New insights for valorization of polyolefins/light alkanes: catalytic dehydrogenation of n-alkanes by immobilized pincer-iridium complexes.

This scientific review delves into the innovative realm of polyolefins/light alkanes valorization through their catalytic dehydrogenation employing pincer-ligated iridium organometallic complexes. These widely studied catalysts exhibit outstanding properties, although the intrinsic characteristics of homogeneous catalysis (such as challenging product-catalyst separation, poor applicability to continuous-flow processes and low recyclability) limit their activity and industrial application, as well as their thermal stability. Through the immobilization of complexes on inorganic supports, these downsides have been bypassed, harnessing the true potential of these catalysts, affording more selective and stable catalysts in addition to facilitating their implementation in industrial processes. The findings described herein contribute to the advancement in the understanding of catalytic processes in hydrocarbon transformations, offering promising avenues for sustainable and selective production of valuable chemical intermediates from readily available feedstocks.

Highly Effective Non-Noble MnO2 Catalysts for 5-Hydroxymethylfurfural Oxidation to 2,5-Furandicarboxylic Acid.

Noble metal-free catalyst or catalytic oxidation of 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid are proposed in this study as a proposal to solve one of the great disadvantages of this reaction of using preferably noble metal-based catalysts. The catalytic activity of six MnO2 crystal structures is studied as alternative. The obtained results showed a strong connection between catalytic activity the type of MnO2 structure organization and redox behavior. Among all tested catalysts, ϵ-MnO2 showed the best performance with an excellent yield of 74 % of 2,5-furandicarboxylic acid at full -hydroxymethylfurfural conversion.

Decoding protein methylation function with thermal stability analysis.

Protein methylation is an important modification beyond epigenetics. However, systems analyses of protein methylation lag behind compared to other modifications. Recently, thermal stability analyses have been developed which provide a proxy of a protein functional status. Here, we show that molecular and functional events closely linked to protein methylation can be revealed by the analysis of thermal stability. Using mouse embryonic stem cells as a model, we show that Prmt5 regulates mRNA binding proteins that are enriched in intrinsically disordered regions and involved in liquid-liquid phase separation mechanisms, including the formation of stress granules. Moreover, we reveal a non-canonical function of Ezh2 in mitotic chromosomes and the perichromosomal layer, and identify Mki67 as a putative Ezh2 substrate. Our approach provides an opportunity to systematically explore protein methylation function and represents a rich resource for understanding its role in pluripotency.

Functionalized Biochars as Supports for Ru/C Catalysts: Tunable and Efficient Materials for γ-Valerolactone Production.

Cotton stalks-based biochars were prepared and used to synthetize Ru-supported catalysts for selective production of γ-valerolactone from levulinic acid in aqueous media. Different biochars' pre-treatments (HNO3, ZnCl2, CO2 or a combination of them) were carried out to activate the final carbonaceous support. Nitric acid treatment resulted in microporous biochars with high surface area, whereas the chemical activation with ZnCl2 substantially increases the mesoporous surface. The combination of both treatments led to a support with exceptional textural properties allowing the preparation of Ru/C catalyst with 1422 m2/g surface area, 1210 m2/g of it being a mesoporous surface. The impact of the biochars' pre-treatments on the catalytic performance of Ru-based catalysts is fully discussed.

Highly Active Ce- and Mg-Promoted Ni Catalysts Supported on Cellulose-Derived Carbon for Low-Temperature CO2 Methanation.

The CO2 methanation performance of Mg- and/or Ce-promoted Ni catalysts supported on cellulose-derived carbon (CDC) was investigated. The samples, prepared by biomorphic mineralization techniques, exhibit pore distributions correlated to the particle sizes, revealing a direct effect of the metal content in the textural properties of the samples. The catalytic performance, evaluated as CO2 conversion and CH4 selectivity, reveals that Ce is a better promoter than Mg, reaching higher conversion values in all of the studied temperature range (150-500 °C). In the interval of 350-400 °C, Ni-Mg-Ce/CDC attains the maximum yield to methane, 80%, reaching near 100% CH4 selectivity. Ce-promoted catalysts were highly active at low temperatures (175 °C), achieving 54% CO2 conversion with near 100% CH4 selectivity. Furthermore, the large potential stability of the Ni-Mg-Ce/CDC catalyst during consecutive cycles of reaction opens a promising route for the optimization of the Sabatier process using this type of catalyst.

