MR imaging (DW-MRI). Consecutive patients with at least one disappearing liver metastasis (DLM) or small residual liver metastases (≤10 mm) assessed by hepatobiliary contrast-enhanced and DW-MRI during first-line chemotherapy were included. Liver lesions were categorized into three groups: DLM; residual tiny liver metastases (RTLM) when ≤5 mm; small residual liver metastases (SRLM) when >5mm and ≤10 mm. The outcome of resected liver metastases was assessed in terms of pathological response, whereas lesions left in situ were evaluated in terms of local relapse or progression. Fifty-two outpatients with 265 liver lesions were radiologically reviewed; 185 metastases fulfilled the inclusion criteria: 40 DLM, 82 RTLM and 60 SRLM. We observed a pCR rate of 75% (3/4) in resected DLM and 33% (12/36) of local relapse for DLM left in situ. We observed a risk of relapse of 29% and 57% for RTLM and SRLM left in situ, respectively, and a pCR rate of about 40% overall for resected lesions. DLM assessed via hepatobiliary contrast-enhanced and DW-MRI very probably indicates a complete response. The surgical removal of small remnants of liver metastases should always be advocated whenever technically possible.

Tetrel bonds involving a CF3 group participate in protein-drug recognition: a combined crystallographic and computational study.

In this study, the ability of CF3 groups to bind to the electron-rich side chains and backbone groups of proteins has been investigated by combining a Protein Data Bank (PDB) survey and ab initio quantum mechanics calculations. More precisely, an inspection of the PDB involving organic ligands containing a CF3 group and electron-rich atoms (A = N, O and S) in the vicinity revealed 419 X-ray structures exhibiting CF3⋯A tetrel bonds (TtBs). In a posterior stage, those hits that exhibited the most relevant features in terms of directionality and intermolecular distance were selected for theoretical calculations at the RI-MP2/def2-TZVPD level of theory. Also, Hammett's regression plots of several TtB complexes involving meta- and para-substituted benzene derivatives were computed to shed light on the substituent effects. Moreover, the TtBs were characterized through several state-of-the-art computational techniques, such as the Quantum Theory of Atoms in Molecules (QTAIM) and Noncovalent Interactions plot (NCIplot) methodologies. We believe that the results gathered from our study will be useful for rational drug design and biological communities as well as for further expanding the role of this interaction to biomedical applications.

Highin vitroactivity of gold and silver nanoparticles from Solanum mammosum L. against SARS-CoV-2 surrogate Phi6 and viral model PhiX174.

The search for new strategies to curb the spread of the SARS-CoV-2 coronavirus, which causes COVID-19, has become a global priority. Various nanomaterials have been proposed as ideal candidates to inactivate the virus; however, because of the high level of biosecurity required for their use, alternative models should be determined. This study aimed to compare the effects of two types of nanomaterials gold (AuNPs) and silver nanoparticles (AgNPs), recognized for their antiviral activity and affinity with the coronavirus spike protein using PhiX174 and enveloped Phi6 bacteriophages as models. To reduce the toxicity of nanoparticles, a species known for its intermediate antiviral activity,Solanum mammosumL. (Sm), was used. NPs prepared with sodium borohydride (NaBH4) functioned as the control. Antiviral activity against PhiX174 and Phi6 was analyzed using its seed, fruit, leaves, and essential oil; the leaves were the most effective on Phi6. Using the aqueous extract of the leaves, AuNPs-Sm of 5.34 ± 2.25 nm and AgNPs-Sm of 15.92 ± 8.03 nm, measured by transmission electron microscopy, were obtained. When comparing NPs with precursors, both gold(III) acetate and silver nitrate were more toxic than their respective NPs (99.99% at 1 mg ml-1). The AuNPs-Sm were less toxic, reaching 99.30% viral inactivation at 1 mg ml-1, unlike the AgNPs-Sm, which reached 99.94% at 0.01 mg ml-1. In addition, cell toxicity was tested in human adenocarcinoma alveolar basal epithelial cells (A549) and human foreskin fibroblasts. Gallic acid was the main component identified in the leaf extract using high performance liquid chromatography with diode array detection (HPLC-DAD). The FT-IR spectra showed the presence of a large proportion of polyphenolic compounds, and the antioxidant analysis confirmed the antiradical activity. The control NPs showed less antiviral activity than the AuNPs-Sm and AgNPs-Sm, which was statistically significant; this demonstrates that both theS. mammosumextract and its corresponding NPs have a greater antiviral effect on the surrogate Phi bacteriophage, which is an appropriate model for studying SARS-CoV-2.