5-Hydroxymethyl-2-Furfural Oxidation Over Au/CexZr1-xO2 Catalysts.

A series of gold catalysts supported on pure CeO2, ZrO2, and two different Ce-Zr mixed oxides have been prepared and tested in the 5-hydroxymethyl-2-furfural oxidation reaction. All catalysts show high catalytic activity (100% conversion) and important selectivity (27-41%) to the desired product i.e., 2,5-furandicarboxylic acid at low base concentration. Products selectivity changes with the support nature as expected, however, the observed trend cannot be related neither to gold particle size, nor to catalyst reducibility and oxygen mobility. An important relation between the FDCA selectivity and the support textural properties is observed, conducing to the general requirement for optimal pore size for this reaction.

A Decoupled Automation Platform for Hydrogen/Deuterium Exchange Mass Spectrometry Experiments.

Hydrogen/deuterium exchange mass spectrometry (HDX-MS) is a biophysical technique well suited to the characterization of protein dynamics and protein-ligand interactions. In order to accurately define the rate of exchange, HDX experiments require the repeated measure of deuterium incorporation into the target protein across a range of time points. Accordingly, the HDX-MS experiment is well suited to automation, and a number of automated systems for HDX-MS have been developed. The most widely utilized platforms all operate an integrated design, where robotic liquid handling is interfaced directly with a mass spectrometer. With integrated designs, the exchange samples are prepared and injected into the LC-MS following a "real-time" serial workflow. Here we describe a new HDX-MS platform that is comprised of two complementary pieces of automation that disconnect the sample preparation from the LC-MS analysis. For preparation, a plate-based automation system is used to prepare samples in parallel, followed by immediate freezing and storage. A second piece of automation has been constructed to perform the thawing and LC-MS analysis of frozen samples in a serial mode and has been optimized to maximize the duty cycle of the mass spectrometer. The decoupled configuration described here reduces experiment time, significantly improves capacity, and improves the flexibility of the platform when compared with a fully integrated system.

PFG-NMR as a Tool for Determining Self-Diffusivities of Various Probe Molecules through H-ZSM-5 Zeolites.

The understanding of major zeolite applications is partially based on diffusion of molecules inside or outside microporous networks. However, it is still a challenge to measure such phenomena. The diffusion ordered nuclear magnetic resonance spectroscopy (DOSY) technique has been reported to measure a probe molecule's diffusion inside porous solids. Pulsed-field gradient (PFG)-NMR has been used herein to measure the self-diffusivity of different probe molecules, such as neopentane, benzene, toluene and 1-dodecene with increasing dynamic diameter, respectively, on a series of H-ZSM-5 zeolites. The latter materials exhibit different crystal sizes, Si/Al ratios and the presence (or absence) of crystalline defects. In addition, shaped zeolite bodies representing industrial catalysts were compared with the afore-mentioned samples.

CO2 Adsorption Capacities in Zeolites and Layered Double Hydroxide Materials.

The development of technologies that allow us to reduce CO2 emissions is mandatory in today's society. In this regard, we present herein a comparative study of CO2 adsorption over three types of materials: zeolites, layered double hydroxides (LDH), and zeolites coated LDH composites. The influence of the zeolite Si/Al ratio on zeolites sorption capacity along with the presence of mesopores was investigated. By comparing these results with the well-known performance of LDHs, we aim to provide insights on the factors that may influence the CO2 capture capacity over zeolites, thus providing useful tools for tuning their properties upon post-treatments.

Au/CeO2-ZnO/Al2O3 as Versatile Catalysts for Oxidation Reactions: Application in Gas/Liquid Environmental Processes.

The present work showcases the versatility of nanogold systems supported on Zn-doped ceria when applied in two important environmental processes, the total CO oxidation, and the liquid phase oxidation of glucose to gluconic acid. In the CO oxidation the suitability of these materials is clearly demonstrated achieving full conversions even at sub-ambient conditions. Regarding the glucose oxidation our materials display high conversion values (always over 50%) and very importantly full or almost full selectivity toward gluconic acid-an added value platform chemical in the context of biomass upgrading routes. The key factors controlling the successful performance on both reactions are carefully discussed and compared to previous studies in literature. To our knowledge this is one of the very few works in catalysis by gold combining liquid and gas phase reactions and represents a step forward in the flexible behavior of nano gold catalysts.

Proteotyping pluripotency with mass spectrometry.

INTRODUCTION: Pluripotency emerges transiently during embryogenesis in two main forms with different developmental potential, termed naïve and primed states. Importantly, these pluripotent states can be recapitulated in vitro under specific culture conditions, representing a unique model to study the regulatory principles of development and cellular plasticity. Areas covered: A complex network of signaling pathways that senses intrinsic and extrinsic cues controls the fine balance between self-renewal and differentiation. Much of our knowledge on this tight regulation originates from epigenetic and transcriptomic approaches. However, the presence of post-transcriptional and post-translational mechanisms demands a direct assessment of the proteome in its multiple facets. Mass spectrometry-based proteomics is now a mature technique and has started to deliver new insights in the stem cell field. Expert opinion: Here, we review our current understanding on the mechanisms that dictate the spectrum of pluripotency levels. We put special emphasis on the emerging proteomic studies that focused on the molecular properties behind the naïve and primed states. In addition, we hypothesize on the impact that future developments in proteomic technologies can have to improve our view of pluripotency.

Deciphering Binding Interactions of IL-23R with HDX-MS: Mapping Protein and Macrocyclic Dodecapeptide Ligands.

Molecular characterization of the binding epitope of IL-23R and its cognate cytokine IL-23 is paramount to understand the role in autoimmune diseases and to support the discovery of new inhibitors of this protein-protein interaction. Our results revealed that HDX-MS was able to identify the binding epitope of IL-23R:IL-23, which opened the way to evaluate a peptide macrocycle described in the literature as disrupter of this autoimmune target. Thus, the characterization of the interactions of this chemotype by HDX-MS in combination with computational approaches was achieved. To our knowledge, this is the first reported structural evidence regarding the site where a small compound binds to IL-23R.

Perfil clínico e cognitivo de usuários de crack internados / Clinical and cognitive profile of hospitalized crack users

Trata-se de estudo transversal que objetivou avaliar: consumo de crack (entrevista semi-estruturada), funcionamento adaptativo (relativo às amizades, trabalho e família), psicopatológico (Adult Self-Report) e funções cognitivas (Screening Cognitivo do WAIS-III) de usuários de crack internados. Dos 84 participantes (90,5% homens), 53,6% fez uso diário de crack no último ano, com consumo médio usual de 1,54 gramas (DP=0,53; Mín.=0,5; Máx.=2,5). Houve grande prevalência de classificação na faixa clínica nos problemas internalizantes (77,4%), externalizantes (77,4%), funcionamento adaptativo (variando de 84,6 a 97,6%) e de comportamentos transgressores (70,3% comportamentos de quebra de regras e 59,6% comportamentos anti-sociais). As funções cognitivas encontraram-se preservadas (médio inferior/médio/médio superior) na grande maioria (>75%) dos entrevistados, com pior desempenho no subteste Vocabulário (22,6% classificação inferior).

The aim of this cross-sectional study was to assess the use of crack cocaine (semi-structured interview), adaptive functioning (concerning friends, work, and family), psychopathological functioning (Adult Self-Report) and cognitive functions (WAIS-III) among hospitalized crack cocaine users. From the 84 respondents (90.5% male), 53.6% used crack cocaine on a daily basis in the previous year, with an usual average consumption of 1.54 grams (SD=.53; Min.=.5; Max.=2.5). There was a large prevalence of internalizing (77.4%) and externalizing (77.4%) problems, adaptive functioning (84.6 to 97.6%) and wrongful behavior (70.3% of rule-breaking behavior and 59.6% of antisocial behavior). Cognitive functions were preserved (low average/average/high average) in most respondents (>75%), with worse performance on the Vocabulary subtest (22.6% in the low average range).