Análise espacial da morbimortalidade materna em usuárias do Sistema Único de Saúde no Município do Rio de Janeiro, Brasil, 2014-2016 / Spatial analysis of maternal morbidity and mortality in users of the Brazilian Unified National Health System in the city of Rio de Janeiro, Brazil, 2014-2016 / Análisis espacial de la morbimortalidad materna en usuarias del Sistema Único de Salud en el municipio de Rio de Janeiro, Brasil, 2014-2016

O objetivo deste estudo é analisar a morbimortalidade materna de mulheres atendidas em hospitais do Sistema Único de Saúde (SUS) no Município do Rio de Janeiro, Brasil, no período de 2014 a 2016. Foi realizado estudo ecológico, por meio da coleta de dados do Sistema de Informações sobre Nascidos Vivos (SINASC), Sistema de Informação sobre Mortalidade (SIM) e Sistema de Informações Hospitalares (SIH/SUS). Para analisar a razão de mortalidade materna (RMM), foram utilizados dados do SIM. Para investigar a morbidade materna, adotaram-se critérios da Organização Mundial da Saúde para estimar as razões de near miss materno e de condições potencialmente ameaçadoras à vida. Dados do SINASC foram usados para número de nascidos vivos e caracterização demográfica, social e de acesso a serviço de pré-natal. Para avaliar a associação espacial entre os indicadores RMM, razões de near miss materno e condições potencialmente ameaçadoras à vida e os indicadores demográficos, sociais, obstétricos e de acesso obtidos no SINASC, foi calculado o índice de Moran bivariado com nível de 0,05 de significância, por meio do programa GeoDa. No período analisado, a RMM no Município do Rio de Janeiro foi de 94,16/100 mil nascidos vivos, a razão de near miss materno de 28,21/1.000 nascidos vivos e a razão de condições potencialmente ameaçadoras à vida de 34,31/1.000 nascidos vivos. Casos de condições potencialmente ameaçadoras à vida foram utilizados pela primeira vez neste estudo e apresentaram diagnósticos de internação e procedimentos realizados mais condizentes com o perfil de mortalidade materna no Município do Rio de Janeiro. Houve associação significativa entre RMM e percentual de nascidos vivos no SUS, razão de condições potencialmente ameaçadoras à vida e percentual de nascidos vivos no SUS e razão de condições potencialmente ameaçadoras à vida e ser solteira.

The objective of this study is to analyze the maternal morbidity and mortality of women treated in hospitals of the Brazilian Unified National Health System (SUS) in the city of Rio de Janeiro in the period 2014-2016. An ecological study was conducted using data from the Brazilian Information System on Live Birth (SINASC), the Brazilian Mortality Information System (SIM), and the Brazilian Hospital Information System (SIH/SUS). For the analysis of the maternal mortality ratio (MMR), data from the SIM were used. For the analysis of maternal morbidity, World Health Organization criteria were used to estimate the ratios of maternal near miss and potentially life-threatening conditions. SINASC was used to retrieve data on the number of live births, for demographic characterization, social aspects, and access to prenatal care. To evaluate the spatial association between the indicators MMR, ratios of maternal near miss, and potentially life-threatening conditions and the demographic, social, obstetric, and access indicators, obtained from SINASC, the bivariate Moran Index was estimated with a significance level of 0.05, using the GeoDa program. In the period analyzed, the MMR in the Rio de Janeiro was 94.16/100,000 live births, the ratio of maternal near miss was 28.21/1,000 live births, and the potentially life-threatening conditions was 34.31/1,000 live births. Cases of potentially life-threatening conditions were used for the first time in this study and presented diagnoses and procedures during hospitalization more consistent with the maternal mortality profile in the city of Rio de Janeiro. There was a significant association between MMR and percentage of live births in SUS, potentially life-threatening conditions and percentage of live births in SUS, and potentially life-threatening conditions and being single.