Perfil clínico e cognitivo de usuários de crack internados / Clinical and cognitive profile of hospitalized crack users

Trata-se de estudo transversal que objetivou avaliar: consumo de crack (entrevista semi-estruturada), funcionamento adaptativo (relativo às amizades, trabalho e família), psicopatológico (Adult Self-Report) e funções cognitivas (Screening Cognitivo do WAIS-III) de usuários de crack internados. Dos 84 participantes (90,5% homens), 53,6% fez uso diário de crack no último ano, com consumo médio usual de 1,54 gramas (DP=0,53; Mín.=0,5; Máx.=2,5). Houve grande prevalência de classificação na faixa clínica nos problemas internalizantes (77,4%), externalizantes (77,4%), funcionamento adaptativo (variando de 84,6 a 97,6%) e de comportamentos transgressores (70,3% comportamentos de quebra de regras e 59,6% comportamentos anti-sociais). As funções cognitivas encontraram-se preservadas (médio inferior/médio/médio superior) na grande maioria (>75%) dos entrevistados, com pior desempenho no subteste Vocabulário (22,6% classificação inferior).(AU)

The aim of this cross-sectional study was to assess the use of crack cocaine (semi-structured interview), adaptive functioning (concerning friends, work, and family), psychopathological functioning (Adult Self-Report) and cognitive functions (WAIS-III) among hospitalized crack cocaine users. From the 84 respondents (90.5% male), 53.6% used crack cocaine on a daily basis in the previous year, with an usual average consumption of 1.54 grams (SD=.53; Min.=.5; Max.=2.5). There was a large prevalence of internalizing (77.4%) and externalizing (77.4%) problems, adaptive functioning (84.6 to 97.6%) and wrongful behavior (70.3% of rule-breaking behavior and 59.6% of antisocial behavior). Cognitive functions were preserved (low average/average/high average) in most respondents (>75%), with worse performance on the Vocabulary subtest (22.6% in the low average range).(AU)

Fatores protetivos e de risco para o uso de crack e danos decorrentes de sua utilização: revisão de literatura / Protective and risk factors for the use of crack and damages from its use: review of literature

INTRODUÇÃO: Este estudo objetivou revisar pesquisas que relatam danos decorrentes do uso de crack e possíveis fatores protetivos ou de risco para o uso. MÉTODO: Foram realizadas buscas no PsycInfo, PubMed e LILACS. Os descritores utilizados foram: (Crack Cocaine) AND (Street Drugs OR Population Characteristics OR Epidemiology). RESULTADOS: A facilidade de acesso do crack, uso frequente de cocaína injetável, cristais de metanfetamina, envolvimento em comércio sexual e variedade de drogas utilizadas nos últimos seis meses foram considerados fatores de risco para o uso. Não usuários de crack percebem o condicionamento vicário, informações fornecidas pela família e o medo de morrer como fatores protetivos para o uso da droga. O uso de crack pode causar danos físicos, problemas psiquiátricos, neurocognitivos e prejuízos sociais. CONCLUSÃO: O uso de crack está associado a danos físicos, mentas e sociais. Fatores protetivos e de risco devem ser considerados na elaboração de políticas públicas de saúde.(AU)

BACKGROUND: The aim of this paper was to review studies that describe the damage caused by crack and the possible protective or risk factors for this use. METHOD: The PsycInfo, PubMed and LILACS databases were searched using the following terms: (Crack Cocaine) AND (Street Drugs OR Population Characteristics OR Epidemiology). RESULTS: The easy access to crack, the frequent use of injectable cocaine, crystal methamphetamine, the involvement in sex trade, and the variety of drugs used in the past six months were regarded as risk factors for drug use. For crack non-users, vicarious conditioning, information given by the family and fear of death were protective factors for drug use. The use of crack can cause physical damage, psychiatric and neurocognitive problems and social impairment. CONCLUSION: The use of crack is associated with physical, mental and social damage. Protective and risk factors must be contemplated in the design of public health policies.(AU)

Prontidão para mudança e alterações das funções cognitivas em alcoolistas / Preparación para cambio y alteracion de las funciones cognoscitivas en alcoholicos / Readiness to change and cognitive function alterations in alcoholics

Analisa-se a relação entre a cultura trabalho-família existente numa empresa de serviços financeiros e o compromisso organizacional dos empregados, controlando-se variáveis sociodemográficas. A 219 trabalhadores técnicos e profissionais entre 19 e 64 anos, pertencentes a 16 sucursais localizadas na região do Maule (Chile), foram aplicados três instrumentos de medida das variáveis referidas. Observa-se uma relação significativa entre as variáveis constitutivas da dimensão cultura trabalho-família e o compromisso organizacional, estando a cultura fortemente associada a este (r = 0,483, p=0,05). Observou-se que quanto mais apoio diretivo da empresa é percebido por parte dos trabalhadores, maior é o compromisso destes com aquela e, particularmente, seu compromisso dos tipos normativo (r =0,417; p>0,000) e afetivo (r=0,347; p>0,000).

It is analyzed the relationship between work-family culture with the organizational commitment of employees, controlling sociodemographical variables. 219 technical workers and professionals, between 19 and 64 years old, from a financial services company located in the region of Maule (Chile) , responded three instruments of measurement. There was a significant relationship between work-family culture variables and organizational commitment, where the culture appears strongly associated to the commitment (r = 0,483, p = 0.05). While most executive support from the company is perceived by workers, the greater the commitment to them with company, particularly with its normative (r =0,417, p< 0,000) and affective commitment (r = 0,347, p < 0,000).

Se analiza la relación entre la cultura trabajo-familia existente en una empresa de servicios financieros y el compromiso organizacional en los empleados, controlando variables sociodemográficas. A 219 trabajadores técnicos y profesionales entre 19 y 64 años, pertenecientes a 16 sucursales ubicadas en la región del Maule (Chile) les fueron aplicados tres instrumentos de medición de las variables referidas. Se observa una relación significativa entre las variables constitutivas de la dimensión cultura trabajo-familia y el compromiso organizacional donde la cultura está fuertemente asociada a éste (r = 0,483, p = 0,05), Se registra que mientras más apoyo directivo desde la empresa es percibido por parte de los trabajadores mayor es el compromiso de éstos con aquélla y, particularmente, con su compromiso de tipos normativo (r = 0,417; p>0,000) y afectivo (r = 0,347; p>0,000).

Prontidão para mudança e alterações das funções cognitivas em alcoolistas / Preparación para cambio y alteracion de las funciones cognoscitivas en alcoholicos / Readiness to change and cognitive function alterations in alcoholics

Analisa-se a relação entre a cultura trabalho-família existente numa empresa de serviços financeiros e o compromisso organizacional dos empregados, controlando-se variáveis sociodemográficas. A 219 trabalhadores técnicos e profissionais entre 19 e 64 anos, pertencentes a 16 sucursais localizadas na região do Maule (Chile), foram aplicados três instrumentos de medida das variáveis referidas. Observa-se uma relação significativa entre as variáveis constitutivas da dimensão cultura trabalho-família e o compromisso organizacional, estando a cultura fortemente associada a este (r = 0,483, p=0,05). Observou-se que quanto mais apoio diretivo da empresa é percebido por parte dos trabalhadores, maior é o compromisso destes com aquela e, particularmente, seu compromisso dos tipos normativo (r =0,417; p>0,000) e afetivo (r=0,347; p>0,000).(AU)

It is analyzed the relationship between work-family culture with the organizational commitment of employees, controlling sociodemographical variables. 219 technical workers and professionals, between 19 and 64 years old, from a financial services company located in the region of Maule (Chile) , responded three instruments of measurement. There was a significant relationship between work-family culture variables and organizational commitment, where the culture appears strongly associated to the commitment (r = 0,483, p = 0.05). While most executive support from the company is perceived by workers, the greater the commitment to them with company, particularly with its normative (r =0,417, p< 0,000) and affective commitment (r = 0,347, p < 0,000).(AU)

Se analiza la relación entre la cultura trabajo-familia existente en una empresa de servicios financieros y el compromiso organizacional en los empleados, controlando variables sociodemográficas. A 219 trabajadores técnicos y profesionales entre 19 y 64 años, pertenecientes a 16 sucursales ubicadas en la región del Maule (Chile) les fueron aplicados tres instrumentos de medición de las variables referidas. Se observa una relación significativa entre las variables constitutivas de la dimensión cultura trabajo-familia y el compromiso organizacional donde la cultura está fuertemente asociada a éste (r = 0,483, p = 0,05), Se registra que mientras más apoyo directivo desde la empresa es percibido por parte de los trabajadores mayor es el compromiso de éstos con aquélla y, particularmente, con su compromiso de tipos normativo (r = 0,417; p>0,000) y afectivo (r = 0,347; p>0,000).(AU)