El objetivo de este estudio es analizar la morbimortalidad materna de las mujeres atendidas en hospitales del Sistema Único de Salud (SUS) del municipio de Rio de Janeiro, Brasil, en el período 2014-2016. Fue realizado un estudio ecológico, por medio del uso de datos del Sistema de Información sobre Nacidos Vivos (SINASC), Sistema de Información sobre Mortalidad (SIM) y del Sistema de Información Hospitalaria (SIH/SUS). Para el análisis de la razón de mortalidad materna (RMM) se utilizaron los datos SIM. Para el análisis de la morbilidad materna se utilizaron los criterios de la Organización Mundial de la Salud para estimar las razón de near miss materno y de condiciones potencialmente amenazantes a la vida. Para el número de nacidos vivos y la información demográfica, social y de acceso al servicio de atención prenatal fueron utilizados datos del SINASC. Para evaluar la asociación espacial entre los indicadores RMM, razon de near miss materno y razon de condiciones potencialmente amenazantes a la vida y los indicadores demográficos, sociales, obstétricos y de accesos obtenidos en el SINASC fue calculado el Índice de Moran bivariado con nivel de 0,05 de significación, usando el programa GeoDa. En el período analizado, la RMM en el municipio de Rio de Janeiro fue de 94,16/100.000 nascidos vivos, la razón de near miss materno de 28,21/1.000 nascidos vivos y la razón de condiciones potencialmente amenazantes a la vida de 34,31/1.000 nascidos vivos. Los casos de condiciones potencialmente amenazantes a la vida se utilizaron por primera vez en este estudio y presentaron diagnósticos de hospitalización y procedimientos realizados más acordes con el perfil de mortalidad materna en el Municipio de Rio de Janeiro Hubo una asociación significativa entre RMM y el porcentaje de nacidos vivos en el SUS, razón de condiciones potencialmente amenazantes a la vida y el porcentaje de nacidos vivos en el SUS y razón de condiciones potencialmente amenazantes a la vida y ser soltera.

One-Pot Environmentally Friendly Synthesis of Nanomaterials Based on Phytate-Coated Fe3O4 Nanoparticles for Efficient Removal of the Radioactive Metal Ions 90Sr, 90Y and (UO2)2+ from Water.

We report the fast (three minutes) synthesis of green nanoparticles based on nanoparticles coated with the natural organic receptor phytate for the recognition and capture of 90Sr, 90Y, and (UO2)2+. The new material shows excellent retention for (UO2)2+, 97%; these values were 73% and 100% for 90Sr and 90Y, respectively. Recovery of the three radioactive metal ions occurs through a non-competitive process. The new hybrid material is harmless, easy to prepare, and immobilizes these radioactive contaminants in water with great efficiency.

Importance of Cu and Ag regium-π bonds in supramolecular chemistry and biology: a combined crystallographic and ab initio study.

Identifying and characterizing new binding events between electron donor and acceptor counterparts represents a crucial step to complete the molecular recognition and aggregation picture, which is key to chemistry and biology. In this study we interrogated both the PDB (Protein Data Bank) and CSD (Cambridge Structural Database) for the presence of Cu and Ag regium-π (Rg-π) bonds (an attractive noncovalent force between elements from group 11 and π-systems). Concretely, we found evidence of the plausible biological role of the interaction in protein-DNA systems, bacterial Ag extrusion processes and Heme group redox functionality. Furthermore, we also highlighted the implications of Rg-π bonds in the crystal packing of two host-guest systems, where this interaction is key for the binding and recognition of small organic molecules as well as for the encapsulation of organometallic complexes. Theoretical models were used to analyse the strength of the interaction (RI-MP2/def2-TZVP level of theory) together with QTAIM (Quantum Theory of Atoms in Molecules), NBO (Natural Bonding Orbital) and NCIplot (Non Covalent Interactions plot) analyses, which further assisted in the characterization of the regium-π interactions described herein. We expect the results from this study will be useful to attract the attention of chemical biologists as well as to expand the potential of the interaction to the supramolecular chemistry and crystal engineering communities.

Editing melon eIF4E associates with virus resistance and male sterility.

The cap-binding protein eIF4E, through its interaction with eIF4G, constitutes the core of the eIF4F complex, which plays a key role in the circularization of mRNAs and their subsequent cap-dependent translation. In addition to its fundamental role in mRNA translation initiation, other functions have been described or suggested for eIF4E, including acting as a proviral factor and participating in sexual development. We used CRISPR/Cas9 genome editing to generate melon eif4e knockout mutant lines. Editing worked efficiently in melon, as we obtained transformed plants with a single-nucleotide deletion in homozygosis in the first eIF4E exon already in a T0 generation. Edited and non-transgenic plants of a segregating F2 generation were inoculated with Moroccan watermelon mosaic virus (MWMV); homozygous mutant plants showed virus resistance, while heterozygous and non-mutant plants were infected, in agreement with our previous results with plants silenced in eIF4E. Interestingly, all homozygous edited plants of the T0 and F2 generations showed a male sterility phenotype, while crossing with wild-type plants restored fertility, displaying a perfect correlation between the segregation of the male sterility phenotype and the segregation of the eif4e mutation. Morphological comparative analysis of melon male flowers along consecutive developmental stages showed postmeiotic abnormal development for both microsporocytes and tapetum, with clear differences in the timing of tapetum degradation in the mutant versus wild-type. An RNA-Seq analysis identified critical genes in pollen development that were down-regulated in flowers of eif4e/eif4e plants, and suggested that eIF4E-specific mRNA translation initiation is a limiting factor for male gametes formation in melon.

High-performance delignification of invasive tree species wood with ionic liquid and deep eutectic solvent for the production of cellulose-based polyelectrolytes.

An efficient and eco-friendly process for lignocellulosic biomass fractionation is essential for the production of high value-added bioproducts from biomass. The present work aimed to obtain cellulose-rich materials from the wood of an invasive tree species (Acacia dealbata) using an appropriate choice of ionic liquids (ILs) and deep eutectic solvents (DESs), and of the processing conditions, for the subsequent production of cationic wood-based polyelectrolytes. In the pretreatment step, the 1-butyl-3-methylimidazolium methyl sulfate (IL) + H2O and choline chloride + imidazole (DES) systems demonstrated a remarkable ability to remove lignin from acacia, reaching up to 92.4 and 90.2% of delignification, respectively. However, the DES pretreatment revealed to be more selective for lignin removal with lower cellulose losses (less than 15%) than the IL treatment (up to 30%) and less cellulose depolymerization. The hemicellulose was also removed but in a lesser extent with the DES treatment. Both systems could provide treated materials with a very high cellulose content (≥89%). Afterwards, cationic polyelectrolytes having a considerable content of quaternary ammonium groups (up to 3.6 mmol g-1) were obtained directly from the IL- and DES-pretreated woods. The treated woods, when used as raw materials for cationization reaction, allow to synthesize water-soluble polyelectrolytes with potential to be applied in wastewater treatment, pharmaceutical or cosmetic products.

Urban landscape and street-design factors associated with road-traffic mortality in Latin America between 2010 and 2016 (SALURBAL): an ecological study.

BACKGROUND: Road-traffic injuries are a key cause of death and disability in low-income and middle-income countries, but the effect of city characteristics on road-traffic mortality is unknown in these countries. The aim of this study was to determine associations between city-level built environment factors and road-traffic mortality in large Latin American cities. METHODS: We selected cities from Argentina, Brazil, Chile, Colombia, Costa Rica, El Salvador, Guatemala, Mexico, Panama, and Peru; cities included in the analysis had a population of at least 100 000 people. We extracted data for road-traffic deaths that occurred between 2010 and 2016 from country vital registries. Deaths were grouped by 5-year age groups and sex. Road-traffic deaths were identified using ICD-10 codes, with adjustments for ill-defined codes and incomplete registration. City-level measures included population, urban development, street design, public transportation, and social environment. Associations were estimated using multilevel negative binomial models with robust variances. FINDINGS: 366 cities were included in the analysis. There were 328 408 road-traffic deaths in nearly 3·5 billion person-years across all countries, with an average crude rate of 17·1 deaths per 100 000 person-years. Nearly half of the people who died were younger than 35 years. In multivariable models, road-traffic mortality was higher in cities where urban development was more isolated (rate ratio [RR] 1·05 per 1 SD increase, 95% CI 1·02-1·09), but lower in cities with higher population density (0·94, 0·90-0·98), higher gross domestic product per capita (0·96, 0·94-0·98), and higher intersection density (0·92, 0·89-0·95). Cities with mass transit had lower road mortality rates than did those without (0·92, 0·86-0·99). INTERPRETATION: Urban development policies that reduce isolated and disconnected urban development and that promote walkable street networks and public transport could be important strategies to reduce road-traffic deaths in Latin America and elsewhere. FUNDING: Wellcome Trust.